Resist composition and pattern formation method using the same

Abstract

Provided are a resist composition and a pattern forming method using the same. 【Solution means】A resist composition containing an organometallic compound represented by the following chemical formula 1 and an additive represented by the following chemical formula 2, and a pattern forming method using the same: M 11 (R x ) n (R y ) (m-n) [Chemical formula 1] (X2) c2 -(L2) a2 -[Y2-Z2] b2 [Chemical formula 2] In the above chemical formulas 1 and 2, for the explanations of M 11 , R x , R y , n, m, X2, Y2, Z2, L2, a2, b2 and c2, refer to the specification.

Description

[Technical Field]

[0001] The present invention relates to a resist composition and a pattern formation 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] However, in the case of chemically amplified resists, problems such as decreased pattern uniformity and increased surface roughness occur as the formed acid diffuses to the unexposed areas. Furthermore, as semiconductor processes become increasingly miniaturized, controlling acid diffusion becomes difficult, necessitating the development of new resist types.

[0004] In recent years, attempts have been made to develop materials whose physical properties change upon exposure in order to overcome the limitations of chemically amplified resists. However, there is still the problem of the high dose required during exposure. [Overview of the project] [Problems that the invention aims to solve]

[0005] The problem that the present invention aims to solve is to provide a resist composition that has improved storage stability, whose physical properties change even with low dose exposure, and which provides a pattern with improved resolution, as well as a pattern formation method using the same. [Means for solving the problem]

[0006] A resist composition is provided that includes an organometallic compound represented by the following Chemical Formula 1 and an additive represented by the following Chemical Formula 2 on one side: M , , , 30 , , , 30 , , x , a1 , x , , , 11 , , , , , 30 , , y , b1 , y (R x ) n (R y ) (m-n) [Chemical Formula 1] (X2) c2 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​It is a linear, branched, or cyclic monovalent hydrocarbon group, and of the multiple R1 groups, two adjacent groups can selectively bond to each other to form a ring. b1 is an integer between 1 and 4. X2 is OH, SH, C(=O)OH, S(=O)OH, S(=O)2OH, or P(=O)(OH)2. c2 is an integer between 1 and 4. L2 may independently and selectively contain heteroatoms C1-C 30 It is a linear, branched, or cyclic divalent hydrocarbon group. a2 is an integer between 0 and 4. Y2-Z2 is a photoreactive unit, b2 is an integer between 1 and 4. * indicates a bonding site with an adjacent atom.

[0007] In other aspects, a pattern forming method is provided, comprising the steps of: applying the aforementioned 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]

[0008] Embodiments of the present invention can provide a resist composition that has improved storage stability and improved sensitivity, and that provides a pattern with improved resolution. [Brief explanation of the drawing]

[0009] [Figure 1] This is a flowchart showing a pattern formation method according to one embodiment of the present invention. [Figure 2A] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 2B] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 2C] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 3A]This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3B] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3C] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3D] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3E] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 4A] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4B] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4C] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4D] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4E] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 5] This diagram shows the FT-IR analysis results for compound M1, compound A1, a mixture of compound M1 and compound A1, and compound X1. [Figure 6A] This diagram shows the change in film thickness after development using the dose in Example 1-1. [Figure 6B] This diagram shows the change in film thickness after development using the doses in Examples 1-2. [Figure 6C] This diagram shows the change in film thickness after development depending on the dose of Comparative Example 1-1. [Figure 6D] This diagram shows the change in film thickness after development depending on the dose for Comparative Example 1-2. [Figure 7] This diagram shows the change in film thickness after development using the dose in Example 2-1. [Modes for carrying out the invention]

[0010] 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.

[0011] 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. In this specification, when a part such as a layer, film, region, or plate is described as being "on top of" or "above" another part, this includes not only parts that are immediately above, below, left, or right in contact, but also parts that are above, below, left, or right in non-contact.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] In this specification, "monovalent hydrocarbon group" means a monovalent residue derived from an organic compound or its derivative containing carbon and hydrogen, and specific examples include linear or branched alkyl groups (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, 2-ethylhexyl group, and nonyl group); monovalent saturated cyclic aliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, 1-adamantyl group, 2-adamantyl group, 1-adamantylmethyl group, norbornyl group, norbornylmethyl group, tricyclodecanyl group, tetracyclododecanyl group) This includes groups such as 1-L group, tetracyclododecanylmethyl group, and dicyclohexylmethyl group; monounsaturated aliphatic hydrocarbon groups (alkenyl group, alkynyl group) (e.g., allyl group); monounsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl group) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl group, 1-naphthyl group, and 2-naphthyl group); arylalkyl groups (e.g., benzyl group and diphenylmethyl group); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, methylthiomethyl group, acetamidomethyl group, trifluoroethyl group, (2-methoxyethoxy)methyl group, acetoxymethyl group, 2-carboxy-1-cyclohexyl group, 2-oxopropyl group, 4-oxo-1-adamantyl group, and 3-oxocyclohexyl group), or any combination thereof.Furthermore, in these groups, some hydrogen atoms may be substituted by a moiety containing a heteroatom, such as oxygen, sulfur, nitrogen, phosphorus, or halogen atom, or some carbon atoms may be substituted by a moiety containing a heteroatom, such as oxygen, sulfur, nitrogen, or phosphorus. Thus, these groups may also include cyano groups, nitro groups, hydroxyl groups, thiol groups, amino groups, carboxylic acid groups, ether moieties, thioether moieties, carbonyl moieties, ester moieties, phosphonate moieties, sulfonate moieties, carbonate moieties, amide moieties, lactone moieties, sultone moieties, carboxylic acid anhydride moieties, and the like.

[0016] In this specification, “divalent hydrocarbon group” means a divalent residue in which any one hydrogen of the 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, cycloalkenylene groups, arylene groups, and those in which some of their carbon atoms are replaced by heteroatoms.

[0017] 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, ter-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. In this specification, "halogenated alkyl group" means a group in which one or more hydrogen atoms of an alkyl group are substituted with a halogen, and specific examples include CF3, where the halogen is F, Cl, Br, or I.

[0018] In this specification, "alkoxy group" is defined as -OA 101 This refers to a monovalent group having the chemical formula A 101These are alkyl groups. Specific examples include methoxy groups, ethoxy groups, and isopropyloxy groups. 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. 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. 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.

[0019] 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.

[0020] 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. 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.

[0021] In this specification, "heterocycloalkyl group" is defined as a cycloalkyl group in which some of the carbon atoms are replaced by a heteroatom, for example, a molecule containing oxygen, sulfur, or nitrogen. Specifically, heterocycloalkyl groups 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 of the carbon atoms are replaced by a heteroatom, for example, a molecule containing oxygen, sulfur, or nitrogen.

[0022] 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. In this specification, "heterocycloalkylthio group" is defined as -SA 103 This refers to a monovalent group having the chemical formula A 103 It is a heterocycloalkyl group. 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.

[0023] In this specification, "cycloalkenyl group" means a monovalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds and having no aromatic properties. In this specification, "cycloalkenylene group" means a divalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds and having no aromatic properties. In this specification, a "heterocycloalkenyl group" is defined as a group in which some of the carbon atoms of the cycloalkenylene group are replaced by a heteroatom, such as oxygen, sulfur, or nitrogen.

[0024] 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. In this specification, "aryl group" means a monovalent group having a carbocyclic aromatic system, and specific examples include phenyl group, naphthyl group, anthracenyl group, phenantrenyl group, pyrenyl group, chrysenyl group, etc. In this specification, "arylene group" means a divalent group having a carbocyclic aromatic system. In this specification, "aryloxy group" is defined as -OA 104 This refers to a monovalent group having the chemical formula A 104 It is an aryl group. In this specification, "arylthio group" is defined as -SA 104 This refers to a monovalent group having the chemical formula A 104 It is an aryl group.

[0025] 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. In this specification, "heteroaryloxy group" is defined as -OA 105 This refers to a monovalent group having the chemical formula A 105 It is a heteroaryl group. In this specification, "heteroarylthio group" is defined as -SA 105 This refers to a monovalent group having the chemical formula A 105 It is a heteroaryl group. In this specification, "arylalkyl group" means a group in which an alkyl group is substituted with a monovalent group having a carbocyclic aromatic system, and specific examples include the benzyl group and the diphenylmethyl group. In this specification, "heteroarylalkyl group" means a group in which an alkyl group is substituted with a monovalent group having a heterocyclic aromatic system. In this specification, "heterocyclic group" means a monocyclic or polycyclic group having 1 to 60 carbon atoms that contains at least one heteroatom, and can be monovalent, divalent, trivalent, or any other type of group.

[0026] In this specification, "substituent" means deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryl group, C1-C 20 Heteroaryloxy group, or C1-C 20 heteroarylthio group; Deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether moisture, thioether moisture, carbonyl moisture, ester moisture, phosphonate moisture, sulfonate moisture, carbonate moisture, amide moisture, lactone moisture, sultone moisture, carboxylic acid anhydride moisture, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20Halide 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 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, and C1-C 20 Includes heteroarylthio groups; or any combination thereof.

[0027] 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.

[0028] [Resist composition] The resist composition according to an exemplary embodiment includes an organometallic compound represented by the following Chemical Formula 1 and an additive represented by the following Chemical Formula 2: M 11 (R x ) n (R y ) (m-n) [Chemical Formula 1] (X2) c2 -(L2) a2 -[Y2-Z2] b2 [Chemical Formula 2] In the above Chemical Formulas 1 and 2, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), R x is *-X1-Y1, R y is *-(L1) a1 -(R1) b1 where, n is an integer from 1 to 6, m is an integer from 1 to 6, m - n is 0 or more, a plurality of R x may be the same as or different from each other, a plurality of R y may be the same as or different from each other, X1 is O, OC(=O), C(=O)O, OS(=O), S(=O)O, OS(=O)2, S(=O)2O, S, SC(=O), or C(=O)S, Y1 is hydrogen, deuterium, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to C 30 which may optionally contain heteroatoms, L1 is a single bond or a linear, branched, or cyclic divalent hydrocarbon group having 1 to C 30 which may optionally contain heteroatoms, a1 is an integer from 0 to 4, R1 may selectively contain heteroatoms C1-C 30 It is a linear, branched, or cyclic monovalent hydrocarbon group, and of the multiple R1 groups, two adjacent groups can selectively bond to each other to form a ring. b1 is an integer between 1 and 4. X2 is OH, SH, C(=O)OH, S(=O)OH, S(=O)2OH, or P(=O)(OH)2. c2 is an integer between 1 and 4. L2 may independently and selectively contain heteroatoms C1-C 30 It is a linear, branched, or cyclic divalent hydrocarbon group. a2 is an integer between 0 and 4. Y2-Z2 is a photoreactive unit, b2 is an integer between 1 and 4. * indicates a bonding site with an adjacent atom.

[0029] The molecular weight of the organometallic compound is 3000 g / mol or less. Specifically, the molecular weight of the organometallic compound is 2000 g / mol or less. For example, in the above chemical formula 1, M 11 is Sn, Sb, Te, or Bi. Specifically, in the above chemical formula 1, M 11 is Sn. In the above chemical formula 1, m is M 11 It shows the valence of the atoms. For example, in the above chemical formula 1, n is an integer between 1 and 4. For example, in the above chemical formula 1, m is an integer between 1 and 4.

[0030] In one embodiment, in the chemical formula 1, n is an integer from 1 to 4, m is an integer from 1 to 4, and M 11 is Sn. For example, in the above chemical formula 1, M 11 and R x The combination with M 11 - Single oxygen bond or M 11 -It is a single sulfur bond. Specifically, in the above chemical formula 1, M 11and R x The combination with M 11 -It is a single oxygen bond. Specifically, in the above chemical formula 1, M 11 and R y The combination with M 11 -It is a single carbon bond. For example, in the above chemical formula 1, X1 is O, OC(=O), C(=O)O, S, SC(=O), or C(=O)S.

[0031] For example, in the above chemical formula 1, Y1 is hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C1-C 20 Heteroaryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryloxy group, C1-C 20 A C1-C group substituted or unsubstituted with a heteroarylthio group, or any combination thereof. 30 Alkyl alkyl group, C1-C 30 Alkyl halogens, C1-C 30 Alkoxy group, C1-C 30 Alkylthio group, C1-C 30 Halide alkoxy group, C1-C30 Alkylthio halide group, C3-C 30 Cycloalkyl groups, C3-C 30 Cycloalkoxy group, C3-C 30 Cycloalkylthio group, C3-C 30 Heterocycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C3-C 30 Heterocycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, C6-C 30 Aryloxy group, C6-C 30 Arylthio group, C7-C 30 Arylalkyl groups, C1-C 30 Heteroaryl group, C1-C 30 Heteroaryloxy group, C1-C 30 Heteroarylthio group, and C2-C 30 Selected from heteroarylalkyl groups.

[0032] Specifically, in the above chemical formula 1, Y1 is hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, 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. 30 Alkyl alkyl group, C1-C 30 Alkyl halogens, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C3-C 30 Heterocycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, C7-C30 Arylalkyl groups, C1-C 30 Heteroaryl group, and C2-C 30 Selected from heteroarylalkyl groups.

[0033] More specifically, in the above chemical formula 1, Y1 is hydrogen; deuterium; and C1-C which is substituted or unsubstituted with deuterium, halogen, or any combination thereof. 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, and C6-C 30 Selected from aryl groups. In particular, in the above chemical formula 1, Y1 is selected from hydrogen; deuterium; and methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, ethenyl group, cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl group, ethynyl group, phenyl group, and naphthyl group, which are substituted or unsubstituted with deuterium, halogen, methyl group, ethyl group, ethyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, ethynyl group, phenyl group, and naphthyl group;

[0034] For example, in the above chemical formula 1, L1 is a single bond, substituted or unsubstituted C1-C 30 Alkylene group, substituted or unsubstituted C3-C 30 Cycloalkylene group, substituted or unsubstituted C3-C 30 Heterocycloalkylene group, substituted or unsubstituted C2-C 30 Alkenylene group, substituted or unsubstituted C3-C 30 Cycloalkenylene group, substituted or unsubstituted C3-C 30 Heterocycloalkenylene group, substituted or unsubstituted C6-C 30 Arylene group, or substituted or unsubstituted C1-C 30 It is a heteroarylene group.

[0035] Specifically, in the above chemical formula 1, L1 is a single bond; and deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C1-C 20 Heteroaryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryloxy group, C1-C 20 A C1-C group substituted or unsubstituted with a heteroarylthio group, or any combination thereof. 30 Alkylene group, C3-C 30 Cycloalkylene group, C3-C 30 Heterocycloalkylene group, C2-C 30 Alkenylene group, C3-C 30 Cycloalkenylene group, C3-C 30 Heterocycloalkenylene group, C6-C 30 Arylene group, and C1-C 30 Selected from heteroarylene groups.

[0036] More specifically, in the above chemical formula 1, L1 is a single bond; and deuterium, halogen, hydroxyl group, cyano group, C1-C 20 Alkyl alkyl group, C1-C 20C1-C 30 Alkylene group and C6-C 30 Selected from the arylene group; For example, in the above chemical formula 1, a1 is 0, 1, or 2.

[0037] For example, in the above chemical formula 1, R1 is deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C1-C 20 Heteroaryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryloxy group, C1-C 20 A C1-C group substituted or unsubstituted with a heteroarylthio group, or any combination thereof. 30 Alkyl, C3-C 30 Cycloalkyl groups, C3-C 30 Heterocycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C3-C 30 Heterocycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, C7-C30 Arylalkyl groups, C1-C 30 Heteroaryl group, and C2-C 30 Selected from heteroarylalkyl groups.

[0038] Specifically, in the above chemical formula 1, R1 is deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C1-C 20 Heteroaryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryloxy group, C1-C 20 A C1-C group substituted or unsubstituted with a heteroarylthio group, or any combination thereof. 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Selected from arylalkyl groups.

[0039] More specifically, in the aforementioned chemical formula 1, R1 is selected from any one of the following chemical formulas 3-1 to 3-21: [ka]

[0040] In the above chemical formulas 3-1 to 3-21, At least one hydrogen is deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 It can be optionally substituted with heteroaryl groups, or any combination thereof. In the aforementioned chemical formula 1, b1 represents the number of substitutions of R1, for example, in the aforementioned chemical formula 1, b1 is 1 or 2. Two adjacent R1 elements can selectively bond to each other to form a ring.

[0041] In one embodiment, in the chemical formula 1, b1 is 2 or more, and R1 is deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 A C2-C group that is substituted or unsubstituted with a heteroaryl group, or any combination thereof. 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, and C6-C 30 Selected from aryl groups.

[0042] In one embodiment, the organometallic compound represented by chemical formula 1 can be represented by any one of the following chemical formulas 1-1 to 1-4: [ka] In the above chemical formulas 1-1 to 1-4, M 11 This is the same as the one mentioned above, L 11 ~L 13 Each of these can be considered independently by referring to the explanation relating to L1 in the above chemical formula 1. a11 to a13 are each independent and refer to the explanation relating to a1 in the above chemical formula 1. R 11 ~R 13 Each of these can be considered independently by referring to the explanation relating to R1 in the above chemical formula 1. b11 to b13 are each independent and refer to the explanation relating to b1 in the above chemical formula 1. X 11 ~X 14 Each of these can be considered independently by referring to the explanation relating to X1 in the above chemical formula 1. Y 11 ~Y 13 Each of these terms should be referred to independently for the explanation relating to Y1 in the aforementioned chemical formula 1.

[0043] In one embodiment, the organometallic compound represented by chemical formula 1 is selected from the following group I: <Group I> [ka] [ka] [ka] [ka]

[0044] In group I, n is an integer between 0 and 3. For example, in group I, n is 2. The organometallic compound may be any one of those represented by chemical formula 1, or two or more may be used in mixture form. For example, in the above chemical formula 2, X2 is either OH or C(=O)OH. For example, in the above chemical formula 2, c2 is 1. In the aforementioned chemical formula 2, L2 is as described in the explanation for L1. For example, in the above chemical formula 2, a2 ​​is either 1 or 2.

[0045] In one embodiment, in the chemical formula 2, (L2) a2 It can be represented by one of the following chemical formulas 5-1 to 5-7: [ka]

[0046] In the above chemical formulas 5-1 to 5-7, R 51 ~R 53 Each of these is independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, C1-C4 alkyl group, or C1-C4 halogenated alkyl group. b51 is an integer between 1 and 4. n51 is an integer between 1 and 3. * and *' are bonding sites with adjacent atoms.

[0047] For example, in the above chemical formula 2, Y2 is OC(=O), C(=O)O, OS(=O)2, or S(=O)2O. For example, in the chemical formula 2 above, Z2 is *-C(R2)(R3)(R4), *-C(R2)=N(R3), *-N=C(R2)(R3), or *-N(R2)(R3).

[0048] For example, in the chemical formula 2, R2 to R4 are independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, -C(=O)R5, -C(R5)=NR6, -OR5, -S(=O)R5, -S(=O)2R5, -S(=O)2OR5, and substituted or unsubstituted C1-C 30 Alkyl alkyl groups, substituted or unsubstituted C1-C 30Alkyl halogens, substituted or unsubstituted C1-C 30 Alkoxy group, substituted or unsubstituted C1-C 30 Alkylthio group, substituted or unsubstituted C1-C 30 Halide alkoxy groups, substituted or unsubstituted C1-C 30 Alkylthio halide group, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkoxy group, substituted or unsubstituted C3-C 30 Cycloalkylthio group, substituted or unsubstituted C3-C 30 Heterocycloalkyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkoxy group, substituted or unsubstituted C3-C 30 Heterocycloalkylthio group, substituted or unsubstituted C2-C 30 Alkenyl group, substituted or unsubstituted C2-C 30 Alkenyloxy group, substituted or unsubstituted C2-C 30 Alkenylthio group, substituted or unsubstituted C3-C 30 Cycloalkenyl group, substituted or unsubstituted C3-C 30 Cycloalkenyloxy group, substituted or unsubstituted C3-C 30 Cycloalkenylthio group, substituted or unsubstituted C3-C 30 Heterocycloalkenyl group, substituted or unsubstituted C3-C 30 Heterocycloalkenyloxy group, substituted or unsubstituted C3-C 30 Heterocycloalkenylthio group, substituted or unsubstituted C2-C 30 Alkynyl group, substituted or unsubstituted C2-C 30 Alkynyloxy group, substituted or unsubstituted C2-C 30 Alkynylthio group, substituted or unsubstituted C6-C 30 Aryl group, substituted or unsubstituted C6-C 30 Aryloxy group, substituted or unsubstituted C6-C 30 Arylthio group, substituted or unsubstituted C1-C 30 Heteroaryl group, substituted or unsubstituted C1-C30 Heteroaryloxy group, or substituted or unsubstituted C1-C 30 It is a heteroarylthio group, R2 and R3 can selectively bond to each other to form a ring. R5 and R6 are, independently, hydrogen, deuterium, a hydroxyl group, and a substituted or unsubstituted C1-C1 group. 30 Alkyl alkyl groups, substituted or unsubstituted C1-C 30 Alkyl halogens, substituted or unsubstituted C1-C 30 Alkoxy group, substituted or unsubstituted C1-C 30 Alkylthio group, substituted or unsubstituted C1-C 30 Halide alkoxy groups, substituted or unsubstituted C1-C 30 Alkylthio halide group, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkoxy group, substituted or unsubstituted C3-C 30 Cycloalkylthio group, substituted or unsubstituted C3-C 30 Heterocycloalkyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkoxy group, substituted or unsubstituted C3-C 30 Heterocycloalkylthio group, substituted or unsubstituted C2-C 30 Alkenyl group, substituted or unsubstituted C2-C 30 Alkenyloxy group, substituted or unsubstituted C2-C 30 Alkenylthio group, substituted or unsubstituted C3-C 30 Cycloalkenyl group, substituted or unsubstituted C3-C 30 Cycloalkenyloxy group, substituted or unsubstituted C3-C 30 Cycloalkenylthio group, substituted or unsubstituted C3-C 30 Heterocycloalkenyl group, substituted or unsubstituted C3-C 30 Heterocycloalkenyloxy group, substituted or unsubstituted C3-C 30 Heterocycloalkenylthio group, substituted or unsubstituted C2-C 30 Alkynyl group, substituted or unsubstituted C2-C30 Alkynyloxy group, substituted or unsubstituted C2-C 30 Alkynylthio group, substituted or unsubstituted C6-C 30 Aryl group, substituted or unsubstituted C6-C 30 Aryloxy group, substituted or unsubstituted C6-C 30 Arylthio group, substituted or unsubstituted C1-C 30 Heteroaryl group, substituted or unsubstituted C1-C 30 Heteroaryloxy group, or substituted or unsubstituted C1-C 30 It is a heteroarylthio group.

[0049] Specifically, in the above chemical formula 2, R2 to R4 are independently hydrogen; deuterium; halogen; cyano group; nitro group; hydroxyl group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether moisture, thioether moisture, carbonyl moisture, ester moisture, phosphonate moisture, sulfonate moisture, carbonate moisture, amide moisture, lactone moisture, sultone moisture, carboxylic acid anhydride moisture, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C1-C 20 Heteroaryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryloxy group, C1-C 20A C1-C group substituted or unsubstituted with a heteroarylthio group, or any combination thereof. 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Selected from arylalkyl groups, R2 and R3 can selectively bond to each other to form a ring. R5 and R6 are, independently, hydrogen; deuterium; hydroxyl group; and deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether moisture, thioether moisture, carbonyl moisture, ester moisture, phosphonate moisture, sulfonate moisture, carbonate moisture, amide moisture, lactone moisture, sultone moisture, carboxylic acid anhydride moisture, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C1-C 20 Heteroaryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryloxy group, C1-C 20 A C1-C group substituted or unsubstituted with a heteroarylthio group, or any combination thereof. 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Selected from arylalkyl groups.

[0050] More specifically, in the above chemical formula 2, R2 to R4 are independently hydrogen; deuterium; halogen; cyano group; nitro group; hydroxyl group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 A heteroaryl group, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Selected from arylalkyl groups, R2 and R3 can selectively bond to each other to form a ring. R5 and R6 are independently hydrogen; deuterium; hydroxyl group; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 A heteroaryl group, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C30 Aryl group, and C7-C 30 Selected from arylalkyl groups.

[0051] In particular, in the above chemical formula 2, R2 to R4 are each independently selected from hydrogen; deuterium; halogen; cyano group; nitro group; hydroxyl group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and one of the following chemical formulas 3-1 to 3-21. R2 and R3 can selectively bond to each other to form a ring. R5 and R6 are independently selected from hydrogen; deuterium; a hydroxyl group; and one of the following chemical formulas 3-1 to 3-21: [ka]

[0052] In the above chemical formulas 3-1 to 3-21, At least one hydrogen is deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 It can be selectively substituted with heteroaryl groups, or any combination thereof.

[0053] In one embodiment, in chemical formula 2, Z2 is represented by one of the following chemical formulas 4-1 to 4-9: [ka]

[0054] In the above chemical formulas 4-1 to 4-9, R2~R4 are independently hydrogen; deuterium; halogen; cyano group; nitro group; hydroxyl group; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 A heteroaryl group, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Selected from arylalkyl groups, R5, R 5a , R 5b R6 is independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C1-C 20 A heteroaryl group, or any combination thereof, substituted or unsubstituted, C1-C 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Selected from arylalkyl groups, R2~R6, R 5a and R 5b Two adjacent groups can selectively bond to each other to form a ring. A 41 and A 42 Each of these C1-C atoms may independently and selectively contain heteroatoms. 30 C1-C which may selectively contain cyclic alkyl groups or heteroatoms. 30 It is an aryl group, R 41and R 42 These are, independently, hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, and C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, or C1-C 20 It is a heteroaryl group, b41 and b42 are each independent integers between 1 and 10. * indicates a bonding site with an adjacent atom.

[0055] In one embodiment, in chemical formula 2, Z2 is represented by one of the following chemical formulas 4-11 to 4-50: [ka] [ka]

[0056] In the aforementioned chemical formulas 4-11 to 4-50, * indicates a bonding site with an adjacent atom. In one embodiment, in the chemical formula 2, at least one of the Z2 groups is an electron-withdrawing group. Specifically, in the above chemical formula 2, at least one of R2 to R4 is an electron-withdrawing group.

[0057] More specifically, in the chemical formula 2, at least one of R2 to R4 is a halogen; a cyano group; a nitro group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and halogen, cyano group, nitro group, C1-C 20 C1-C substituted with halogenated alkyl groups or any combination thereof 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30A cycloalkenyl group, C2-C 30 An alkynyl group, C6-C 30 An aryl group, and C7-C 30 An arylalkyl group; selected from; R5 and R6 are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 An alkyl group, C1-C 20 A halogenated alkyl group, C3-C 20 A cycloalkyl group, C6-C<00 20 <00An aryl group, C1-C 20 A heteroaryl group, or a C1-C optionally substituted or unsubstituted with any combination thereof 30 An alkyl group, C3-C 30 A cycloalkyl group, C2-C 30 An alkenyl group, C3-C 30 A cycloalkenyl group, C2-C 30 An alkynyl group, C6-C 30 An aryl group, and C7-C 30 An arylalkyl group; selected from. For example, in Chemical Formula 2 above, b2 is 1.

[0058] In one embodiment, the additive represented by Chemical Formula 2 is selected from the following Group II: <Group II>

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0059] In the Group II, Ph is a phenyl group. The additive may be any one represented by Chemical Formula 2, or two or more thereof may be used in combination. The aforementioned additive can improve the chemical stability of the organometallic compound by being replaced with the ligand of the organometallic compound.

[0060] In the resist composition, the organometallic compound is present in an amount of 0.01 to 100 parts by weight per 100 parts by weight of the resist composition, specifically, 0.2 or more, 0.5 or more, 1 or more, 1.5 or more, 90 or less, or 80 or less by weight. If the above range is satisfied, a resist composition with improved sensitivity and / or resolution can be provided in which chemical bonds between organometallic compounds are sufficiently formed while side reactions are suppressed.

[0061] In the resist composition, the additive is present in an amount of 0.01 to 100 parts by weight per 100 parts by weight of the resist composition, specifically, 0.2 or more, 0.5 or more, 1 or more, 1.5 or more, 90 or less, or 80 or less by weight. If the above range is satisfied, a resist composition with improved sensitivity and / or resolution can be provided in which chemical bonds between organometallic compounds are sufficiently formed while side reactions are suppressed. In the resist composition, the additive is present in an amount of 0.1 to 100,000 parts by weight per 100 parts by weight of the organometallic compound. Specifically, the additive is present in an amount of 10 to 1,000 parts by weight per 100 parts by weight of the organometallic compound. If the above range is satisfied, the photosensitivity of the resist composition can be maintained at the level of a resist composition without additives, while significantly improving its storage stability.

[0062] Since the resist composition is non-chemically amplified, it substantially does not contain a photoacid generator. The resist composition substantially contains no compounds with a molecular weight of 1,000 or more other than the organometallic compound, since the physical properties of the organometallic compound change upon exposure.

[0063] The resist composition's solubility in the developer changes upon exposure to high-energy rays. The resist composition 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, or a positive-type resist composition in which the exposed areas are dissolved and removed to form a positive-type resist pattern. The resist composition can be modified in various ways, such as becoming negative or positive, depending on the exposure intensity and / or the type of developer.

[0064] Furthermore, the resist composition may be for a distilled water development process using distilled water (DI) for development during resist pattern formation, 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). Specifically, the resist composition is for a distilled water development process or a solvent development process.

[0065] Specifically, if distilled water, an alkaline developer, or any combination thereof is used as the developer, the exposed areas are washed away and removed by the developer, while the unexposed areas remain unwashed and exhibit the characteristics of a positive-type resist composition. Conversely, if an organic solvent is used as the developer, the unexposed areas are washed away and removed by the developer, while the exposed areas remain unwashed and exhibit the characteristics of a negative-type resist composition. In other words, the resist composition may be a negative-type resist composition or a positive-type resist composition depending on the polarity of the developer.

[0066] Although not limited to a specific theory, the organometallic compound reacts with the additive to form a ligand for the organometallic compound, specifically R x The ligand can be substituted with the additive. Then, the organometallic compound in which the ligand has been substituted with the additive may undergo a change in polarity when exposed to high-energy rays, such as the dissociation of specific bonds, for example, bonds within a photoreactive unit.

[0067] Specifically, in organometallic compounds in which ligands have been substituted with additives, radicals are generated from the photoreactive units when exposed to high-energy rays. These radicals then react in an atmosphere where water is selectively present to generate polar functional groups. As a result, the physical properties of the organometallic compound, particularly its solubility in the developer, may change when exposed to high-energy rays.

[0068] The organometallic compounds and additives may be manufactured by any suitable method, or commercially available products may be used. The structure (composition) of the organometallic compound and additive can be confirmed by Fourier-transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), X-ray fluorescence (XRF), mass spectrometry, UV analysis, single-crystal X-ray structure analysis, powder X-ray diffraction (PXRD), liquid chromatography, size exclusion chromatography (SEC), and thermal analysis. Detailed confirmation methods are described in the examples.

[0069] <Solvent> The resist composition may further contain a solvent. The solvent contained in the resist composition is not particularly limited, as long as it can dissolve or disperse the organometallic compound, additives, and any optional components that may be included as needed. The solvent may be used alone, or two or more different solvents may be used in combination. The solvent includes nonpolar solvents, polar aprotic solvents, or any combination thereof. For example, the solvent is a polar aprotic solvent.

[0070] Nonpolar solvents include ether-based solvents, hydrocarbon-based solvents, and any combination thereof. Polar aprotic solvents include ether solvents, ketone solvents, amide solvents, ester solvents, sulfoxide solvents, and any combination thereof. Examples of ether-based solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether; cyclic ether solvents such as 1,4-dioxane, tetrahydrofuran, and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0071] 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.

[0072] Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and linear amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0073] Examples of ester solvents include acetate ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate; polyhydric alcohol-containing ether carboxylate solvents such as 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 monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone, δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate; ethylene glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like.

[0074] Examples of sulfoxide solvents include dimethyl sulfoxide, diethyl sulfoxide, and the like. 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.

[0075] Specifically, the solvent is selected from ketone solvents, ester solvents, and any combination thereof. More specifically, the solvent is selected from linear ketone solvents, cyclic ketone solvents, polyhydric alcohol-containing ether carboxylate solvents, lactone solvents, acetate ester solvents, and any combination thereof. In particular, the solvent is selected from methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, n-butyl acetate, and any combination thereof.

[0076] Since the resist composition is substantially water-free, the solvent is water-free. Specifically, the resist composition contains 3% by weight or less of water, and the solvent contains 3% by weight or less of water. The solvent is present in an amount of 0 to 99.9 parts by weight per 100 parts by weight of the resist composition. The solvent may be used alone, or two or more different solvents may be used in mixture form.

[0077] <Optional ingredients> The resist composition may further contain, if necessary, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof. The resist composition may further contain a surfactant to improve its applicability, developability, and other properties. 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.).

[0078] The surfactant is present in an amount of 0 to 20 parts by weight per 100 parts by weight of the resist composition. One type of surfactant may be used, or two or more different types may be used in mixture form. The method for producing the resist composition is not particularly limited, and for example, a method of mixing organometallic compounds, additives, and optional components added as needed in an organic solvent can be used. The temperature and time during mixing are not particularly limited. Filtration can be performed after mixing as needed.

[0079] [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.

[0080] Referring to 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). These steps can be omitted as needed, and the order in which they are performed can also be changed.

[0081] 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. A resist composition can be applied to the substrate 100 to a desired thickness by a coating method to form a resist film 110. If necessary, a post-application bake (PAB) can be performed to remove any organic solvent remaining on the resist film 110.

[0082] 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. 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.

[0083] 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.

[0084] 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. In one embodiment, a protective film may be further provided on the resist film 100 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 100 to avoid direct contact between the immersion medium and the resist film 100.

[0085] 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 an exposed portion 111 and an unexposed portion 112.

[0086] Although not limited to any particular theory, exposure can generate radicals in the exposed area 111, which then generate polar functional groups, potentially altering the physical properties of the resist composition. As a result, the exposed area 111 and the unexposed area 112 can have different water contact angles, and the difference between the water contact angle of the unexposed area 112 and the water contact angle of the exposed area 111 is 25° or more, specifically 40° or more, more specifically 50° or more, and especially 60° or more.

[0087] In one embodiment, the exposure dose for the exposure is 100 mJ / cm². 2 Specifically, 80 mJ / cm² 2 To be more specific, the following is 60 mJ / cm². 2 The following, in particular, 50 mJ / cm² 2 The following conditions apply: the difference between the water contact angle of the non-exposed area 112 and the water contact angle of the exposed area 111 is 25° or more, specifically 40° or more, more specifically 50° or more, and especially 60° or more.

[0088] The exposure dose for the aforementioned exposure was 100 mJ / cm². 2 When the following conditions are met, the difference between the water contact angle of the unexposed area 112 and the water contact angle of the exposed area 111 is 25° or more, specifically 30° or more, and in particular, the exposure dose of the exposure is 80 mJ / cm². 2 When the following conditions are met, the difference between the water contact angle of the unexposed area 112 and the water contact angle of the exposed area 111 is 25° or more, specifically 30° or more. In some cases, this exposure is carried out by irradiating a material with high-energy rays through a mask having a predetermined pattern, using a liquid such as water as a medium. Examples of such 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."

[0089] 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.

[0090] 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 applies. Furthermore, when using electron beams as high-energy beams, the cumulative dose is 5000 μC / cm². 2 Below, specifically 1000 μC / cm 2 The following applies:

[0091] 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 250°C or lower, specifically 200°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. Next, the exposed resist film 110 can be developed using a developer to form a resist pattern 115.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] As the organic solvent contained in the organic developer, for example, one similar to the organic solvent exemplified in the <solvent> part of the [resist composition] can be used. Alternatively, an alcohol-based solvent or a lactate-based solvent can be used as the organic solvent.

[0096] Examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, 4-methyl-2-pentanol (MIBC), sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, and 2,6-dimethyl-4-heptanol. Monoalcohol solvents such as n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;Examples include polyhydric alcohol-containing ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

[0097] Examples of lactate-based solvents include methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate. Specifically, the organic developer used may include nBA (n-butyl acetate), PGME, PGMEA, ethyl lactate, GBL (γ-butyrolactone), IPA (isopropanol), etc. The organic developer may further contain organic acids such as acetic acid, formic acid, and citric acid.

[0098] 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. In one embodiment, the developer comprises distilled water, an alkaline developer, or any combination thereof, and the exposed area 111 is removed by the developer.

[0099] 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.

[0100] The resist pattern 115 can be further cleaned after development. Ultrapure water, a rinsing solution, etc., can be used as the cleaning solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern; a general organic solvent solution can be used. For example, the rinsing solution may be an alcohol-based solvent or an ester-based solvent. After cleaning, any remaining rinsing solution on the substrate and pattern can be removed. Furthermore, if ultrapure water is used, any remaining water on the substrate and pattern can be removed. Furthermore, the developing solution can be used individually or in combination of two or more types.

[0101] 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. 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.

[0102] 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.

[0103] 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. Although not shown in the figures, the resist composition may be a negative-type composition. If the resist composition is a negative-type composition, the developer contains an organic solvent, and the unexposed areas 112 are removed by the developer.

[0104] 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. 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.

[0105] 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. 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.

[0106] 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. As shown in Figure 3E, the resist pattern 115 can be removed.

[0107] Figures 4A to 4E are side cross-sectional views showing a method for forming a semiconductor device according to one embodiment. 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. 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.

[0108] 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. 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.

[0109] 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. Figures 4A to 4E show examples of transistor formation, but the present invention is not limited thereto.

[0110] A resist composition according to one embodiment can be used in a patterning process for forming other types of semiconductor devices. 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.

[0111] [Examples] Synthesis Example 1: Synthesis of M1 [ka]

[0112] (1) Synthesis of M1-1 8.2 g (69.2 mmol) of Sn powder and 120 ml of dry toluene were placed in a 250 ml three-necked flask, and the temperature was raised to 90°C. Approximately 1.0 ml of DI water was added, and then 10.0 g (69.2 mmol) of 4-fluorobenzyl chloride was added dropwise for 10 minutes. After heating under reflux and stirring at 130°C for 4 hours, the unreacted Sn powder was filtered using a Buchner funnel. Simultaneously, as the filtered solution cooled, 6.5 g (36% yield) of the product, white crystals M1-1, was obtained.

[0113] (2) Synthesis of M1 1.5 g (3.7 mmol) of M1-1 and 21.0 ml of dry acetone were placed in a 50 ml one-necked flask, and the temperature was lowered to 0°C. 0.6 g (7.4 mmol) of sodium acetate was added, and the mixture was stirred for 12 hours. The NaCl salt generated in the solution was filtered through a 0.45 μm filter, and the solution was concentrated by rotational evaporation and vacuum drying to obtain M1 (1.6 g) in 74% yield. 1 H-NMR(500MHz,DMSO-d6):δ~6.9(8H),~2.6(4H),~1.6(6H)

[0114] Synthesis Example 2: Synthesis of M2 [ka]

[0115] (1) Synthesis of M2-2 Diphenylmethane (4.89 g, 29.1 mmol) was placed in a two-necked round-bottom flask purged with N2 and diluted with THF (30 ml). n-BuLi (2.5 M in hexane, 29.1 mmol) was added dropwise at -78°C, and the mixture was stirred at 0°C for 0.5 hours. Dichlorodiphenyl stannane (5 g, 14.5 mmol) was placed in a vial and diluted with THF (28 ml, total THF (58 ml, 0.25 M)). The solution from the vial was added dropwise to the round-bottom flask at -78°C, and the mixture was stirred for 0.5 hours, then the temperature was raised to room temperature and the mixture was stirred again for 0.5 hours. After confirming the completion of the reaction, the solvent was removed, the mixture was filtered through silica / Celite, and then purified by column chromatography (ethyl acetate (EA): n-hexane (EA 5 v%)) to obtain M2-2 (6.8 g, 77%).

[0116] (2) Synthesis of M2-1 M2-2 (6.2 g, 10.2 mmol) was placed in a round-bottom flask and replaced with N2. After dilution with dichloromethane (102 ml, 0.1 M), 2 M HCl in Et2O solution (15.3 ml, 30.67 mmol) was added dropwise at -78°C. After stirring at -78°C for 1 hour, the temperature was raised to room temperature and the reaction was continued for another 12 hours. The solvent was removed and the resulting solid was washed with methyl t-butyl ether:n-hexane (5 ml:100 ml) and dried under vacuum to obtain M2-1 (4.3 g, 80%).

[0117] (3) Synthesis of M2 M2-1 (1.0 g, 1.91 mmol) was placed in a round-bottom flask and replaced with N2. After dilution with acetone (19 ml, 0.1 M), sodium acetate (0.31 g, 3.82 mmol) was added at 0°C. The reaction was carried out at 0°C for 16 hours, and then filtered using Celite. After removing the solvent, recrystallization was performed (methyl t-butyl ether:n-hexane = 3 ml:30 ml). After filtering, the precipitate was dried under vacuum to obtain M2 (0.54 g, 50%). 1 H NMR(500MHz,CD2Cl2)δ7.42-6.98(m,20H),4.71(s,2H),1.64(s,6H) 13 C NMR(126MHz,CD2Cl2)δ182.13,138.99,129.41,128.78,126.68,57.91,19.88 119 Sn NMR(186MHz,CD2Cl2)δ-345.10

[0118] Manufacturing example: Production of casting solution Casting solutions A-1 and A-2 were prepared by dissolving the organometallic compounds and additives synthesized in Synthesis Examples 1 and 2 in cyclopentanone at a weight of 2%. Here, the weight ratio of the additive to the organometallic compound was 1:1.5. Furthermore, casting solution B-1 was prepared, which has the same composition as casting solution A-1 except that it does not contain additives.

[0119] [Table 1]

[0120] [ka]

[0121] Evaluation Example 1: FT-IR Analysis Solutions of compound M1, compound A1, a mixture of compound M1 and compound A1, and compound X1, each dissolved in cyclopentanone, were coated to a thickness of 50 nm onto an Au-coated Si wafer. After drying, samples were prepared, and FT-IR analysis was performed. The results are shown in Figure 5. Referring to Figure 5, characteristic peaks for M1 and A1 were observed in the mixture of M1 and A1, as well as in X1. This confirms that in the mixture of M1 and A1, the ligand of M1 was replaced by A1 to form X1.

[0122] [ka]

[0123] Evaluation Example 2: Thin Film Stability Evaluation After cutting an 8-inch diameter silicon wafer into quarters, it was treated with O2 plasma for 30 minutes. Then, casting solutions A-1, A-2, and B-1 were spin-coated at 1200 rpm for 1 minute each, followed by PAB at 100°C for 1 minute to produce films with the predetermined initial thicknesses shown below. Subsequently, the thickness of the films was measured again after 5, 10, 20, and 30 days, and the thicknesses are shown in Table 2 below as relative values ​​to the initial thickness.

[0124] [Table 2]

[0125] Referring to Table 2 above, in the case of B-1 without additives, the thin film thickness decreased significantly over time after coating, confirming low thin film stability. However, in the cases of A-1 and A-2 with additives, the thin film thickness remained substantially the same over time after coating, confirming relatively high thin film stability.

[0126] Evaluation Example 3: Thin Film Development Evaluation (1) Terminology In Examples 1-1 and 1-2, E0 represents the exposure level at the point where the thin film is completely developed (the thickness of the thin film cannot be reduced any further), and E1 represents the exposure level at the point where the development of the thin film begins. In Comparative Examples 1-1, 1-2, and Example 2-1, E0 represents the exposure level at which the thin film begins to harden, and E1 represents the exposure level at the saturation point where the thin film does not become any thicker. γ is a contrast curve, and its value is calculated using the following formula 1.

number

[0127] After cutting an 8-inch diameter silicon wafer into quarters, it was treated with O2 plasma for 30 minutes. Then, casting solutions A-1, A-2, and B-1 were spin-coated for 1 minute at the coating rates shown in Table 3 below, and then PAB was performed at 100°C for 1 minute to fabricate a film with a predetermined initial thickness. Next, a 1 cm thick mask (4 cm × 4 cm) with rectangular holes (1 cm × 1 cm) was placed on top, and 254 nm wavelength DUV was applied to each hole at a rate of 0 to 100 mJ / cm². 2 The film was exposed with the specified dose and subjected to PEB for 1 minute at the temperature shown in Table 3 below. The dried film was immersed in distilled water (DI), PGME:acetic acid (AA) (98:2 wt%), or PGMEA as the developer at 25°C for 60 seconds, and the remaining film thickness was measured and is shown in Figures 6A to 6C and Figure 7. Figure 6A shows the change in film thickness after development with the doses of Example 1-1, Figure 6B shows Example 1-2, Figure 6C shows Comparative Example 1-1, Figure 6D shows Comparative Example 1-2, and Figure 7 shows the change in film thickness after development with the doses of Example 2-1.

[0128] [Table 3]

[0129] Referring to Figures 6A to 6D and Figure 7, it was confirmed that casting solutions A-1 and A-2, which contain additives, exhibit the characteristics of either a positive-type or negative-type resist composition depending on the polarity of the developer, while casting solution B-1, which does not contain additives, does not remove the exposed area even when the polarity of the developer is changed.

[0130] Evaluation Example 4: Water Contact Angle (WCA) Evaluation After cutting an 8-inch diameter silicon wafer into quarters, it was treated with O2 plasma, then spin-coated with casting solutions A-1 and A-2 at 1200 rpm for 1 minute each, followed by drying at 100°C for 1 minute (PAB) to create a film with an initial thickness of 40 nm. Next, a 1 cm thick mask (4 cm × 4 cm) with rectangular holes (1 cm × 1 cm) was placed on top, and 254 nm wavelength DUV light was applied to each hole at a rate of 0-100 mJ / cm². 2 The samples were exposed to light with a specific dose and dried at 170°C for 90 seconds (PEB). Then, 3 μL of water was dropped into each hole, and the water contact angle (in degrees) was measured. The results are shown in Table 4 below.

[0131] [Table 4]

[0132] Referring to Table 4 above, it can be seen that the water contact angles of resist compositions A-1 and A-2, which contain both M1 or M2 and A1, changed significantly before and after DUV irradiation, confirming that a change in the polarity of the organometallic compound occurred.

Claims

1. A resist composition comprising an organometallic compound represented by the following chemical formula 1 and an additive represented by the following chemical formula 2: M １１ (R) ｘ ) ｎ (R) ｙ ) （ｍ－ｎ） [Chemical Formula 1] (X) ２ ) ｃ２ - (L) ２ ) ａ２ - [Y] ２ -Z ２ ] ｂ２ [Chemical Formula 2] In the aforementioned chemical formulas 1 and 2, M １１ These are indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po). R ｘ *-X １ -Y １ And, R ｙ *-(L １ ) ａ１ - (R １ ) ｂ１ And, n is an integer from 1 to 6. m is an integer from 1 to 6. m-n is greater than or equal to 0, Multiple R ｘ They may be the same or different from each other. Multiple R ｙ They may be the same or different from each other. 6 １ は、O、OC(=O)、C(=O)O、OS(=O)、S(=O)O、OS(=O) ２ 、S(=O) ２ O、S、SC(=O)、またはC(=O)Sであり、 Y １ C may selectively contain hydrogen, deuterium, or heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. L １ C may selectively contain single bonds or heteroatoms. １ -C ３０ It is a linear, branched, or cyclic divalent hydrocarbon group. a1 is an integer between 0 and 4. R １ C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group, with multiple R １ Two adjacent groups can selectively bond to each other to form a ring. b1 is an integer from 1 to 4, X ２ are OH, SH, C(=O)OH, S(=O)OH, S(=O) ２ OH, or P(=O)(OH) ２ And, c2 is an integer between 1 and 4. L ２ Each of these C elements may independently selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic divalent hydrocarbon group. a2 is an integer between 0 and 4. Y ２ -Z ２ It is a photoreactive unit, b2 is an integer between 1 and 4. * indicates a bonding site with an adjacent atom.

2. M １１ The resist composition according to claim 1, wherein is Sn, Sb, Te, or Bi.

3. X １ These are O, OC(=O), C(=O)O, S, SC(=O), or C(=O)S, Y １ hydrogen; deuterium; and deuterium, halogens, cyano groups, nitro groups, hydroxyl groups, thiol groups, amino groups, carboxylic acid groups, ether molecules, thioether molecules, carbonyl molecules, ester molecules, phosphonate molecules, sulfonate molecules, carbonate molecules, amide molecules, lactone molecules, sultone molecules, carboxylic acid anhydride molecules, C １ -C ２０ alkyl group, C １ -C ２０ Alkyl halogenated compounds, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halide alkoxy group, C １ -C ２０ Alkylthio halogenated group, C ３ -C ２０ Cycloalkyl groups, C ３ -C ２０ Cycloalkoxy group, C ３ -C ２０ Cycloalkylthio group, C ６ -C ２０ Aryl group, C １ -C ２０ heteroaryl group, C ６ -C ２０ Aryloxy group, C ６ -C ２０ Arylthio group, C １ -C ２０ Heteroaryloxy group, C １ -C ２０ A heteroarylthio group, or any combination thereof, substituted or unsubstituted, C １ -C ３０ alkyl group, C １ -C ３０ Alkyl halogenated compounds, C １ -C ３０ Alkoxy group, C １ -C ３０ Alkylthio group, C １ -C ３０ Halide alkoxy group, C １ -C ３０ an alkylthiohalide group, C ３ -C ３０ a cycloalkyl group, C ３ -C ３０ a cycloalkoxy group, C ３ -C ３０ a cycloalkylthio group, C ３ -C ３０ a heterocycloalkyl group, C ２ -C ３０ an alkenyl group, C ３ -C ３０ a cycloalkenyl group, C ３ -C ３０ a heterocycloalkenyl group, C ２ -C ３０ an alkynyl group, C ６ -C ３０ an aryl group, C ６ -C ３０ an aryloxy group, C ６ -C ３０ an arylthio group, C ７ -C ３０ an arylalkyl group, C １ -C ３０ a heteroaryl group, C １ -C ３０ a heteroaryloxy group, C １ -C ３０ a heteroarylthio group, and C ２ -C ３０ a heteroarylalkyl group; The resist composition according to claim 1, which is selected from.

4. L １ C is a single bond, substituted, or unsubstituted bond. １ -C ３０ Alkylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group, substituted or unsubstituted C ２ -C ３０ Alkenylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group, substituted or unsubstituted C ６ -C ３０ Arylene group, or substituted or unsubstituted C １ -C ３０ It is a heteroarylene group, a1 is 0, 1, or 2. R １ This includes deuterium, halogens, cyano groups, nitro groups, hydroxyl groups, thiol groups, amino groups, carboxylic acid groups, ether molecules, thioether molecules, carbonyl molecules, ester molecules, phosphonate molecules, sulfonate molecules, carbonate molecules, amide molecules, lactone molecules, sultone molecules, carboxylic acid anhydride molecules, C １ -C ２０ alkyl group, C １ -C ２０ Alkyl halogenated compounds, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halide alkoxy group, C １ -C ２０ Alkylthio halogenated group, C ３ -C ２０ Cycloalkyl groups, C ３ -C ２０ Cycloalkoxy group, C ３ -C ２０ Cycloalkylthio group, C ６ -C ２０ Aryl group, C １ -C ２０ heteroaryl group, C ６ -C ２０ Aryloxy group, C ６ -C ２０ Arylthio group, C １ -C ２０ Heteroaryloxy group, C １ -C ２０ A heteroarylthio group, or any combination thereof, substituted or unsubstituted, C １ -C ３０ alkyl group, C ３ -C ３０ Cycloalkyl groups, C ３ -C ３０ Heterocycloalkyl groups, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ３ -C ３０ Heterocycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ Aryl group, C ７ -C ３０ Arylalkyl group, C １ -C ３０ Heteroaryl group, and C ２ -C ３０ A resist composition according to claim 1, selected from heteroarylalkyl groups.

5. The organometallic compound represented by the chemical formula 1 is selected from the following group I, the resist composition according to claim 1: <Group I> 【Chemistry 1A】 【Chemistry 1B】 【Chemical 1C】 【Transform 1D】 In group I, n is an integer between 0 and 3.

6. X ２ The resist composition according to claim 1, wherein is OH or C(=O)OH.

7. (L ２ ) ａ２ The resist composition according to claim 1, wherein is represented by any one of the following chemical formulas 5-1 to 5-7: 【Chemistry 2】 In the aforementioned chemical formulas 5-1 to 5-7, R ５１ ~R ５３ These are, independently, hydrogen, deuterium, halogen, hydroxyl group, cyano group, and C １ -C ４ alkyl group, or C １ -C ４ It is a halogenated alkyl group, b51 is an integer between 1 and 4. n51 is an integer between 1 and 3. * and *' are bonding sites with adjacent atoms.

8. Y ２ are OC(=O), C(=O)O, OS(=O) ２ , or S (=O) ２ It is O, Z ２ is *-C(R ２ ) (Caution ３ ) (Caution ４ ), *-C(R ２ ) = N(R ３ ), * - N = C ( R ２ ) (Caution ３ ), or *-N (R ２ ) (Caution ３ ) and R ２ ~R ４ These are, independently, hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, and -C(=O)R. ５ , -C(R ５ ) = NR ６ , -OR ５ , -S(=O)R ５ , -S (=O) ２ R ５ , -S (=O) ２ OR ５ , substitution or non-substitution of C １ -C ３０ Alkyl, substituted or unsubstituted C １ -C ３０ Alkyl halogenated groups, substituted or unsubstituted C １ -C ３０ alkoxy group, substituted or unsubstituted C １ -C ３０ Alkylthio group, substituted or unsubstituted C １ -C ３０ Halide alkoxy groups, substituted or unsubstituted C １ -C ３０ Alkylthio halogenated group, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C ３ -C ３０ Cycloalkoxy group, substituted or unsubstituted C ３ -C ３０ Cycloalkylthio group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkyl groups, substituted or unsubstituted C ３ -C ３０ Heterocycloalkoxy groups, substituted or unsubstituted C ３ -C ３０ Heterocycloalkylthio group, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ２ -C ３０ Alkenyloxy group, substituted or unsubstituted C ２ -C ３０ Alkenylthio group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyloxy group, substituted or unsubstituted C ３ -C ３０ Cycloalkenylthio group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyloxy group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylthio group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ２ -C ３０ Alkynyloxy group, substituted or unsubstituted C ２ -C ３０ Alkynylthio group, substituted or unsubstituted C ６ -C ３０ Aryl group, substituted or unsubstituted carbon ６ -C ３０ Aryloxy group, substituted or unsubstituted C ６ -C ３０ Arylthio group, substituted or unsubstituted C １ -C ３０ heteroaryl group, substituted or unsubstituted C １ -C ３０ Heteroaryloxy group, or substituted or unsubstituted C １ -C ３０ It is a heteroarylthio group, R ２ and R ３ They can selectively bond to each other to form a ring, R ５ and R ６ These are, independently, hydrogen, deuterium, a hydroxyl group, and a substituted or unsubstituted C. １ -C ３０ Alkyl, substituted or unsubstituted C １ -C ３０ Alkyl halogenated groups, substituted or unsubstituted C １ -C ３０ alkoxy group, substituted or unsubstituted C １ -C ３０ Alkylthio group, substituted or unsubstituted C １ -C ３０ Halide alkoxy groups, substituted or unsubstituted C １ -C ３０ Alkylthio halogenated group, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C ３ -C ３０ Cycloalkoxy group, substituted or unsubstituted C ３ -C ３０ Cycloalkylthio group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkyl groups, substituted or unsubstituted C ３ -C ３０ Heterocycloalkoxy groups, substituted or unsubstituted C ３ -C ３０ Heterocycloalkylthio group, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ２ -C ３０ Alkenyloxy group, substituted or unsubstituted C ２ -C ３０ Alkenylthio group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyloxy group, substituted or unsubstituted C ３ -C ３０ Cycloalkenylthio group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyloxy group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylthio group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ２ -C ３０ Alkynyloxy group, substituted or unsubstituted C ２ -C ３０ Alkynylthio group, substituted or unsubstituted C ６ -C ３０ Aryl group, substituted or unsubstituted carbon ６ -C ３０ Aryloxy group, substituted or unsubstituted C ６ -C ３０ Arylthio group, substituted or unsubstituted C １ -C ３０ heteroaryl group, substituted or unsubstituted C １ -C ３０ Heteroaryloxy group, or substituted or unsubstituted C １ -C ３０ The resist composition according to claim 1, wherein the group is a heteroarylthio group.

9. The resist composition according to claim 1, wherein the additive is selected from the following group II: <Group II> 【Chemistry 3A】 【Chemistry 3B】 【Chemicals 3C】 [3D Transformation] In the aforementioned group II, Ph is a phenyl group.

10. The resist composition according to claim 1, wherein the additive is contained in an amount of 0.1 to 100,000 parts by weight per 100 parts by weight of the organometallic compound.

11. The resist composition according to claim 1, further comprising a solvent.

12. The resist composition according to claim 11, wherein the solvent is a polar aprotic solvent.

13. The resist composition according to claim 11, wherein the solvent is selected from ketone solvents, ester solvents, and any combination thereof.

14. The resist composition according to claim 11, wherein the solvent is selected from a chain-type ketone solvent, a cyclic ketone solvent, a polyhydric alcohol-containing ether carboxylate solvent, a lactone solvent, an acetate ester solvent, and any combination thereof.

15. The resist composition according to claim 11, wherein the solvent is selected from methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, n-butyl acetate, and any combination thereof.

16. A step of forming a resist film by applying the resist composition according to any one of claims 1 to 15 onto a substrate, 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.

17. The pattern forming method according to claim 16, wherein the exposure step is performed by irradiating with ultraviolet light, far ultraviolet light (DUV), extreme ultraviolet light (EUV), X-rays, gamma rays, electron beams (EB) and / or alpha rays.

18. The exposed resist film includes an exposed portion and an unexposed portion. The pattern forming method according to claim 16, wherein the difference between the water contact angle of the non-exposed area and the water contact angle of the exposed area is 25° or more.

19. The exposed resist film includes an exposed portion and an unexposed portion. The developer comprises distilled water, an alkaline developer, or any combination thereof. The pattern forming method according to claim 16, wherein the exposed portion is removed during the developing step.

20. The exposed resist film includes an exposed portion and an unexposed portion. The developer contains an organic solvent. The pattern forming method according to claim 16, wherein the unexposed portion is removed during the developing step.

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