Organometallic compound, resist composition containing the same, and pattern forming method using the same

Abstract

To provide an organometallic compound, a resist composition containing the same, and a pattern forming method using the same.SOLUTION: There are provided: an organometallic compound represented by one of the following chemical formulae 1-1 to 1-4; a resist composition containing the same; and a pattern forming method using the same. In the chemical formulae 1-1 to 1-4, explanations regarding M11, Q11 to Q14, b11 to b14, R11 to R14, Y11 to Y13, and X11 to X14 are described in the specification.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] In the manufacture of semiconductors, resists whose physical properties change in response to light are used to form fine patterns. Among them, chemically amplified resists have been widely used. In chemically amplified resists, an acid formed by the reaction of light with a photoacid generator reacts again with a base resin, changing the solubility of the base resin in a developer, thereby enabling patterning.

[0003] However, in the case of chemically amplified resists, as the formed acid diffuses into non-exposed areas, problems such as reduced pattern uniformity, increased surface roughness, etc. In addition, as semiconductor processes become increasingly miniaturized, it is no longer easy to control the diffusion of acid, making it necessary to develop a new type of resist.

[0004] In recent years, in order to overcome the limitations of chemically amplified resists, attempts have been made to develop materials whose physical properties change upon exposure, but the problem remains that the dose required for exposure is still too high. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a resist composition that changes physical properties even by exposure to low doses, thereby providing a pattern with improved resolution, and a method for forming a pattern using the same. [Means for solving the problem]

[0006] According to one aspect, there is provided an organometallic compound represented by any one of the following chemical formulas 1-1 to 1-4: [ka]

[0007] In the above Chemical Formulas 1-1 to 1-4, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), Q 11 ~Q 14 each independently represents a substituted or unsubstituted C 2 -C 30 Alkenyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 2 -C 30 Alkynyl group, substituted or unsubstituted C 6 -C 30 Aryl group, or substituted or unsubstituted C 1 -C 30 is a heteroaryl group, b11 is 2 or 3; b12 to b14 each independently represent an integer of 0 to 3; R 11 ~R 14 each independently represents hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, a substituted or unsubstituted C 1 -C 30 Alkyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl groups, substituted or unsubstituted C 2 -C 30 Alkenyl groups, substituted or unsubstituted C 3 -C30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 2 -C 30 Alkynyl group, substituted or unsubstituted C 6 -C 30 Aryl group, or substituted or unsubstituted C 1 -C 30 is a heteroaryl group, Q 11 ~Q 14 and R 11 ~R 14 two adjacent ones of the groups may be selectively bonded to each other to form a ring; Y 11 ~Y 13 are each independently O, O(C=O), S, S(C=O), NX 14 or N(C=O)X 14 and X 11 ~X 14 each independently represents a hydrogen atom, a deuterium atom, or a C which may optionally contain a heteroatom; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

[0008] According to another aspect, there is provided a resist composition comprising the organometallic compound described above. In still another aspect, there is provided a pattern forming method including the steps of applying the resist composition to form a resist film, exposing at least a portion of the resist film to high-energy radiation, and developing the exposed resist film using a developer. Effect of the Invention

[0009] Embodiments of the present invention can provide resist compositions that have improved sensitivity and provide patterns of improved resolution. [Brief description of the drawings]

[0010] [Figure 1]1 is a flow chart illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2A] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2B] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2C] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 3A] 1 is a drawing showing 1H-NMR data of A-2. [Figure 3B] 1 is a drawing showing 13C-NMR data of A-2. [Figure 3C] 1 is a drawing showing 119Sn-NMR data of A-2. [Figure 4A] 1 is a drawing showing 1H-NMR data of A-1. [Figure 4B] 1 is a drawing showing 13C-NMR data of A-1. [Figure 4C] 1 is a drawing showing 119Sn-NMR data of A-1. [Figure 5A] 1 is a diagram showing 1H-NMR data of OM-A. [Figure 5B] 1 is a diagram showing 13C-NMR data of OM-A. [Figure 5C] 1 is a diagram showing 119Sn-NMR data of OM-A. [Figure 6A] 1 is a drawing showing 1H-NMR data of B-2. [Figure 6B] 1 is a drawing showing 13C-NMR data of B-2. [Figure 6C] 1 is a diagram showing 119Sn-NMR data of B-2. [Figure 7A] 1 is a drawing showing 1H-NMR data of B-1. [Figure 7B] 1 is a diagram showing 13C-NMR data of B-1. [Figure 7C] 1 is a diagram showing 119Sn-NMR data of B-1. [Figure 8A] 1 is a diagram showing 1H-NMR data of OM-B. [Figure 8B] 1 is a diagram showing 13C-NMR data of OM-B. [Figure 8C] 1 is a diagram showing 119Sn-NMR data of OM-B. [Figure 9A] 1 is a graph showing the change in film thickness after development depending on the dose in Example 1-1. [Figure 9B] 1 is a graph showing the change in film thickness after development depending on the dose in Example 1-2. [Figure 9C] 1 is a graph showing the change in film thickness after development depending on the dose in Examples 1-3. [Figure 9D] 1 is a graph showing the change in film thickness after development depending on the dose in Examples 1-4. [Figure 9E] 1 is a graph showing the change in film thickness after development depending on the dose in Examples 1-5. [Figure 10A] 1 is a graph showing the change in film thickness after development depending on the dose in Example 2-1. [Figure 11A] 1 is a graph showing the change in film thickness after development depending on the dose in Comparative Example 1. [Figure 11B] 13 is a graph showing the change in film thickness after development depending on the dose in Comparative Example 2. [Figure 11C] 13 is a graph showing the change in film thickness after development depending on the dose in Comparative Example 3. [Figure 12A] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 12B] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 12C] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 12D] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 12E] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 13A] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 13B]1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 13C] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 13D] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 13E] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention can be modified in various ways and can have various embodiments, and a specific embodiment will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to a specific embodiment, and the present invention should be understood to include all modifications, equivalents, or alternatives included in the spirit and technical scope of the present invention. When a detailed description of a known technology related to the description of the present invention is considered to make the gist of the present invention unclear, the detailed description will be omitted.

[0012] Terms such as "first," "second," and "third" are used to describe various components, but are used only for the purpose of distinguishing one component from other components, and do not limit the order, types, etc. of the components. In this specification, when a layer, film, region, plate or other part is described as being "on" or "above" another part, this includes not only parts that are in contact with each other and are immediately above, below, to the left or right of each other, but also parts that are not in contact with each other and are immediately above, below, to the left or right of each other.

[0013] The singular expression includes the plural expression unless the context clearly dictates otherwise. Terms such as "comprise" or "have" should be understood to indicate the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof described in the specification, unless specifically stated to the contrary, and not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof.

[0014] Whenever a range of values ​​is recited, the range includes all values ​​that fall within the range as expressly recorded, and further includes the boundaries of the range. Thus, a range "from X to Y" includes all values ​​between X and Y, including X and Y.

[0015] In this specification, "C x -C y " means that the number of carbon atoms constituting the substituent is x to y. For example, "C 1 -C 6 " means that the number of carbon atoms constituting the substituent is 1 to 6, and "C 6 -C 20 " means that the number of carbon atoms constituting the substituent is 6 to 20.

[0016] In this specification, the term "monovalent hydrocarbon group" refers to a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and specific examples include linear or branched alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); monovalent saturated cyclic aliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, and the like). monovalent unsaturated aliphatic hydrocarbon groups (alkenyl groups, alkynyl groups) (e.g., allyl groups); monovalent unsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl groups) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl groups, 1-naphthyl groups, and 2-naphthyl groups); arylalkyl groups (e.g., benzyl groups and diphenylmethyl groups); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl groups, methoxymethyl groups, ethoxymethyl groups, methylthiomethyl groups, acetamidomethyl groups, trifluoroethyl groups, (2-methoxyethoxy)methyl groups, acetoxymethyl groups, 2-carboxy-1-cyclohexyl groups, 2-oxopropyl groups, 4-oxo-1-adamantyl groups, and 3-oxocyclohexyl groups), or any combination thereof. In addition, in these groups, some of the hydrogen atoms are replaced by moieties containing heteroatoms, such as oxygen, sulfur, nitrogen, or halogen atoms, or some of the carbons are replaced by moieties containing heteroatoms, such as oxygen, sulfur, or nitrogen, so that these groups can also contain hydroxy groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonates, lactone rings, sultone rings, carboxylic acid anhydride moieties, or haloalkyl moieties.

[0017] In this specification, the term "divalent hydrocarbon group" refers to a divalent residue in which any one of the hydrogen atoms of the monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. The divalent hydrocarbon group may include, for example, a linear or branched alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, or groups in which some of the carbon atoms are replaced by heteroatoms.

[0018] As used herein, "alkyl group" means a linear or branched saturated aliphatic hydrocarbon monovalent group, specific examples of which include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, etc. As used herein, "alkylene group" means a linear or branched saturated aliphatic hydrocarbon divalent group, specific examples of which include methylene, ethylene, propylene, butylene, isobutylene, etc.

[0019] As used herein, the term "halogenated alkyl group" refers to an alkyl group in which one or more substituents are substituted with halogen. Specific examples include CF 3 Here, halogen is F, Cl, Br or I.

[0020] As used herein, an "alkoxy group" is -OA 101 where A means a monovalent group having the formula 101 is an alkyl group. Specific examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group. As used herein, an "alkylthio group" is defined as -SA 101 where A means a monovalent group having the formula 101 is an alkyl group.

[0021] In the present specification, the term "halogenated alkoxy group" refers to an alkoxy group in which one or more hydrogen atoms are replaced with halogen, and a specific example is -OCF 3 etc. As used herein, the term "halogenated alkylthio group" refers to an alkylthio group in which one or more hydrogen atoms have been replaced with halogen. Specific examples include -SCF 3 etc.

[0022] In this specification, "cycloalkyl group" means a monovalent saturated hydrocarbon cyclic group, specific examples of which include monocyclic groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and condensed polycyclic groups such as a norbornyl group and an adamantyl group. In this specification, "cycloalkylene group" means a divalent saturated hydrocarbon cyclic group, specific examples of which include a cyclopentylene group, a cyclohexylene group, an adamantylene group, an adamantylmethylene group, a norbornylene group, a norbornylmethylene group, a tricyclodecanylene group, a tetracyclododecanylene group, a tetracyclododecanylmethylene group, a dicyclohexylmethylene group, and the like.

[0023] As used herein, a "cycloalkoxy group" is defined as -OA 102 where A means a monovalent group having the formula 102 is a cycloalkyl group. Specific examples thereof include a cyclopropoxy group, a cyclobutoxy group, and the like. As used herein, a "cycloalkylthio group" is defined as -SA 102 where A means a monovalent group having the formula 102 is a cycloalkyl group.

[0024] As used herein, a "heterocycloalkyl group" refers to a cycloalkyl group in which some of the carbons are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen, and the heterocycloalkyl group may specifically contain an ether bond, an ester bond, a sulfonate ester bond, a carbonate, a lactone ring, a sultone ring, or a carboxylic anhydride moiety. As used herein, a "heterocycloalkylene group" refers to a cycloalkylene group in which some of the carbons are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen. As used herein, a "heterocycloalkoxy group" is defined as -OA 103 where A means a monovalent group having the formula 103 is a heterocycloalkyl group.

[0025] As used herein, an "alkenyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon double bonds. As used herein, an "alkenylene group" refers to a linear or branched, unsaturated aliphatic hydrocarbon divalent group containing one or more carbon-carbon double bonds. As used herein, the term "cycloalkenyl group" refers to a monovalent unsaturated cyclic hydrocarbon group containing one or more carbon-carbon double bonds. As used herein, the term "cycloalkenylene group" refers to a divalent unsaturated cyclic hydrocarbon group containing one or more carbon-carbon double bonds. As used herein, a "heterocycloalkenyl group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen. As used herein, a "heterocycloalkenylene group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0026] As used herein, "alkynyl group" means a linear or branched unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon triple bonds. As used herein, an "aryl group" refers to a monovalent group having a carbocyclic aromatic system, and specific examples include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, etc. As used herein, an "arylene group" refers to a divalent group having a carbocyclic aromatic system. As used herein, a "heteroaryl group" refers to a monovalent group having a heteroaromatic system, and specific examples include pyridinyl groups, pyrimidinyl groups, pyrazinyl groups, etc. As used herein, a "heteroarylene group" refers to a divalent group having a heteroaromatic system.

[0027] In the present specification, the term "substituent" refers to a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carbonyl group, a carboxylic acid group, an amino group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, a C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, 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 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group, or C 1 -C 20 Heteroarylthio groups; Deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether moiety, ester moiety, sulfonic acid ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, 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 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C substituted with heteroarylthio groups, and any combination thereof 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, 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 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C20 Heteroaryloxy group, C 1 -C 20 heteroarylthio groups; and any combination thereof.

[0028] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the description with reference to the drawings, substantially the same or corresponding components are given the same drawing numbers, and duplicated description thereof will be omitted. In the drawings, thicknesses of a plurality of layers and regions are exaggerated to clearly express them. In the drawings, thicknesses of some layers and regions are exaggerated for convenience of description. Meanwhile, the embodiments described below are merely examples, and various modifications are possible from such embodiments.

[0029] [Organometallic compound] The organometallic compound according to an exemplary embodiment is represented by any one of the following chemical formulas 1-1 to 1-4: [ka]

[0030] In the above Chemical Formulas 1-1 to 1-4, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), Q 11 ~Q 14 each independently represents a substituted or unsubstituted C 2 -C 30 Alkenyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 2 -C 30 Alkynyl group, substituted or unsubstituted C 6 -C 30 Aryl group, or substituted or unsubstituted C 1 -C30 is a heteroaryl group, b11 is 2 or 3; b12 to b14 each independently represent an integer of 0 to 3; R 11 ~R 14 each independently represents hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, a substituted or unsubstituted C 1 -C 30 Alkyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl groups, substituted or unsubstituted C 2 -C 30 Alkenyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 2 -C 30 Alkynyl group, substituted or unsubstituted C 6 -C 30 Aryl group, or substituted or unsubstituted C 1 -C 30 is a heteroaryl group, Q 11 ~Q 14 and R 11 ~R 14 two adjacent ones of the groups may be selectively bonded to each other to form a ring; Y 11 ~Y 13 are each independently O, O(C=O), S, S(C=O), NX 14 or N(C=O)X 14 and X 11 ~X 14 each independently represents a hydrogen atom, a deuterium atom, or a C which may optionally contain a heteroatom; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

[0031] 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.

[0032] M of the organometallic compound 11 The bond dissociation energy (calculated value) of the bond between and C is less than 30 kcal / mol. Without being limited to a particular theory, the b11 Q bonded to C 11 is M 11 The radicals generated during the decomposition of the bond between M and C can be stabilized. 11 The bond dissociation energy of the bond between Q and C is lower. 11 The double or triple bond contained in 11 Since it is directly bonded to the carbon (C) connected to M 11 The radical generated when the bond between and C is broken down is Q 11 It can be resonance stabilized by

[0033] For example, in the above chemical formulas 1-1 to 1-4, M 11 is In, Sn or Sb. Specifically, in the above Chemical Formulas 1-1 to 1-4, M 11 is Sn. For example, in the above chemical formulas 1-1 to 1-4, Q 11 ~Q 14 each independently represents deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, 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 groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof 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 groups, and C 1 -C 30 The aryl group may be selected from heteroaryl groups.

[0034] Specifically, in the above chemical formulas 1-1 to 1-4, Q 11 ~Q 14 each independently represents deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, 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 groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 2 -C 30 Alkynyl groups, and C 6 -C 30 The aryl group may be selected from the group consisting of aryl groups.

[0035] More specifically, in the above chemical formulas 1-1 to 1-4, Q 11 ~Q 14 are each independently deuterium, halogen, hydroxyl group, cyano group, nitro group, C 1 -C 10 Alkyl group, C 1 -C 10 Halogenated alkyl groups, C 1 -C 10 Alkoxy group, C 1 -C 10 Alkylthio group, C 1 -C 10 Halogenated alkoxy groups, C 1 -C10 Halogenated alkylthio groups, C 3 -C 10 Cycloalkyl groups, C 3 -C 10 Cycloalkoxy group, C 3 -C 10 The aryl group may be selected from ethenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl groups, substituted or unsubstituted with cycloalkylthio, phenyl, naphthyl, phenyloxy, naphthyloxy, phenylthio, naphthylthio, or any combination thereof.

[0036] For example, in the chemical formulae 1-1 to 1-4, b11 is 2 or 3, b12 is 2 or 3, b13 is 2 or 3, or b14 is 2 or 3. Alternatively, in the chemical formulae 1-1 to 1-4, b11 to b14 are each independently 2 or 3.

[0037] For example, in the above chemical formulas 1-1 to 1-4, R 11 ~R 14 are each independently hydrogen; deuterium; halogen; hydroxyl group; cyano group; nitro group; carboxylic acid group; and deuterium, halogen, hydroxyl group, cyano group, nitro group, amino group, carboxylic acid group, ether moiety, ester moiety, sulfonate ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof 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 groups, and C 1 -C 30 heteroaryl groups;

[0038] Specifically, in the above chemical formulas 1-1 to 1-4, R 11 ~R 14 are each independently hydrogen; deuterium; halogen; hydroxyl group; cyano group; nitro group; carboxylic acid group; and deuterium, halogen, hydroxyl group, cyano group, nitro group, amino group, carboxylic acid group, ether moiety, ester moiety, sulfonate ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C 1 -C 20 Alkyl group, C 1-C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, 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 groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof 1 -C 30 Alkyl group, C 3 -C 30 Cycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 2 -C 30 Alkynyl groups, and C 6 -C 30 aryl groups;

[0039] More specifically, in the above chemical formulas 1-1 to 1-4, R 11 ~R 14 are each independently hydrogen; deuterium; halogen; hydroxyl group; cyano group; nitro group; carboxylic acid group; and deuterium, halogen, hydroxyl group, cyano group, nitro group, C 1 -C 10 Alkyl group, C 1-C 10 Halogenated alkyl groups, C 1 -C 10 Alkoxy group, C 1 -C 10 Alkylthio group, C 1 -C 10 Halogenated alkoxy groups, C 1 -C 10 Halogenated alkylthio groups, C 3 -C 10 Cycloalkyl groups, C 3 -C 10 Cycloalkoxy group, C 3 -C 10 cycloalkylthio, phenyl, naphthyl, phenyloxy, naphthyloxy, phenylthio, naphthylthio, or any combination thereof, substituted or unsubstituted, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, cyclopentyl, cyclohexyl, ethenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl.

[0040] In one embodiment, in the chemical formulae 1-1 to 1-4, b11 is 2. Alternatively, in the chemical formulae 1-1 to 1-4, b11 to b14 are each independently 2.

[0041] In one embodiment, in the chemical formulas 1-1 to 1-4, [ka] is represented by any one of the following chemical formulas 2-11 to 2-14, [ka] is represented by any one of the following chemical formulas 2-21 to 2-30, [ka] is represented by any one of the following chemical formulas 2-31 to 2-40, [ka] is represented by any one of the following chemical formulas 2-41 to 2-50: [ka] [ka]

[0042] In the above Chemical Formulas 2-11 to 2-14 and 2-21 to 2-50, Q 11a ~Q 11f , Q 12a ~Q 12f , Q 13a ~Q 13f and Q 14a ~Q 14f are Q in chemical formulas 1-1 to 1-4, respectively. 11 Refer to the explanation regarding R 11c , R 11d , R 12a ~R 12f , R 13a ~R 13f and R 14a ~R 14f R in chemical formulas 1-1 to 1-4 11 Refer to the explanation regarding L 11 ~L 14 are each independently a single bond, O, S, or C. 1 -C 10 Alkylene group, or C 2 -C 10 is an alkenylene group, a11 to a14 are each independently selected from integers of 1 to 3; * indicates a bonding site with an adjacent atom. For example, in the above chemical formulas 2-11, 2-12, 2-21 to 2-26, 2-31 to 2-36, and 2-41 to 2-46, L 11 ~L 14are each independently a single bond or O.

[0043] For example, in the above chemical formulas 2-11, 2-12, 2-21 to 2-26, 2-31 to 2-36, and 2-41 to 2-46, a11 to a14 are each independently 1.

[0044] For example, in the above chemical formulas 2-11 to 2-14 and 2-21 to 2-50, Q 11a , Q 11b , Q 12a , Q 12b , Q 13a , Q 13b , Q 14a , Q 14b , R 12a , R 12b , R 13a , R 13b , R 14a and R 14b each independently represents a substituted or unsubstituted C 3 -C 30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 6 -C 30 Aryl group, or substituted or unsubstituted C 1 -C 30 It is a heteroaryl group.

[0045] In another embodiment, [ka] is represented by any one of the following chemical formulas 3-11 to 3-14, [ka] is represented by any one of the following chemical formulas 3-21 to 3-24, [ka] is represented by any one of the following chemical formulas 3-31 to 3-34, [ka] is represented by any one of the following chemical formulas 3-41 to 3-44: [ka]

[0046] In the chemical formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44, Q 11c , Q 11f , Q 12c , Q 12f , Q 13c , Q 13f , Q 14c and Q 14f are Q in chemical formulas 1-1 to 1-4, respectively. 11 Refer to the explanation regarding R 11c , R 11d , R 12c , R 12f , R 13c , R 13f , R 14c and R 14f R in chemical formulas 1-1 to 1-4 11 Refer to the explanation regarding L 11 ~L 14 are each independently a single bond, O, S, or C. 1 -C 10 Alkylene group, or C 2 -C 10 is an alkenylene group, a11 to a14 are each independently selected from integers of 1 to 3; A 31 and A 32 are each independently 3 -C 20 Cycloalkenyl group, C 3 -C 20 Heterocycloalkenyl group, C 6 -C 20 Aryl group, or C 1 -C 20 is a heteroaryl group, R31 ~R 36 each independently represents hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C 1 -C 10 Alkyl group, C 1 -C 10 Halogenated alkyl groups, C 1 -C 10 Alkoxy group, C 1 -C 10 Alkylthio group, C 1 -C 10 Halogenated alkoxy groups, C 1 -C 10 Halogenated alkylthio groups, C 3 -C 10 Cycloalkyl groups, C 3 -C 10 Cycloalkoxy group, C 3 -C 10 Cycloalkylthio group, C 6 -C 10 Aryl group, C 1 -C 10 Heteroaryl groups, C 6 -C 10 Aryloxy group, C 6 -C 10 Arylthio group, C 1 -C 10 Heteroaryloxy group, or C 1 -C 10 is a heteroarylthio group, b31 and b32 are each independently selected from integers of 1 to 8; * indicates a bonding site with an adjacent atom.

[0047] For example, in the chemical formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44, L 11 ~L 14 are each independently a single bond or O. For example, in the chemical formulae 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44, a11 to a14 are each independently 1.

[0048] For example, in the chemical formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44, A 31 and A 32 are each independently a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, a cyclohexadienyl group, a phenyl group, or a naphthyl group. For example, in the above chemical formulas 1-1 to 1-4, Y 11 ~Y 13 are each independently O, O(C=O), S or S(C=O).

[0049] For example, in the above chemical formulas 1-1 to 1-4, X 11 ~X 14 are each independently hydrogen; deuterium; and deuterium, halogen, hydroxy group, cyano group, nitro group, amino group, carboxylic acid group, ether moiety, ester moiety, sulfonic acid ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20aryl groups, or any combination thereof, substituted or unsubstituted, 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 3 -C 20 Cycloalkyl 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 20 Aryl groups, and C 1 -C 20 heteroaryl groups;

[0050] Specifically, in the above chemical formulas 1-1 to 1-4, X 11 ~X 14 are each independently hydrogen; deuterium; and deuterium, halogen, hydroxy group, amino group, carboxylic acid group, ether moiety, ester moiety, sulfonate ester moiety, carbonate moiety, amide moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 3 -C 20 Cycloalkyl groups, C 6 -C 20 aryl groups, or any combination thereof, substituted or unsubstituted, 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 3 -C 20 Cycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 3 -C 30 Heterocycloalkenyl group, C 2 -C30 Alkynyl group, C 6 -C 20 Aryl groups, and C 1 -C 20 heteroaryl groups;

[0051] More specifically, in the above chemical formulas 1-1 to 1-4, X 11 ~X 14 are each independently hydrogen; deuterium; and C which is unsubstituted or substituted with deuterium, halogen, methyl, ethyl, phenyl, naphthyl, or any combination thereof. 1 -C 20 Alkyl group, C 3 -C 20 Cycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 2 -C 30 Alkynyl groups, and C 6 -C 20 aryl groups;

[0052] In particular, in the above chemical formulas 1-1 to 1-4, X 11 ~X 14 may each independently be selected from hydrogen; deuterium; and methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, cyclopentyl, cyclohexyl, ethenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl, substituted or unsubstituted with deuterium, a halogen, methyl, ethyl, phenyl, naphthyl, or any combination thereof.

[0053] In one embodiment, the organometallic compound is represented by formula 1-2: [ka] is represented by any one of the chemical formulas 3-11 and 3-13; [ka] is represented by any one of the above chemical formulas 3-21 and 3-23.

[0054] In one embodiment, the organometallic compound represented by any one of the formulas 1-1 to 1-4 may be selected from the following Group I: <Group I> [ka] [ka] [ka]

[0055] Without being limited to a particular theory, the organometallic compound may generate radicals when exposed to heat and / or high energy radiation. 11 A radical is formed from the -carbon bond, and the radical reacts with the organometallic compound in an atmosphere containing water to form a chemical bond between the organometallic compound, which may change the physical properties of the organometallic compound, particularly its solubility in a developer.

[0056] In particular, the organometallic compound represented by any one of the chemical formulas 1-1 to 1-4 is 11 Since it always contains two or more, radical stability is improved, and as a result, M 11 The bond dissociation energy of the -carbon bond is lowered, which may improve the sensitivity to high-energy radiation, especially EUV.

[0057] For some of the organometallic compounds represented by any one of the above chemical formulas 1-1 to 1-4, the enthalpy change value due to homolysis of the Sn-C bond was calculated using density functional theory (DFT) calculations, and based on this, the bond dissociation energy of the Sn-C bond was defined and shown in Table 1 below.

[0058] [Table 1]

[0059] [ka]

[0060] The organometallic compounds may be prepared by any suitable method. The structure (composition) of the organometallic compound can be confirmed by FT-IR analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, UV analysis, single crystal X-ray structural analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC) analysis, size exclusion chromatography (SEC) analysis, thermal analysis, etc. Detailed confirmation methods are as described in the Examples.

[0061] [Resist composition] According to another aspect, there is provided a resist composition comprising the organometallic compound described above, which may have improved photosensitivity and / or storage stability properties. The resist composition has a change in solubility in a developer by exposure to high-energy rays. The resist composition is also a negative resist composition in which unexposed areas of the resist film are dissolved and removed to form a negative resist pattern.

[0062] Furthermore, the resist composition according to one embodiment may be for an alkaline development process that utilizes an alkaline developer in the development treatment during resist pattern formation, or may be for a solvent development process that utilizes a developer containing an organic solvent (hereinafter also referred to as an organic developer) in the development treatment.

[0063] The resist composition is of a non-chemically amplified type and therefore does not substantially contain a photoacid generator. The resist composition does not substantially contain any compound having a molecular weight of 1,000 or more other than the organometallic compound, since the physical properties of the organometallic compound change upon exposure to light.

[0064] In the resist composition, the organometallic compound is present in an amount of 0.1 to 100 parts by weight, specifically, 0.2 or more, 0.5 or more, 1 or more, 2 or more, and 90 or less, or 80 or less, per 100 parts by weight of the composition. If the above-mentioned range is satisfied, chemical bonds between the organometallic compounds are sufficiently formed while side reactions are suppressed, making it possible to provide a resist composition with improved sensitivity and / or resolution.

[0065] <Organic solvent> The resist composition may further contain an organic solvent. The organic solvent contained in the resist composition is not particularly limited as long as it can dissolve or disperse the organometallic compound and any optional components contained as necessary. The organic solvent may be used alone or in combination of two or more different organic solvents.

[0066] In one embodiment, the organic solvent may include a protic organic solvent, an aprotic organic solvent, or any combination thereof. In other embodiments, the organic solvent may be a mixture of aprotic and protic organic solvents.

[0067] The resist composition is substantially free of water, and the organic solvent is free of water. Specifically, the resist composition contains 3 wt % or less of water, and the organic solvent contains 3 wt % or less of water.

[0068] Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and hydrocarbon-based solvents.

[0069] More specifically, examples of the alcohol-based solvent 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, 2,6-dimethyl-4-heptanol, and the like. monoalcohol solvents such as ethanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; 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 of the polyhydric alcohol-containing ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

[0070] Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, and propylene glycol dimethyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0071] Examples of ketone solvents include chain ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, and acetophenone.

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

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

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

[0075] Examples of the hydrocarbon solvent 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.

[0076] Specifically, the organic solvent is selected from alcohol solvents, ketone solvents, ester solvents, and any combination thereof. More specifically, the organic solvent is selected from 4-methyl-2-pentanol (MIBC), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and any combination thereof.

[0077] <Optional ingredients> The resist composition may further include, as necessary, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0078] The resist composition may further contain a surfactant to improve coating properties, developability, etc. Specific examples of the surfactant include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. The surfactant may be a commercially available product or a synthetic product. Examples of commercially available surfactants include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75 and POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, FTOP EF303 and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE (registered trademark) F171, MEGAFACE F173, R40, R41 and R43 (manufactured by DIC Corporation), Fluorad (registered trademark) FC430 and Fluorad FC431 (manufactured by 3M), AsahiGuard AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105 and Surflon Examples include SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0079] The surfactant is contained in an amount of 0 to 20 parts by weight based on 100 parts by weight of the organometallic compound. One type of the surfactant may be used, or two or more different types may be mixed and used.

[0080] The method for producing the resist composition is not particularly limited, and for example, a method of mixing the organometallic compound and any optional components added as necessary in an organic solvent can be used. The temperature and time during mixing are not particularly limited. If necessary, filtration can be performed after mixing.

[0081] [Pattern formation method] Hereinafter, a pattern forming method according to an exemplary embodiment will be described in more detail with reference to Fig. 1 and Fig. 2A to Fig. 2C. Fig. 1 is a flow chart showing a pattern forming method according to an exemplary embodiment, and Fig. 2A to Fig. 2C are side cross-sectional views showing a pattern forming method according to an exemplary embodiment. Hereinafter, a pattern forming method using a negative resist composition will be specifically described as an example, but is not limited thereto.

[0082] 1, the method for forming a pattern includes a step of forming a resist film by applying a resist composition (S101), a step of exposing at least a part of the resist film to high energy radiation (S102), and a step of developing the exposed resist film using a developer (S103). The steps may be omitted or may be performed in a different order, if necessary.

[0083] First, a substrate 100 is provided. The substrate 100 can be, for example, a semiconductor substrate such as a silicon substrate or a germanium substrate, glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 can also include III-V compounds such as GaP, GaAs, GaSb, etc.

[0084] A resist composition can be applied to a substrate 100 to a desired thickness, specifically by a coating method, to form a resist film 110. If necessary, the resist film 110 can be heated (pre-baked (PB)) to remove any organic solvent remaining therein. Alternatively, the resist film 110 can be heated to generate radicals, and then the radicals can be chemically bonded by exposure to light to form crosslinks.

[0085] The coating method may be spin coating, dipping, roller coating, or other common coating methods. Among them, spin coating may be used, and the viscosity, concentration, and / or spin speed of the resist composition may be adjusted to form a resist film 110 of a desired thickness. Specifically, the thickness of the resist film 110 may be 10 nm to 300 nm. More specifically, the thickness of the resist film 110 may be 30 nm to 200 nm.

[0086] The lower limit of the pre-baking temperature is 60° C. or more, specifically 80° C. or more. The upper limit of the pre-baking temperature is 150° C. or less, specifically 140° C. or less. The lower limit of the pre-baking time is 5 seconds or more, specifically 10 seconds or more. The upper limit of the pre-baking time is 600 seconds or less, specifically 300 seconds or less.

[0087] Before applying the resist composition to the substrate 100, a layer to be etched (not shown) may be further formed on the substrate 100. The layer to be etched refers to a layer to which an image from a resist pattern is transferred and converted into a predetermined pattern. In one embodiment, the layer to be etched may be formed to include an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the layer to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicide nitride. In some embodiments, the layer to be etched may be formed to include a semiconductor material such as polysilicon.

[0088] In one embodiment, in order to maximize the efficiency of the resist, an anti-reflective coating may be further formed on the substrate 100. The anti-reflective coating may be an organic or inorganic anti-reflective coating.

[0089] In one embodiment, in order to reduce the influence of alkaline impurities and the like contained in the process, a protective film can be further provided on the resist film 100. Furthermore, when performing immersion exposure, in order to prevent direct contact between the immersion medium and the resist film 100, for example, a protective film for immersion can be provided on the resist film 100. Next, at least a portion of the resist film 110 can be exposed to high-energy rays. For example, high-energy rays that have passed through a mask 120 are irradiated onto at least a portion of the resist film 110. As a result, the resist film 110 can have an exposed portion 111 and a non-exposed portion 112.

[0090] Without being limited to a particular theory, it is believed that exposure to light generates radicals in the exposed areas 111, and chemical bonds are formed between the radicals, which may change the physical properties of the resist composition.

[0091] In some cases, the exposure is performed by irradiating a high-energy beam through a mask having a predetermined pattern using a liquid such as water as a medium. Examples of the high-energy beam include electromagnetic waves such as ultraviolet rays, far ultraviolet rays, 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. Irradiation with these high-energy beams is collectively called "exposure".

[0092] The exposure light source is a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or a F 2 A variety of lasers can be used, including those that emit laser light in the ultraviolet region such as an excimer laser (wavelength 157 nm), those that convert the wavelength of laser light from a solid-state laser light source (such as a YAG or semiconductor laser) and emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, and those that irradiate electron beams or extreme ultraviolet (EUV). During exposure, exposure is usually performed through a mask that corresponds to the desired pattern, but if the exposure light source is an electron beam, exposure can also be performed by direct writing without using a mask.

[0093] For example, when extreme ultraviolet rays are used as high-energy rays, the cumulative dose is 2000 mJ / cm 2 Specifically, 500 mJ / cm 2 In addition, when an electron beam is used as the high energy beam, the cumulative dose is 5000 μC / cm 2 Specifically, 1000μC / cm 2 Also the following:

[0094] Also, a post-exposure bake (PEB) can be performed after the exposure. The lower limit of the PEB temperature is 50° C. or more, specifically 80° C. or more. The upper limit of the PEB temperature is 250° C. or less, specifically 200° C. or less. The lower limit of the PEB time is 5 seconds or more, specifically 10 seconds or more. The upper limit of the PEB time is 600 seconds or less, specifically 300 seconds or less. A developer can then be used to develop the exposed resist film 110. The non-exposed areas 112 are washed away by the developer, while the exposed areas 111 remain.

[0095] Examples of the developer include an alkaline developer and a developer containing an organic solvent (hereinafter, also referred to as an "organic developer"). Examples of the development method include a dipping method, a paddle method, a spray method, and a dynamic administration method. The development temperature is, for example, 5° C. or higher and 60° C. or lower, and the development time is, for example, 5 seconds or higher and 300 seconds or lower. Examples of the alkaline developer include an alkaline aqueous solution in which 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) are dissolved. The alkaline developer may further contain a surfactant.

[0096] The lower limit of the content of the alkaline compound in the alkaline developer is 0.1% by weight or more, specifically 0.5% by weight or more, more specifically 1% by weight or more, and the upper limit of the content of the alkaline compound in the alkaline developer is 20% by weight or less, specifically 10% by weight or less, more specifically 5% by weight or less.

[0097] The organic solvent contained in the organic developer may be, for example, the same as the organic solvent exemplified in the <Organic Solvent> section of the [Resist Composition]. Specifically, nBA (n-butyl acetate), PGME (propylene glycol methyl ether), PGMEA (propylene glycol methyl ether acetate), GBL (γ-butyrolactone), IPA (isopropanol), etc. may be used as the organic developer. The organic developer may further contain an organic acid such as acetic acid, formic acid, or citric acid.

[0098] The lower limit of the content of the organic solvent in the organic developer is 80% by weight or more, specifically 90% by weight or more, more specifically 95% by weight or more, and even more specifically 99% by weight or more. The organic developer may contain a surfactant. The organic developer may contain a small amount of water. During development, the organic developer may be replaced with a different type of solvent to stop the development.

[0099] The resist pattern after development can be further washed. As the washing liquid, ultrapure water, a rinse liquid, etc. can be used. As the rinse liquid, there is no particular limitation as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. For example, the rinse liquid may be an alcohol-based solvent or an ester-based solvent. After washing, the rinse liquid remaining on the substrate and the pattern can be removed. In addition, when ultrapure water is used, the water remaining on the substrate and the pattern can be removed. The developer may be used alone or in combination of two or more kinds.

[0100] After forming the resist pattern as described above, the resist pattern is etched to obtain a patterned wiring board. The etching method is carried out by a known method such as dry etching using plasma gas, or wet etching using an alkaline solution, a cupric chloride solution, a ferric chloride solution, or the like.

[0101] After forming the resist pattern, plating can be carried out. The plating method is not particularly limited, but examples thereof include copper plating, solder plating, nickel plating, and gold plating.

[0102] The remaining resist pattern after etching can be peeled off with an organic solvent. Examples of such organic solvents include, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), etc. The peeling method includes, but is not limited to, a dipping method, a spray method, etc. In addition, the wiring board on which the resist pattern is formed can also be a multi-layer wiring board and can have a small diameter through hole.

[0103] In one embodiment, the wiring board can also be formed by a method in which a resist pattern is formed, a metal is evaporated in a vacuum, and then the resist pattern is dissolved in a solution, that is, a lift-off method.

[0104] 12A-12E are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. 12A, before forming the resist film 110 on the substrate 100, a material layer 130 may be formed on the substrate 100. The resist film 110 may be formed on top of the material layer 130. The material layer 130 may include an insulating material (e.g., silicon oxide, silicon nitride), a semiconductor material (e.g., silicon), or a metal (e.g., copper). In some embodiments, the material layer 130 may also have a multi-layer structure. The material of the material layer 130 is different from the material of the substrate 100.

[0105] As shown in FIG. 12B, the resist film 110 undergoes a pre-exposure bake process and is exposed to high energy rays through a mask 120, after which the resist film 110 includes an exposed region 111 and a non-exposed region 112. 12C, the exposed resist film 110 is developed using a developer (e.g., a developer). The exposed portion 111 is washed away by the developer, and the non-exposed portion 112 is not washed away by the developer and remains. As shown in FIG. 12D, the exposed portions of the material layer 130 may be etched using the resist pattern 110 as a mask to form a material pattern 135 on the substrate 100. As shown in FIG. As shown in FIG. 12E, the resist pattern 110 may be removed.

[0106] 13A-13E are cross-sectional side views illustrating a method of forming a semiconductor device according to one embodiment. 13A, a gate dielectric 505 (e.g., silicon oxide) is formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (e.g., doped polysilicon) is formed on the gate dielectric 505. A hard mask layer 520 is formed on the gate layer 515. 13B, a resist pattern 540b may be formed on the hard mask layer 520. The resist pattern 540b may be formed using a resist composition according to an embodiment of the present invention. The resist composition may include an organic solvent.

[0107] As shown in FIG. 13C, the gate layer 515 and the gate dielectric 505 may be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a. As shown in FIG. 13D, a spacer layer may be formed on the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layer may be formed using a deposition process (e.g., CVD). The spacer layer may be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After the spacers 535a are formed, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0108] 13E, an interlayer insulating film 560 (e.g., oxide) may be formed on the substrate 500 to cover the gate electrode pattern 515a, the gate dielectric pattern 505a, and the spacer 535a. Then, electrical contacts 570a, 570b, and 570c connected to the gate electrode 515a and the S / D regions are formed in the interlayer insulating film 560. The electrical contacts 570a, 570b, and 570c are formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating film 560 and the electrical contacts 570a, 570b, and 570c. Although FIGS. 13A to 13E show an example of forming a transistor, the present invention is not limited thereto.

[0109] The resist composition according to one or more embodiments can be used in patterning processes to form other types of semiconductor devices. The resist composition may include an organic solvent. 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 only the following examples.

[0110] [Example] Synthesis Example 1: Synthesis of OM-A [ka]

[0111] (1) Synthesis of A-2 N 2Diphenylmethane (4.89g, 29.1mmol) was placed in a substituted two-necked round-bottom flask and diluted with THF (50ml). n-BuLi (2.5M in hexane, 29.1mmol) was added dropwise at -78°C, and the mixture was stirred at 0°C for 0.5 hours. Dichlorodiphenylstannane (5g, 14.5mmol) was placed in a vial and diluted with THF (28ml, total THF (58ml, 0.25M)). The solution in 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, filtered through silica / celite, and purified by column chromatography (ethyl acetate (EA): n-hexane (EA 5v%) to obtain A-2 (6.8g, 77%).

[0112] (2) Synthesis of A-1 A-2 (6.2 g, 10.2 mmol) was placed in a round-bottom flask and N 2 After dilution with dichloromethane (102 ml, 0.1 M), the solution was diluted with 2 M HCl in Et 2 O solution (15.3 ml, 30.67 mmol) was added dropwise. After stirring at -78°C for 1 hour, the temperature was raised to room temperature and reacted again for 12 hours. After removing the solvent, the precipitate was washed with methyl t-butyl ether:n-hexane (5 ml:100 ml) and then dried under vacuum to obtain A-1 (4.3 g, 80%).

[0113] (3) Synthesis of OM-A A-1 (1.0 g, 1.91 mmol) was placed in a round-bottom flask and N 2 After dilution with acetone (19 ml, 0.1 M), sodium acetate (0.31 g, 3.82 mmol) was added at 0°C. After reaction at 0°C for 16 hours, the mixture was filtered using Celite. After removing the solvent, the mixture was recrystallized (methyl t-butyl ether: n-hexane = 3 ml: 30 ml). After filtering, the precipitate was dried under vacuum to obtain OM-A (0.54 g, 50%).

[0114] Synthesis Example 2: Synthesis of OM-B [ka]

[0115] (1) Synthesis of B-2 N 2 Fluorene (8.31g, 50.0mmol) was placed in a substituted two-necked round-bottom flask and diluted with THF (30ml). n-BuLi (2.5M in hexane, 20ml, 50mmol) was added dropwise at -78℃, and then stirred at 0℃ for 0.5 hours. Dichlorodiphenylstannane (8.60g, 25.0mmol) was placed in a vial and diluted with THF (50ml, total THF 100ml (0.25M)). The solution in the vial was added dropwise to the round-bottom flask at -78℃, and then stirred for 0.5 hours, then heated to room temperature and stirred again for 0.5 hours. After confirming the completion of the reaction, the solvent was removed, filtered through silica / celite, and purified by column chromatography (dichloromethane (DCM):n-hexane (DCM 10v%) to obtain B-2 (12.1g, 80%).

[0116] (2) Synthesis of B-1 B-2 (12.0 g, 20.0 mmol) was placed in a round-bottom flask and N 2 After dilution with dichloromethane (200 ml, 0.1 M), the solution was diluted with 2 M HCl in Et 2 O solution (30 ml, 60 mmol) was added dropwise. After stirring at -78°C for 1 hour, the temperature was raised to room temperature and reacted again for 12 hours. After removing the solvent, the precipitate was washed with n-hexane and then dried under vacuum to obtain B-1 (8.8 g, 85%).

[0117] (3) Synthesis of OM-B B-1 (1.5 g, 2.88 mmol) was placed in a round-bottom flask and N 2After dilution with acetone (29 ml, 0.1 M), sodium propionate (0.55 g, 5.77 mmol) was added at 0°C. After reaction at 0°C for 16 hours, the mixture was filtered using Celite. After removing the solvent, the mixture was recrystallized (dichloromethane:n-hexane=5 ml:100 ml). After filtering, the mixture was dried under vacuum to obtain OM-B (1.30 g, 76%).

[0118] Evaluation example: Thin film development evaluation Specifically, the organometallic compounds synthesized in Synthesis Examples 1 and 2 were dissolved in the casting solvent shown in Table 1 below at 2 wt %. A silicon wafer having a diameter of 4 inches was heated in O 2 After the plasma treatment, the casting solution was spin-coated at 1200 rpm for 1 minute and then dried (PAB) at 120°C for 1 minute to produce a film with an initial thickness as shown in Table 1 below. Next, a 3.5 mm thick zig (4 x 4) with rectangular holes (1 cm x 1 cm) was placed on top of the film, and 0 to 50 mJ / cm of DUV with a wavelength of 254 nm was applied to each hole. 2 or 0-100mJ / cm 2 The film was exposed to light at a dose of 100 nm and dried (PEB) at 120 to 160° C. for 1 minute. The dried film was immersed in a PGMEA solution in which 2% by weight of acetic acid was dissolved as a developer at 25° C. for 60 seconds, after which the remaining film thickness was measured and shown in Table 2 below, and in FIGS. 9A to 9E, 10A, and 11A to 11C. In FIGS. 9A to 9E, 10A, and 11A to 11C, "as-coated" is reference data for a sample that was not treated with a developer, and "after develop" is data for a sample that was treated with a developer. In addition, in order to compare the effect of the ligand, E of Examples 1-3, 2-1, and Comparative Examples 1 to 3 was measured. th and E 1 are compared and shown again in Tables 3 and 4 below.

[0119] [Table 2]

[0120] [ka]

[0121] [Table 3]

[0122] [Table 4]

[0123] In Tables 2 to 4, E th means the exposure dose at which the thin film begins to harden, and E 1 means the exposure dose at which the film thickness does not increase any more.

[0124] Referring to Table 2, it can be seen that Examples 1-1 and 1-2 show the same level of contrast as Examples 1-4 and 1-5. In other words, it can be seen that the resist composition including the organometallic compound according to one embodiment of the present invention is advantageous in appropriately adjusting the temperature of the pattern formation process as desired.

[0125] Referring to Table 2, E of Examples 1-1 to 1-5 and 2-1 th and E 1 is E of Comparative Examples 1 to 3 th and E 1 From this, it can be seen that the resist compositions of Examples 1-1 to 1-5 and 2-1 have improved photosensitivity compared to the resist compositions of Comparative Examples 1 to 3.

[0126] Referring to Tables 3 and 4, the organometallic compounds according to one embodiment of the present invention [ka] As the structure of the ligand represented by E th and E 1You can see how Q changes when it is 2 or more. 11 In Examples 1-3, which used an organometallic compound having the formula th and E 1 Similarly, Example 2-1 also showed a significantly reduced E th and E 1 It can be confirmed that the above equation shows the following.

Claims

1. An organometallic compound represented by any one of the following chemical formulas 1-1 to 1-4: 【Chemistry 1】 In the above Chemical Formulas 1-1 to 1-4, M １１ is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po); Q １１ ~Q １４ each independently represents a substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyl group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ６ -C ３０ An aryl group, or a substituted or unsubstituted C １ -C ３０ is a heteroaryl group, b11 is 2 or 3; b12 to b14 each independently represent an integer of 0 to 3; R １１ ~R １４ are each independently hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, a substituted or unsubstituted C １ -C ３０ Alkyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C ３ -C ３０ Heterocycloalkyl groups, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyl group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ６ -C ３０ An aryl group, or a substituted or unsubstituted C １ -C ３０ is a heteroaryl group, Q １１ ~Q １４ and R １１ ~R １４ two adjacent groups may be optionally bonded to each other to form a ring; Y １１ ~Y １３ are each independently O, O(C=O), S, S(C=O), NX １４ Or N(C=O)X １４ and X １１ ~X １４ each independently represents hydrogen, deuterium, or C which may optionally contain a heteroatom; １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

2. M of the organometallic compound １１ 2. The organometallic compound of claim 1, wherein the bond dissociation energy (calculated value) of the bond between and C is 30 kcal / mol or less.

3. M １１ The organometallic compound of claim 1 , wherein is In, Sn or Sb.

4. Q １１ ~Q １４ each independently represents deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halogenated alkoxy group, C １ -C ２０ Halogenated alkylthio groups, C ３ -C ２０ Cycloalkyl group, 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 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 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 groups, and C １ -C ３０ heteroaryl groups; R １１ ~R １４ are each independently hydrogen; deuterium; a halogen; a hydroxyl group; a cyano group; a nitro group; a carboxylic acid group; and deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonate ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halogenated alkoxy group, C １ -C ２０ Halogenated alkylthio groups, C ３ -C ２０ Cycloalkyl group, 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 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; １ -C ３０ Alkyl group, C ３ -C ３０ Cycloalkyl group, C ３ -C ３０ Heterocycloalkyl group, 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 groups, and C １ -C ３０ 2. The organometallic compound of claim 1, wherein the organometallic compound is selected from the group consisting of: a heteroaryl group;

5. b11 is 2 or 3; b12 is 2 or 3; b13 is 2 or 3; or The organometallic compound of claim 1 , wherein b14 is 2 or 3. 【Request 6】 【Chemical 2】 is represented by any one of the following chemical formulas 2-11 to 2-14, 【Chemistry 3】 is represented by any one of the following chemical formulas 2-21 to 2-30, 【Chemistry 4】 is represented by any one of the following chemical formulas 2-31 to 2-40, 【Chemistry 5】 The organometallic compound according to claim 1, which is represented by any one of the following chemical formulas 2-41 to 2-50: 【Chemistry 6A】 【Chemistry 6B】 In the above Chemical Formulas 2-11 to 2-14 and 2-21 to 2-50, Q １１ａ ~Q １１ｆ , Q １２ａ ~Q １２ｆ , Q １３ａ ~Q １３ｆ and Q. １４ａ ~Q １４ｆ represents Q in chemical formulas 1-1 to 1-4, respectively. １１ is the same as the definition of R １１ｃ , R １１ｄ , R １２ａ ~R １２ｆ , R １３ａ ~R １３ｆ and R １４ａ ~R １４ｆ R in Chemical Formulas 1-1 to 1-4 １１ is the same as the definition of L １１ ~L １４ are each independently a single bond, O, S, or C. １ -C １０ Alkylene group, or C ２ -C １０ is an alkenylene group, a11 to a14 are each independently selected from integers of 1 to 3; * indicates a bonding site with an adjacent atom.

7. Q １１ａ , Q １１ｂ , Q １２ａ , Q １２ｂ , Q １３ａ , Q １３ｂ , Q １４ａ , Q １４ｂ , R １２ａ , R １２ｂ , R １３ａ , R １３ｂ , R １４ａ and R １４ｂ each independently represents a substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyl group, substituted or unsubstituted C ６ -C ３０ An aryl group, or a substituted or unsubstituted C １ -C ３０ 7. The organometallic compound of claim 6, which is a heteroaryl group. 【Request 8】 【Chemical 7】 is represented by any one of the following chemical formulas 3-11 to 3-14, 【Chemistry 8】 is represented by any one of the following chemical formulas 3-21 to 3-24, 【Chemistry 9】 is represented by any one of the following chemical formulas 3-31 to 3-34, 【Chemistry 10】 The organometallic compound according to claim 1, which is represented by any one of the following chemical formulas 3-41 to 3-44: 【Chemistry 11】 In the chemical formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44, Q １１ｃ , Q １１ｆ , Q １２ｃ , Q １２ｆ , Q １３ｃ , Q １３ｆ , Q １４ｃ and Q. １４ｆ represents Q in chemical formulas 1-1 to 1-4, respectively. １１ is the same as the definition of R １１ｃ , R １１ｄ , R １２ｃ , R １２ｆ , R １３ｃ , R １３ｆ , R １４ｃ and R １４ｆ R in Chemical Formulas 1-1 to 1-4 １１ is the same as the definition of L １１ ~L １４ are each independently a single bond, O, S, or C. １ -C １０ Alkylene group, or C ２ -C １０ is an alkenylene group, a11 to a14 are each independently selected from integers of 1 to 3; A ３１ and A ３２ are each independently ３ -C ２０ Cycloalkenyl group, C ３ -C ２０ Heterocycloalkenyl group, C ６ -C ２０ Aryl group, or C １ -C ２０ is a heteroaryl group, R ３１ ~R ３６ are each independently hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, １ -C １０ Alkyl group, C １ -C １０ Halogenated alkyl group, C １ -C １０ Alkoxy group, C １ -C １０ Alkylthio group, C １ -C １０ Halogenated alkoxy group, C １ -C １０ Halogenated alkylthio groups, C ３ -C １０ Cycloalkyl group, C ３ -C １０ Cycloalkoxy group, C ３ -C １０ Cycloalkylthio group, C ６ -C １０ Aryl group, C １ -C １０ Heteroaryl group, C ６ -C １０ Aryloxy group, C ６ -C １０ Arylthio group, C １ -C １０ Heteroaryloxy group, or C １ -C １０ is a heteroarylthio group, b31 and b32 are each independently selected from integers of 1 to 8; * indicates a bonding site with an adjacent atom.

9. X １１ ~X １４ are each independently hydrogen; deuterium; and deuterium, halogen, a hydroxy group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halogenated alkoxy group, C １ -C ２０ Halogenated alkylthio groups, C ３ -C ２０ Cycloalkyl group, C ３ -C ２０ Cycloalkoxy group, C ３ -C ２０ Cycloalkylthio group, C ６ -C ２０ aryl groups, or any combination thereof, substituted or unsubstituted, １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, 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 ２０ Aryl groups, and C １ -C ２０ 2. The organometallic compound of claim 1, wherein the organometallic compound is selected from the group consisting of: a heteroaryl group;

10. The organometallic compound represented by any one of the chemical formulas 1-1 to 1-4 is represented by the chemical formula 1-2, 【Chemistry 12】 is represented by any one of the following chemical formulas 3-11 and 3-13, 【Chemistry 13】 The organometallic compound according to claim 1, which is represented by any one of the following chemical formulas 3-21 and 3-23: 【Chemistry 14】 In the above chemical formulas 3-11, 3-13, 3-21 and 3-23, R １１ｃ , R １１ｄ , R １２ｃ , R １２ｆ and R １３ｃ R in Chemical Formulas 1-1 to 1-4 １１ is the same as the definition of L １１ and L １２ are each independently a single bond, O, S, or C. １ -C １０ Alkylene group, or C ２ -C １０ is an alkenylene group, a11 and a12 are each independently selected from an integer of 1 to 3; A ３１ and A ３２ are each independently ３ -C ２０ Cycloalkenyl group, C ３ -C ２０ Heterocycloalkenyl group, C ６ -C ２０ Aryl group, or C １ -C ２０ is a heteroaryl group, R ３１ ~R ３６ are each independently hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxylic acid group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, １ -C １０ Alkyl group, C １ -C １０ Halogenated alkyl group, C １ -C １０ Alkoxy group, C １ -C １０ Alkylthio group, C １ -C １０ Halogenated alkoxy group, C １ -C １０ Halogenated alkylthio groups, C ３ -C １０ Cycloalkyl group, C ３ -C １０ Cycloalkoxy group, C ３ -C １０ Cycloalkylthio group, C ６ -C １０ Aryl group, C １ -C １０ Heteroaryl group, C ６ -C １０ Aryloxy group, C ６ -C １０ Arylthio group, C １ -C １０ Heteroaryloxy group, or C １ -C １０ is a heteroarylthio group, b31 and b32 are each independently selected from integers of 1 to 8; * indicates a bonding site with an adjacent atom.

11. The organometallic compound according to claim 1, wherein the organometallic compound represented by any one of the chemical formulas 1-1 to 1-4 is selected from the following Group I: <Group I> 【Chemical 15A】 【Chemistry 15B】 。

12. A resist composition comprising the organometallic compound according to claim 1 .

13. The resist composition of claim 12 which is substantially free of a photoacid generator.

14. The resist composition according to claim 12, which is substantially free of compounds having a molecular weight of 1,000 or more.

15. The resist composition of claim 12 further comprising an organic solvent.

16. 16. The resist composition of claim 15, wherein the organic solvent comprises a protic organic solvent, an aprotic organic solvent, or any combination thereof.

17. A step of forming a resist film by applying the resist composition according to claim 12; exposing at least a portion of the resist film to high energy radiation; and developing the exposed resist film using a developer.

18. 20. The method of claim 17, wherein the exposing step is performed by irradiating with ultraviolet light, deep ultraviolet light (DUV), extreme ultraviolet light (EUV), X-rays, gamma rays, electron beams (EB), and / or alpha rays.

19. The pattern formation method according to claim 17 , wherein a chemical bond is formed between the organometallic compounds by exposing the resist film to light.

20. the exposed resist film includes an exposed portion and a non-exposed portion, The pattern formation method according to claim 17 , wherein the unexposed portion is removed in the developing step.

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