Organometallic compound, resist composition containing the same, and patterning process using the same

Abstract

To provide an organometallic compound, a resist composition containing the same, and a pattern forming method using the same.SOLUTION: Provided are an organometallic compound represented by the following Chemical Formula 1, a resist composition including the same, and a method of forming a pattern using the same: M11 (R x) n (R y) (m-n) (Chemical Formula 1) In Chemical Formula 1, M11, R x, R y, n, and m are the same as described above.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] Resists whose physical properties change in response to light are used to form fine patterns during semiconductor manufacturing. Among them, chemically amplified resists have been widely used. Chemically amplified resists enable patterning by forming an acid from a photoacid generator in response to light. The acid reacts with the base resin, changing the solubility of the base resin in a developer.

[0003] However, in the case of chemically amplified resists, as the formed acid diffuses into unexposed areas, problems such as reduced pattern uniformity and increased surface roughness occur. Furthermore, as semiconductor processes become increasingly miniaturized, it is no longer easy to control acid diffusion, 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, the required exposure dose remains high. Summary of the Invention [Problem to be solved by the invention]

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

[0006] In one aspect, there is provided an organometallic compound represented by Formula 1: M11 (R x ) n (R y ) (m-n) (chemical formula 1) In the above Chemical Formula 1, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po); R x *-X1-(L1) a1 -[Y1-Z1] c1 and R y is *-(L2) a2 -(R1) b1 and n is an integer from 1 to 6, m is an integer from 1 to 6; mn is 0 or greater, Multiple R's x may be the same or different from each other, Multiple R's y may be the same 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 OC(=O), C(=O)O, OS(=O)2, or S(=O)2O; Z1 is *-C(R2)(R3)(R4), *-C(R2)=N(R3), C(R2)(R3)=N-*, or *-N(R2)(R3); L1 and L2 each independently represent a C1-C 30 is a linear, branched, or cyclic divalent hydrocarbon radical of a1 and a2 each independently represent an integer of 0 to 4, R1 is a C1-C1 group which may optionally contain heteroatoms. 30 two adjacent groups among the plurality of R1 can selectively bond to each other to form a fused ring; R2 to R4 are each independently hydrogen, deuterium, halogen, cyano group, hydroxy group, or C1-C10 alkyl group which may optionally contain a heteroatom. 30 and two adjacent groups among the plurality of R2 to R4 can selectively bond to each other to form a fused ring. b1 and c1 each independently represent an integer of 1 to 4, * indicates a bonding site with an adjacent atom.

[0007] Another aspect provides a resist composition comprising the organometallic compound described above. In yet another aspect, there is provided a pattern formation method including the steps of applying the resist composition described above to form a resist film, exposing at least a portion of the resist film to high-energy rays, and developing the exposed resist film using a developer. [Effects of the Invention]

[0008] Embodiments of the present invention can provide resist compositions that have improved sensitivity and provide patterns with improved resolution. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a flowchart 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] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3B] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3C] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3D] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3E] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4A] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4B] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4C] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4D] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4E] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 5A] 1 is a graph showing the change in film thickness after development depending on the dose in Example 1-1. [Figure 5B] 1 is a graph showing changes in film thickness after development depending on the dose in Comparative Examples 1-1 and 1-2. [Figure 5C] 1 is a graph showing changes in film thickness after development depending on the dose in Comparative Examples 1-3 and 1-4. [Figure 5D] 1 is a graph showing changes in film thickness after development depending on the dose in Comparative Examples 1-5 and 1-6. [Figure 6A] 1 is a diagram showing the relative size of the film remaining rate of Example 1-1 and the film remaining rate of Comparative Example 1-1. [Figure 6B] 1 is a diagram showing the relative size of the film remaining rate of Example 1-1 and the film remaining rate of Comparative Example 1-3. [Figure 6C] 1 is a diagram showing the relative size of the film remaining rate of Example 1-1 and the film remaining rate of Comparative Example 1-5. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention can be modified in various ways and can have various embodiments, and 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 the specific embodiments, and it should be understood that the present invention includes all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention. When a detailed description of known technology related to the description of the present invention is considered to obscure the gist of the present invention, the detailed description will be omitted.

[0011] Terms such as "first," "second," and "third" are used to describe various components, but are used only to distinguish one component from another, and do not limit the order, type, etc. of the components. In this specification, when a layer, film, region, plate, or other part is described as being "on top" or "above" another part, it includes not only parts that are in contact with each other and are immediately above, below, to the left, or right, but also parts that are not in contact with each other and are immediately above, below, to the left, or right.

[0012] The singular includes the plural 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 stated 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.

[0013] 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, and also includes X and Y.

[0014] As used herein, "C x -C y" means that the number of carbon atoms constituting the substituent is x to y. For example, "C1-C6" means that the number of carbon atoms constituting the substituent is 1 to 6, and "C6-C 20 " means that the number of carbon atoms constituting the substituent is 6 to 20.

[0015] 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 groups); 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 hydrogen atoms are replaced by moieties containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, or some carbon atoms 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, sulfonate ester bonds, carbonates, lactone rings, sultone rings, carboxylic anhydride moieties, or haloalkyl moieties.

[0016] As used herein, the term "divalent hydrocarbon group" refers to a divalent residue in which one hydrogen atom of the monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. Examples of divalent hydrocarbon groups include linear or branched alkylene groups, cycloalkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, and groups in which some carbon atoms are replaced by heteroatoms.

[0017] As used herein, "alkyl group" refers to a linear or branched saturated aliphatic hydrocarbon monovalent group, and specific examples include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-amyl group, a hexyl group, etc. As used herein, "alkylene group" refers to a linear or branched saturated aliphatic hydrocarbon divalent group, and specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, etc.

[0018] As used herein, the term "halogenated alkyl group" refers to an alkyl group in which one or more substituents are substituted with halogen, and specific examples include CF. Here, halogen is F, Cl, Br, or I. As used herein, an "alkoxy group" is defined as -OA. 101 where A 101 is an alkyl group. Specific examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.

[0019] As used herein, an "alkylthio group" is defined as -SA 101 where A 101 is an alkyl group. As used herein, the term "halogenated alkoxy group" refers to an alkoxy group in which one or more hydrogen atoms have been substituted with halogen, and specific examples include -OCF3.

[0020] As used herein, the term "halogenated alkylthio group" refers to an alkylthio group in which one or more hydrogen atoms have been substituted with halogen, and specific examples include -SCF3. As used herein, the term "cycloalkyl group" refers to a monovalent saturated hydrocarbon ring 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 fused polycyclic groups such as a norbornyl group and an adamantyl group. As used herein, the term "cycloalkylene group" refers to a divalent saturated hydrocarbon ring 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, and a dicyclohexylmethylene group.

[0021] As used herein, a "cycloalkoxy group" is defined as -OA. 102 where A 102 is a cycloalkyl group. Specific examples thereof include a cyclopropoxy group, a cyclobutoxy group, and the like. As used herein, a "cycloalkylthio group" refers to a group represented by -SA 102 where A 102 is a cycloalkyl group.

[0022] As used herein, a "heterocycloalkyl group" refers to a cycloalkyl group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen, and the heterocycloalkyl group specifically includes an ether bond, an ester bond, a sulfonate ester bond, a carbonate, a lactone ring, a sultone ring, or a carboxylic acid anhydride moiety. As used herein, a "heterocycloalkylene group" refers to a cycloalkylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0023] As used herein, a "heterocycloalkoxy group" is defined as -OA.103 where A 103 is a heterocycloalkyl group. As used herein, the term "alkenyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon double bonds. As used herein, the term "alkenylene group" refers to a linear or branched, unsaturated aliphatic hydrocarbon divalent group containing one or more carbon-carbon double bonds.

[0024] As used herein, a "cycloalkenyl group" refers to a monovalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds. As used herein, a "cycloalkenylene group" refers to a divalent unsaturated hydrocarbon ring 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.

[0025] As used herein, the term "alkynyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon triple bonds. As used herein, the term "aryl group" refers to a monovalent group having a carbocyclic aromatic system, and specific examples include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, etc. As used herein, the term "arylene group" refers to a divalent group having a carbocyclic aromatic system.

[0026] As used herein, the term "heteroaryl group" refers to a monovalent group having a heterocyclic aromatic system, and specific examples include pyridinyl groups, pyrimidinyl groups, pyrazinyl groups, etc. As used herein, the term "heteroarylene group" refers to a divalent group having a heterocyclic aromatic system.

[0027] As used herein, a "substituent" is any of 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, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy group, or C1-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, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy groups, C1-C 20 C-C substituted with heteroarylthio groups, and any combination thereof 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy groups, and C1-C 20 heteroarylthio groups; or 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 identical or corresponding components are given the same drawing numbers, and redundant description thereof will be omitted. In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, in the drawings, thicknesses of some layers and regions are exaggerated for convenience of explanation. Meanwhile, the embodiments described below are merely examples, and various modifications are possible from such embodiments.

[0029] [Organometallic compound] An organometallic compound according to an exemplary embodiment is represented by Formula 1: M 11 (R x ) n (R y ) (m-n) (chemical formula 1) In the above Chemical Formula 1, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po); R x *-X1-(L1) a1 -[Y1-Z1] c1 and R y is *-(L2) a2 -(R1) b1 and n is an integer from 1 to 6, m is an integer from 1 to 6; mn is 0 or greater, Multiple R's x may be the same or different from each other, Multiple R's y may be the same 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 OC(=O), C(=O)O, OS(=O)2, or S(=O)2O; Z1 is *-C(R2)(R3)(R4), *-C(R2)=N(R3), C(R2)(R3)=N-*, or *-N(R2)(R3); L1 and L2 each independently represent a C1-C 30 is a linear, branched, or cyclic divalent hydrocarbon radical of a1 and a2 each independently represent an integer of 0 to 4, R1 is a C1-C1 group which may optionally contain heteroatoms. 30 two adjacent groups among the plurality of R1 can selectively bond to each other to form a fused ring; R2 to R4 are each independently hydrogen, deuterium, halogen, cyano group, hydroxy group, or C1-C10 alkyl group which may optionally contain a heteroatom. 30and two adjacent groups among the plurality of R2 to R4 can selectively bond to each other to form a fused ring. b1 and c1 each independently represent an integer of 1 to 4, * indicates a bonding site with an adjacent atom.

[0030] The organometallic compound has a molecular weight of 3000 g / mol or less, specifically, 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 formula 1, m is M 11 indicates the valence of the atom. For example, in the above Chemical Formula 1, n is an integer of 1 to 4. For example, in the above Chemical Formula 1, m is an integer of 1 to 4.

[0031] In one embodiment, in Formula 1, n is an integer of 1 to 4, m is an integer of 1 to 4, and M 11 is Sn. In the above formula 1, M 11 and R x The bond with M 11 -Oxygen single bond or M 11 Specifically, in the above-mentioned Chemical Formula 1, M 11 and R x The bond with M 11 -oxygen single bond. In the above formula 1, M 11 and R y The bond with M 11 -carbon single bond.

[0032] For example, in the above Chemical Formula 1, X1 is O, OC(=O), or C(=O)O. For example, in the above Chemical Formula 1, Y1 is OC(=O), C(=O)O, OS(=O)2, or S(=O)2O. For example, in the above formula 1, L1 and L2 are each independently a substituted or unsubstituted C1-C 30 Alkylene groups, substituted or unsubstituted C3-C 30 Cycloalkylene groups, substituted or unsubstituted C3-C 30 Heterocycloalkylene groups, 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 an arylene group, or a substituted or unsubstituted C1-C 30 It is a heteroarylene group.

[0033] Specifically, in the above Chemical Formula 1, L1 and L2 each independently represent deuterium, a halogen, a cyano group, a nitro group, a hydroxy group, a thiol group, an amino group, a carboxylic acid group, an ether moiety, a thioether moiety, a carbonyl moiety, an ester moiety, a phosphonate moiety, a sulfonate moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, a C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C1-C 20 Heteroaryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryloxy groups, C1-C 20 C1-C substituted or unsubstituted heteroarylthio groups, or any combination thereof30 Alkylene group, C3-C 30 Cycloalkylene group, C3-C 30 Heterocycloalkylene groups, C2-C 30 Alkenylene group, C3-C 30 Cycloalkenylene group, C3-C 30 Heterocycloalkenylene group, C6-C 30 Arylene groups, and C1-C 30 heteroarylene groups.

[0034] More specifically, in the above Chemical Formula 1, L1 and L2 are each independently a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a C1-C 20 Alkyl groups, C1-C 20 C1-C substituted or unsubstituted with halogenated alkyl groups, or any combination thereof 30 Alkylene groups and C6-C 30 arylene groups.

[0035] For example, in the above Chemical Formula 1, a1 and a2 are each independently an integer of 0 to 2. Specifically, in the above Chemical Formula 1, a1 is 1 or 2. Specifically, in the above Chemical Formula 1, a2 is 0 or 1.

[0036] In one embodiment, in the above Chemical Formula 1, (L1) a1 is represented by any one of the following chemical formulas 5-1 to 5-7: [ka]

[0037] In the chemical formulas 5-1 to 5-7, R 51 ~R 53 are each independently hydrogen, deuterium, halogen, a hydroxy group, a cyano group, a C1-C4 alkyl group, or a C1-C4 halogenated alkyl group; b51 is an integer from 1 to 4, n51 is an integer from 1 to 4, * and *' are bonding sites with adjacent atoms.

[0038] For example, in the above formula 1, R1 is a substituted or unsubstituted C1-C 30 Alkyl groups, substituted or unsubstituted C1-C 30 Halogenated alkyl groups, substituted or unsubstituted C1-C 30 Alkoxy groups, substituted or unsubstituted C1-C 30 Alkylthio groups, substituted or unsubstituted C1-C 30 Halogenated alkoxy groups, substituted or unsubstituted C1-C 30 Halogenated alkylthio groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkoxy groups, substituted or unsubstituted C3-C 30 Cycloalkylthio groups, substituted or unsubstituted C3-C 30 Heterocycloalkyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkoxy groups, substituted or unsubstituted C3-C 30 Heterocycloalkylthio groups, substituted or unsubstituted C2-C 30 Alkenyl groups, substituted or unsubstituted C2-C 30 Alkenyloxy groups, substituted or unsubstituted C2-C 30 Alkenylthio groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyloxy groups, substituted or unsubstituted C3-C 30 Cycloalkenylthio groups, substituted or unsubstituted C3-C 30 Heterocycloalkenyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkenyloxy groups, substituted or unsubstituted C3-C 30 Heterocycloalkenylthio groups, substituted or unsubstituted C2-C 30 Alkynyl groups, substituted or unsubstituted C2-C 30 Alkynyloxy groups, substituted or unsubstituted C2-C30 Alkynylthio groups, substituted or unsubstituted C6-C 30 Aryl groups, substituted or unsubstituted C6-C 30 Aryloxy groups, substituted or unsubstituted C6-C 30 Arylthio groups, substituted or unsubstituted C1-C 30 Heteroaryl groups, substituted or unsubstituted C1-C 30 Heteroaryloxy groups or substituted or unsubstituted C1-C 30 is a heteroarylthio group, R2 to R4 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxy group, -C(=O)R5, -C(R5)=NR6, -OR5, -S(=O)R5, -S(=O)2R5, -S(=O)2OR5, substituted or unsubstituted C1-C 30 Alkyl groups, substituted or unsubstituted C1-C 30 Halogenated alkyl groups, substituted or unsubstituted C1-C 30 Alkoxy groups, substituted or unsubstituted C1-C 30 Alkylthio groups, substituted or unsubstituted C1-C 30 Halogenated alkoxy groups, substituted or unsubstituted C1-C 30 Halogenated alkylthio groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkoxy groups, substituted or unsubstituted C3-C 30 Cycloalkylthio groups, substituted or unsubstituted C3-C 30 Heterocycloalkyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkoxy groups, substituted or unsubstituted C3-C 30 Heterocycloalkylthio groups, substituted or unsubstituted C2-C 30 Alkenyl groups, substituted or unsubstituted C2-C 30 Alkenyloxy groups, substituted or unsubstituted C2-C 30 Alkenylthio groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C3-C 30Cycloalkenyloxy groups, substituted or unsubstituted C3-C 30 Cycloalkenylthio groups, substituted or unsubstituted C3-C 30 Heterocycloalkenyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkenyloxy groups, substituted or unsubstituted C3-C 30 Heterocycloalkenylthio groups, substituted or unsubstituted C2-C 30 Alkynyl groups, substituted or unsubstituted C2-C 30 Alkynyloxy groups, substituted or unsubstituted C2-C 30 Alkynylthio groups, substituted or unsubstituted C6-C 30 Aryl groups, substituted or unsubstituted C6-C 30 Aryloxy groups, substituted or unsubstituted C6-C 30 Arylthio groups, substituted or unsubstituted C1-C 30 Heteroaryl groups, substituted or unsubstituted C1-C 30 Heteroaryloxy groups or substituted or unsubstituted C1-C 30 is a heteroarylthio group, R5 and R6 are each independently hydrogen, deuterium, a hydroxy group, or a substituted or unsubstituted C1-C 30 Alkyl groups, substituted or unsubstituted C1-C 30 Halogenated alkyl groups, substituted or unsubstituted C1-C 30 Alkoxy groups, substituted or unsubstituted C1-C 30 Alkylthio groups, substituted or unsubstituted C1-C 30 Halogenated alkoxy groups, substituted or unsubstituted C1-C 30 Halogenated alkylthio groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkoxy groups, substituted or unsubstituted C3-C 30 Cycloalkylthio groups, substituted or unsubstituted C3-C 30 Heterocycloalkyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkoxy groups, substituted or unsubstituted C3-C 30Heterocycloalkylthio groups, substituted or unsubstituted C2-C 30 Alkenyl groups, substituted or unsubstituted C2-C 30 Alkenyloxy groups, substituted or unsubstituted C2-C 30 Alkenylthio groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyloxy groups, substituted or unsubstituted C3-C 30 Cycloalkenylthio groups, substituted or unsubstituted C3-C 30 Heterocycloalkenyl groups, substituted or unsubstituted C3-C 30 Heterocycloalkenyloxy groups, substituted or unsubstituted C3-C 30 Heterocycloalkenylthio groups, substituted or unsubstituted C2-C 30 Alkynyl groups, substituted or unsubstituted C2-C 30 Alkynyloxy groups, substituted or unsubstituted C2-C 30 Alkynylthio groups, substituted or unsubstituted C6-C 30 Aryl groups, substituted or unsubstituted C6-C 30 Aryloxy groups, substituted or unsubstituted C6-C 30 Arylthio groups, substituted or unsubstituted C1-C 30 Heteroaryl groups, substituted or unsubstituted C1-C 30 Heteroaryloxy groups or substituted or unsubstituted C1-C 30 It is a heteroarylthio group.

[0039] Specifically, R1 is a deuterium atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a thiol group, an amino group, a carboxylic acid group, an ether moiety, a thioether moiety, a carbonyl moiety, an ester moiety, a phosphonate moiety, a sulfonate moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, a C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C1-C 20 Heteroaryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryloxy groups, C1-C 20 C1-C substituted or unsubstituted heteroarylthio groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups, R2 to R4 each independently represent hydrogen; deuterium; halogen; cyano group; nitro group; hydroxy group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20Cycloalkylthio group, C6-C 20 Aryl groups, C1-C 20 Heteroaryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryloxy groups, C1-C 20 C1-C substituted or unsubstituted heteroarylthio groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups; R5 and R6 each independently represent hydrogen; deuterium; a hydroxy group; and deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C1-C 20 Heteroaryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryloxy groups, C1-C 20C1-C substituted or unsubstituted heteroarylthio groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups;

[0040] More specifically, in the above formula 1, R1 is deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups, R2 to R4 each independently represent hydrogen; deuterium; halogen; cyano group; nitro group; hydroxy group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups; R5 and R6 are each independently hydrogen; deuterium; a hydroxy group; and deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups;

[0041] In particular, in the formula 1, R1 is selected from any one of the following formulas 3-1 to 3-21: R2 to R4 are each independently selected from hydrogen; deuterium; halogen; cyano group; nitro group; hydroxy group; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and any one of the following chemical formulas 3-1 to 3-21: R5 and R6 are each independently selected from hydrogen; deuterium; a hydroxyl group; and any one of the following chemical formulas 3-1 to 3-21: [ka]

[0042] In the chemical formulas 3-1 to 3-21, At least one hydrogen atom can be replaced by a deuterium atom, a halogen atom, a cyano group, a nitro group, a carbonyl moiety, or a C1-C 20Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 heteroaryl groups, or any combination thereof. In one embodiment, in Formula 1, Z1 is represented by any one of Formulas 4-1 to 4-9 below: [ka]

[0043] In the chemical formulas 4-1 to 4-9, R2 to R4 each independently represent hydrogen; deuterium; halogen; cyano group; nitro group; hydroxy group; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups; R5, R 5a , R 5b and R6 are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups; R2~R5, R 5a , R 5b and two adjacent groups among R6 can optionally be bonded to each other to form a ring; A 41 and A 42 are each independently a C-C group which may optionally contain a heteroatom. 30 Cyclic alkyl groups or C1-C groups optionally containing heteroatoms 30 is an aryl group, R 41 and R 42 are each independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, or C1-C 20 is a heteroaryl group, b41 and b42 each independently represent an integer of 1 to 10, * indicates a bonding site with an adjacent atom.

[0044] In one embodiment, in Formula 1, Z1 is represented by any one of the following Formulas 4-11 to 4-50: [ka] [ka] In the chemical formulas 4-11 to 4-50, * indicates a bonding site with an adjacent atom.

[0045] In one embodiment, in Formula 1, b1 is 2 or more, and R1 is selected from the group consisting of deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, and C6-C 30 aryl groups.

[0046] In one embodiment, in Formula 1, at least one of R2 to R4 is an electron withdrawing group.

[0047] In one embodiment, in Formula 1, at least one of R2 to R4 is selected from the group consisting of a halogen, a cyano group, a nitro group, —C(═O)R5, —C(R5)═NR6, —S(═O)2R5, and a halogen, a cyano group, a nitro group, a C1-C 20 C1-C substituted with halogenated alkyl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups; R5 and R6 are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 30 Alkyl groups, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C3-C 30 Cycloalkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups and C7-C 30 arylalkyl groups;

[0048] In one embodiment, the organometallic compound represented by Chemical Formula 1 is 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 is the same as defined in Chemical Formula 1 above, L 11 ~L 14 are each independently defined as L1 in Chemical Formula 1 above, L 21 ~L 23 are each independently defined as L2 in Chemical Formula 1 above, a11 to a14 each independently represent the same as the definition of a1 in Chemical Formula 1; a21 to a23 are each independently defined as a2 in Chemical Formula 1, R 11 ~R 13 are each independently defined as R1 in Chemical Formula 1 above, b11 to b13 each independently represent the same as b1 in Chemical Formula 1; Y 11 ~Y 14 are each independently defined as Y in Chemical Formula 1, X 11 ~X 14are each independently defined as X1 in Chemical Formula 1 above, Z 11 ~Z 14 are each independently defined as Z1 in Chemical Formula 1 above, c11 to c14 each independently have the same definition as c1 in Chemical Formula 1 above.

[0049] In one embodiment, the organometallic compound represented by Formula 1 is selected from Group I: [ka] [ka]

[0050] Without being limited to a particular theory, specific bonds in the organometallic compound can be dissociated by high-energy rays, resulting in a change in polarity.

[0051] Specifically, the organometallic compound is converted into R by high energy radiation. x Radicals are formed from the organometallic compound, and the radicals react selectively in the presence of water to generate polar functional groups. As a result, the physical properties of the organometallic compound, particularly its solubility in a developer, can be changed by exposure to high-energy radiation.

[0052] The difference in water contact angle of the organometallic compound before and after exposure is 25° or more, specifically 40° or more, more specifically 50° or more, and particularly 60° or more, at an exposure dose of 100 mJ / cm. 2 Specifically, 80 mJ / cm 2 More specifically, 60 mJ / cm 2 Below, especially 50mJ / cm 2 The following is the result.

[0053] The organometallic compound is 100 mJ / cm 2 The difference in water contact angle before and after exposure using an exposure dose of 25° or more, specifically 30° or more, and particularly 80 mJ / cm2 The difference in water contact angle before and after exposure using the following exposure doses is 25° or more, specifically 30° or more. 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 structure 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.

[0054] [Resist composition] In another aspect, there is provided a resist composition comprising the organometallic compound, which may have improved photosensitivity and / or storage stability. The resist composition has a solubility in a developer that changes upon exposure to high-energy rays. The resist composition is also a positive resist composition that dissolves and removes the exposed areas of the resist film to form a resist pattern.

[0055] The resist composition may be for a distilled water development process in which distilled water (DI) is used for the development treatment during resist pattern formation, an alkaline development process in which an alkaline developer is used, or a solvent development process in which a developer containing an organic solvent (hereinafter also referred to as an organic developer) is used for the development treatment. In particular, the resist composition can provide a pattern with improved critical dimension uniformity by using distilled water (DI) or an organic solvent as a developer, or by using an alkaline developer containing a relatively small amount of alkaline components.

[0056] The resist composition is 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, because the physical properties of the organometallic compound change upon exposure to light. 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, parts by weight, relative to 100 parts by weight of the composition. If the above range is satisfied, a resist composition can be provided that forms a film of a thickness required for pattern formation, while suppressing side reactions and thereby improving sensitivity and / or resolution.

[0057] <Organic solvents> 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 needed, etc. One type of organic solvent may be used, or two or more different types may be used in combination.

[0058] In one embodiment, the organic solvent comprises a non-polar solvent, a polar protic organic solvent, a polar aprotic organic solvent, or any combination thereof. In other embodiments, the organic solvent is a polar aprotic organic solvent. Examples of polar protic solvents include alcohol solvents. Examples of polar aprotic solvents include ether solvents, ketone solvents, amide solvents, ester solvents, and sulfoxide solvents.

[0059] Examples of non-polar solvents include hydrocarbon solvents. More specifically, 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 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; polyalcohol 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.

[0060] Examples of ether 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 tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0061] 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; and 2,4-pentanedione, acetonylacetone, and acetophenone.

[0062] Examples of 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.

[0063] Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, and cyclohexyl acetate. Acetate ester solvents such as acetate, methylcyclohexyl acetate, and n-nonyl acetate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether acetate (PGMEA). Examples of suitable solvents include polyhydric alcohol-containing ether carboxylate solvents such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate; glycol diacetate, methoxytriglyceride 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.

[0064] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0065] 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.

[0066] Specifically, the organic solvent includes a chain ketone solvent, a cyclic ketone solvent, a polyhydric alcohol-containing ether carboxylate solvent, a lactone solvent, an acetate ester solvent, and any combination thereof. More specifically, the organic solvent includes a cyclic ketone solvent, a polyhydric alcohol-containing ether carboxylate solvent, and any combination thereof.

[0067] In particular, the organic solvent includes cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and any combination thereof.

[0068] More particularly, the organic solvent comprises cyclopentanone, cyclohexanone, cycloheptanone, and any combination thereof. 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.

[0069] <Optional ingredients> The resist composition may further contain, as necessary, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0070] 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 SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.) and the like.

[0071] The surfactant is contained in an amount of 0 to 20 parts by weight based on 100 parts by weight of the polymer. One type of surfactant may be used, or two or more different types may be mixed and used. The method for producing the resist composition is not particularly limited, and for example, a method of mixing the polymer and optional components added as needed 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.

[0072] [Pattern formation method] Hereinafter, a pattern formation method according to an exemplary embodiment will be described in more detail with reference to Figures 1 and 2A to 2C. Figure 1 is a flowchart illustrating a pattern formation method according to an exemplary embodiment, and Figures 2A to 2C are side cross-sectional views illustrating a pattern formation method according to an exemplary embodiment. Hereinafter, a pattern formation method using a negative resist composition will be specifically described as an example, but is not limited thereto.

[0073] 1, the pattern forming method includes the steps of applying a resist composition to form a resist film (S101), exposing at least a portion of the resist film to high-energy radiation (S102), and developing the exposed resist film using a developer (S103). These steps may be omitted or performed in a different order, if necessary.

[0074] First, a substrate 100 is prepared. 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 a III-V compound such as GaP, GaAs, or GaSb.

[0075] 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 form crosslinks.

[0076] The coating method can be spin coating, dipping, roller coating, or other common coating methods. Among these, spin coating can be particularly used, 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.

[0077] The lower limit of the pre-baking temperature is 60°C or higher, specifically 80°C or higher. The upper limit of the pre-baking temperature is 150°C or lower, specifically 140°C or lower. The lower limit of the pre-baking time is 5 seconds or higher, specifically 10 seconds or higher. The upper limit of the pre-baking time is 600 seconds or lower, specifically 300 seconds or lower.

[0078] Before applying the resist composition to the substrate 100, a layer to be etched (not shown) may be formed on the substrate 100. The layer to be etched refers to a layer onto 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.

[0079] In one embodiment, 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. 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, for example, an immersion protective film can be provided on the resist film 100 to prevent direct contact between the immersion medium and the resist film 100.

[0080] 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.

[0081] Without being limited to a particular theory, exposure to light generates radicals in the exposed area 111, which then generate polar functional groups, which can change the physical properties of the resist composition. As a result, the exposed portion 111 and the non-exposed portion 112 can have different water contact angles, and the difference between the water contact angle of the non-exposed portion 112 and the water contact angle of the exposed portion 111 is 25° or more, specifically 40° or more, more specifically 50° or more, and particularly 60° or more.

[0082] In one embodiment, the exposure dose of the exposure is 100 mJ / cm 2 Specifically, 80 mJ / cm 2 More specifically, 60 mJ / cm 2 Below, especially 50mJ / cm 2 The difference between the water contact angle of the non-exposed portion 112 and the water contact angle of the exposed portion 111 is 25° or more, specifically 40° or more, more specifically 50° or more, and particularly 60° or more. The exposure dose of the exposure is 100 mJ / cm 2 When 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 30° or more, and particularly when the exposure dose of the exposure is 80 mJ / cm 2 When the water contact angle of the non-exposed portion 112 is equal to or greater than 25°, the difference between the water contact angle of the exposed portion 111 and the water contact angle of the non-exposed portion 112 is equal to or greater than 25°, specifically equal to or greater than 30°.

[0083] In some cases, the exposure is carried out by irradiating a high-energy beam through a mask having a predetermined pattern using a liquid medium such as water. Examples of the high-energy beam include electromagnetic waves such as ultraviolet, far ultraviolet, extreme ultraviolet (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 referred to as "exposure."

[0084] A variety of exposure light sources can be used, including those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 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) 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 writing without using a mask.

[0085] The cumulative dose of high-energy rays, for example, when extreme ultraviolet rays are used as high-energy rays, is 2000 mJ / cm 2 Specifically, 500mJ / cm 2 Below, we will be more specific about 100mJ / cm 2 When using electron beams as high-energy rays, the cumulative dose is 5000 μC / cm 2 Specifically, 1000 μC / cm 2 The following is the result.

[0086] After exposure, 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.

[0087] Next, a developer can be used to develop the exposed resist film 110. The exposed portions 111 are washed away and removed by the developer, while the unexposed portions 112 remain without being washed away by the developer.

[0088] Examples of the developer include distilled water, 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 puddle 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 alkaline developers include alkaline aqueous solutions containing one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN). The alkaline developer may further contain a surfactant.

[0089] 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, more specifically 1% by weight or more, and the upper limit of the alkaline compound content in the alkaline developer is 20% by weight or less, specifically 10% by weight or less, more specifically 5% by weight or less.

[0090] The organic solvent contained in the organic developer may be, for example, the same organic solvents as those exemplified in the "Organic Solvent" section of the "Resist Composition" section. Specifically, n-butyl acetate (nBA), propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), γ-butyrolactone (GBL), isopropanol (IPA), or the like 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.

[0091] 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 particularly 99% by weight or more. The organic developer may contain a surfactant. The organic developer may also contain a trace amount of water. During development, the organic developer may be replaced with a different solvent to stop development.

[0092] The developer may be used alone or in combination of two or more. The resist pattern after development can be further washed. Examples of the washing liquid include pure water, ultrapure water, and rinse liquid. The rinse liquid is not particularly limited 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 is an alcohol-based solvent or an ester-based solvent. After washing, the rinse liquid remaining on the substrate and pattern can be removed. Furthermore, when ultrapure water is used, the water remaining on the substrate and pattern can be removed. After forming the resist pattern as described above, etching is performed to obtain a patterned wiring substrate. The etching method is carried out by a known method such as dry etching using plasma gas or wet etching using an alkaline solution, cupric chloride solution, ferric chloride solution, or the like.

[0093] 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.

[0094] The remaining resist pattern after etching can be stripped using 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), and ethyl lactate (EL). Stripping methods include, but are not limited to, immersion and spraying. The wiring substrate on which the resist pattern is formed can also be a multilayer wiring substrate and can have small through-holes.

[0095] In one embodiment, the wiring substrate can also be formed by a method in which, after forming a resist pattern, a metal is evaporated in a vacuum, and then the resist pattern is dissolved in a solution, that is, by a lift-off method.

[0096] 3A-3E are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. 3A, 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 have a multi-layer structure. The material of the material layer 130 is different from the material of the substrate 100.

[0097] As shown in FIG. 3B, the resist film 110 undergoes a pre-exposure bake process and is then 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. 3C, the exposed resist film 110 is developed using a developer (e.g., a developer). The exposed portions 111 are washed away by the developer, and the unexposed portions 112 remain without being washed away by the developer.

[0098] As shown in FIG. 3D, 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. 3E, the resist pattern 110 can be removed.

[0099] 4A-4E are cross-sectional side views illustrating a method of forming a semiconductor device according to one embodiment. 4A, a gate dielectric 505 (e.g., silicon dioxide) 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.

[0100] 4B, 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. As shown in FIG. 4C, 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.

[0101] As shown in FIG. 4D, 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.

[0102] 4E, 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 spacers 535a. Then, electrical contacts 570a, 570b, and 570c connected to the gate electrode 515a and the source / drain regions are formed in the interlayer insulating film 560. The electrical contacts 570a, 570b, and 570c are made 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.

[0103] 4A-4E illustrate an example of forming a transistor, but the present invention is not limited thereto. The resist composition according to an embodiment may be used in patterning processes 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.

[0104] [Example] Synthesis Example 1: Synthesis of OM-A [ka]

[0105] (1) Synthesis of A-2 N-hydroxy-N-methylbenzamide (0.5 g, 3.31 mmol) was placed in a nitrogen-purged two-neck round-bottom flask (RBF) and diluted with THF (5 mL). Pyridine (0.54 mL, 6.62 mmol) was added at 0°C, followed by a THF solution (6 mL, total 11 mL (0.3 M)) of 3-(chlorosulfonyl)benzoic acid (0.73 g, 3.31 mmol). The mixture was then warmed to room temperature and stirred for 18 hours. After completion of the reaction, the mixture was diluted with ethyl acetate (EA), 1N HCl (3 mL) was added, and the organic layer was washed three times with distilled water. The combined organic layer was dried over NaSO, and the solvent was removed. After purification using short column chromatography (eluent: MC:MeOH (MeOH 5v%)), the residue was recrystallized using EA / n-hexane to give compound A-2 (0.24 g, yield: 21%). 1 H NMR(500MHz,DMSO)δ13.49(s,1H),8.30-8.22(m,2H),8.17(dt,J=7.9,1.4Hz, 1H),7.75(t,J=7.8Hz,1H),7.53-7.45(m,1H),7.41-7.29(m,4H),3.34(s,3H). 13 C NMR(126MHz,DMSO)δ170.95,165.33,135.77,133.13,132.91,132.19,131.81,131.75,130.40,129.26,128.44,128.02,41.32

[0106] (2) Synthesis of A-1 Sodium hydride (0.18 g, 4.5 mmol) was placed in an RBF and, after purging with N2, diluted with THF (22 ml, 0.2 M). Compound A-2 (1.5 g, 4.5 mmol) was added thereto at 0 °C. The reaction mixture was then stirred at 0 °C for 5 hours. After removing the solvent, the product was recrystallized with THF:Et2O = 1:5 (10 ml:50 ml) and filtered to obtain compound A-1 (1.4 g, yield: 89%). 1H NMR(500MHz,DMSO)δ8.39(t,J=1.8Hz,1H),8.20(dt,J=7.6,1.4Hz,1H),7.79(d dd,J=7.8,2.1,1.2Hz,1H),7.55-7.47(m,2H),7.43-7.35(m,4H),3.21(s,3H). 13 C NMR(126MHz,DMSO)δ171.16,166.54,142.19,135.51,132.13,131.91,131.69,129.38,128.69,128.61,128.46,128.02,41.05

[0107] (3) Synthesis of OM-A Dichlorobis(4-fluorobenzyl)stannane (0.5 g, 1.23 mmol) was placed in an RBF and purged with N2. Acetone (12.3 ml, 0.1 M) was added to dilute the mixture, and then compound A-1 (0.88 g, 2.45 mmol) was added at 0°C. The mixture was stirred at 0°C for 18 hours and then filtered through Celite. The solvent was removed from the filtrate, and the mixture was recrystallized using dichloromethane:n-hexane (1:10, 5 ml:50 ml). After filtration, the residue was dried under vacuum to obtain compound OM-A (0.85 g, yield: 69%). 1 H NMR(500MHz,CD2Cl2)δ8.47(t,J=1.9Hz,2H),8.15(d,J=7.8Hz,2H),8.03(dt,J=7.9,1.5Hz,2H),7.56 (t,J=7.9Hz,2H),7.47-7.30(m,10H),7.05-6.94(m,4H),6.79-6.70(m,4H),3.48(s,6H),3.14(s,4H). 13 C NMR(126MHz,CD2Cl2)δ173.84,171.75,161.42(d,J=243.9Hz),136.50,134.66,133.71,132.64,132.1 8,131.60,131.27,130.45(d,J=8.2Hz),129.88,128.84,128.74,115.65(d,J=21.8Hz),41.81,32.38. 119Sn NMR (186MHz, CD2Cl2)δ-246.47. 19 F NMR (471MHz, CD2Cl2)δ-118.70.

[0108] Evaluation example 1: Thin film development evaluation Specifically, the organometallic compound synthesized in Synthesis Example 1 was dissolved in the casting solvent shown in Table 1 below at the concentration shown in Table 1 below to prepare a casting solution. After a 4-inch diameter silicon wafer was treated with O2 plasma for 30 minutes, the casting solution was spin-coated for 1 minute at the coating speed shown in Table 1 below, and then dried (PAB) at 110°C for 1 minute to prepare a film having an initial thickness shown in Table 1 below. Next, a 1cm thick jig (4x4) with rectangular holes (1cm x 1cm) was placed on top of the wafer, and 0-80mJ / cm of DUV light with a wavelength of 254nm was applied to each hole. 2 The film was exposed to light at a dose of 1000 kJ / cm2 and dried at 170°C for 90 seconds (PEB). The dried film was immersed in distilled water (DI) or a PGMEA solution containing 2 wt% acetic acid (PGMEA (2 wt% AA)) as a developer at 25°C for 60 seconds, and the remaining film thickness was measured and shown in Table 1 below and Figures 5A to 5D. Furthermore, the relative film thicknesses of Example 1-1 and Comparative Examples 1-1, 1-3, and 1-5 were compared and shown in Figures 6A to 6C. Here, the remaining film ratio is the ratio of 0 mJ / cm2 after development. 2 and 80mJ / cm 2 This means the ratio of the thickness of the film to the thickness of the film.

[0109] [Table 1] [ka]

[0110] 5A to 5D, and 6A to 6C, comparing the film retention rates of Example 1-1 and Comparative Examples 1-1, 1-3, and 1-5, it was found that the film retention rate of Example 1-1 was improved by 77%, 82%, and 79%, respectively, compared to the film retention rates of Comparative Examples 1-1, 1-3, and 1-5. This confirmed that the resist composition of Example 1-1 had significantly improved solubility in DI compared to the resist compositions of Comparative Examples 1-1, 1-3, and 1-5.

[0111] Evaluation example 2: Water contact angle (WCA) evaluation Specifically, the organometallic compound synthesized in Synthesis Example 1 was dissolved in a cyclohexanone casting solvent at a concentration of 2 wt % to prepare a casting solution. After treating a 4-inch diameter silicon wafer with O2 plasma for 30 minutes, the casting solution was spin-coated at a coating speed of 2000 rpm for 1 minute and then dried (PAB) at 110°C for 1 minute to produce a film with an initial thickness of 40 nm. Next, a 1 cm thick jig (4 x 4) with rectangular holes (1 cm x 1 cm) was placed on top of the wafer, and 254 nm wavelength DUV was applied to each hole at 0-100 mJ / cm. 2 and dried (PEB) at 170° C. for 90 seconds. Then, 3 μL of water was dropped into each hole to measure the water contact angle (unit: °). The results are shown in Table 2 below.

[0112] [Table 2] [ka]

[0113] Referring to Table 2, it can be seen that the resist composition of Example 2-1 exhibited a significant change in water contact angle before and after DUV irradiation, confirming that a change in polarity of the organometallic compound occurred.

Claims

1. An organometallic compound represented by the following chemical formula 1: M １１ (R) ｘ ) ｎ (R) ｙ ) （ｍ－ｎ） (Chemical Formula 1) In the above Chemical Formula 1, M １１ is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po); R ｘ is *-X １ - (L １ ) ａ１ - [Y １ -Z １ ] ｃ１ and R ｙ *-(L ２ ) ａ２ - (R １ ) ｂ１ and n is an integer from 1 to 6, m is an integer from 1 to 6, m-n is 0 or greater, Multiple R's ｘ may be the same or different from each other, Multiple R's ｙ 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 are OC(=O), C(=O)O, OS(=O) ２ , or S(=O) ２ O, Z １ is *-C(R ２ ) (R ３ ) (R ４ ), *-C(R ２ ) = N(R ３ ), C(R ２ ) (R ３ ) = N-*, or *-N(R ２ ) (R ３ ) and L １ and L ２ each independently represents a C group which may optionally contain a heteroatom; １ -C ３０ is a linear, branched, or cyclic divalent hydrocarbon radical of a1 and a2 each independently represent an integer of 0 to 4, R １ is C, which may optionally contain a heteroatom １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon group of the formula １ two adjacent groups among R ２ ~R ４ are each independently hydrogen, deuterium, a halogen, a cyano group, a hydroxy group, or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon group of the formula ２ ~R ４ two adjacent groups among b1 and c1 each independently represent an integer of 1 to 4; * indicates a bonding site with an adjacent atom.

2. M １１ 2. The organometallic compound of claim 1, wherein is Sn, Sb, Te, or Bi.

3. n is an integer from 1 to 4, m is an integer from 1 to 4, M １１ The organometallic compound of claim 1 , wherein is Sn.

4. M １１ and R ｘ The bond with M １１ -oxygen single bond or M １１ -sulfur single bond, M １１ and R ｙ The bond with M １１ 2. The organometallic compound of claim 1, wherein the carbon atom is a -carbon single bond.

5. R １ is a substituted or unsubstituted C １ -C ３０ alkyl group, substituted or unsubstituted C １ -C ３０ Halogenated alkyl 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 Halogenated alkoxy groups, substituted or unsubstituted C １ -C ３０ Halogenated alkylthio groups, 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 group, 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 C ６ -C ３０ aryloxy group, substituted or unsubstituted C ６ -C ３０ arylthio group, substituted or unsubstituted C １ -C ３０ Heteroaryl groups, substituted or unsubstituted C １ -C ３０ heteroaryloxy group, or substituted or unsubstituted C １ -C ３０ is a heteroarylthio group, R ２ ~R ４ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxy group, -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 , substituted or unsubstituted C １ -C ３０ alkyl group, substituted or unsubstituted C １ -C ３０ Halogenated alkyl 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 Halogenated alkoxy groups, substituted or unsubstituted C １ -C ３０ Halogenated alkylthio groups, 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 group, 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 C ６ -C ３０ aryloxy group, substituted or unsubstituted C ６ -C ３０ arylthio group, substituted or unsubstituted C １ -C ３０ Heteroaryl groups, substituted or unsubstituted C １ -C ３０ heteroaryloxy group, or substituted or unsubstituted C １ -C ３０ is a heteroarylthio group, R ５ and R ６ are each independently hydrogen, deuterium, substituted or unsubstituted C １ -C ３０ alkyl group, substituted or unsubstituted C １ -C ３０ Halogenated alkyl 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 Halogenated alkoxy groups, substituted or unsubstituted C １ -C ３０ Halogenated alkylthio groups, 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 group, 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 C ６ -C ３０ aryloxy group, substituted or unsubstituted C ６ -C ３０ arylthio group, substituted or unsubstituted C １ -C ３０ Heteroaryl groups, substituted or unsubstituted C １ -C ３０ heteroaryloxy group, or substituted or unsubstituted C １ -C ３０ 2. The organometallic compound of claim 1, which is a heteroarylthio group.

6. R １ represents deuterium, halogen, cyano group, nitro group, carbonyl moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ３０ Alkyl group, C ３ -C ３０ Cycloalkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ aryl groups, and C ７ -C ３０ arylalkyl groups, R ２ ~R ４ are each independently hydrogen; deuterium; halogen; cyano group; nitro group; hydroxy group; -C(=O)R ５ ; -C(R ５ ) = NR ６ -S(=O) ２ R ５ and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ３０ Alkyl group, C ３ -C ３０ Cycloalkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ aryl groups, and C ７ -C ３０ arylalkyl groups; R ５ and R ６ are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ３０ Alkyl group, C ３ -C ３０ Cycloalkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ aryl groups, and C ７ -C ３０ 10. The organometallic compound of claim 1, selected from the group consisting of: an arylalkyl group;

7. Z １ The organometallic compound according to claim 1, which is represented by any one of the following chemical formulas 4-1 to 4-9: 【Chemistry 1】 In the chemical formulas 4-1 to 4-9, R ２ ~R ４ are each independently hydrogen; deuterium; halogen; cyano group; nitro group; hydroxy group; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ３０ Alkyl group, C ３ -C ３０ Cycloalkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ aryl groups, and C ７ -C ３０ arylalkyl groups; R ５ , R ５ａ , R ５ｂ , and R ６ are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, carbonyl moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ３０ Alkyl group, C ３ -C ３０ Cycloalkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ aryl groups, and C ７ -C ３０ arylalkyl groups; R ２ ~R ５ , R ５ａ , R ５ｂ , and R ６ two adjacent groups among A ４１ and A ４２ each independently represents a C group which may optionally contain a heteroatom; １ -C ３０ a cyclic alkyl group or a C group which may optionally contain a heteroatom; １ -C ３０ is an aryl group, R ４１ and R ４２ are each independently hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ an aryl group, or C １ -C ２０ is a heteroaryl group, b41 and b42 each independently represent an integer of 1 to 10; * indicates a bonding site with an adjacent atom.

8. b1 is 2 or more, R １ represents deuterium, halogen, cyano group, nitro group, carbonyl moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl 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 2. The organometallic compound of claim 1, wherein the aryl group is selected from the group consisting of aryl groups.

9. R ２ ~R ４ 10. The organometallic compound of claim 1, wherein at least one of is an electron withdrawing group.

10. The organometallic compound represented by Chemical Formula 1 is the organometallic compound according to claim 1, which is represented by any one of the following Chemical Formulas 1-1 to 1-4: 【Chemistry 2】 In the chemical formulas 1-1 to 1-4, M １１ is the same as defined in Chemical Formula 1 above, L １１ ~L １４ are each independently L in Chemical Formula 1 １ is the same as the definition of L ２１ ~L ２３ are each independently L in Chemical Formula 1 ２ is the same as the definition of a11 to a14 are each independently the same as defined for a1 in Chemical Formula 1; a21 to a23 are each independently the same as defined for a2 in Chemical Formula 1; R １１ ~R １３ are each independently R in Chemical Formula 1 １ is the same as the definition of b11 to b13 are each independently the same as defined for b1 in Chemical Formula 1; Y １１ ~Y １４ are each independently selected from Y in Chemical Formula 1. １ is the same as the definition of X １１ ~X １４ are each independently X in Chemical Formula 1 １ is the same as the definition of Z １１ ~Z １４ are each independently Z in Chemical Formula 1 １ is the same as the definition of c11 to c14 each independently have the same definition as c1 in Chemical Formula 1 above.

11. The organometallic compound of claim 1 is selected from Group I: 【Chemistry 3A】 【Chemistry 3B】 。

12. A resist composition comprising the organometallic compound of claim 1.

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

14. 13. 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 according to claim 12, further comprising an organic solvent.

16. 16. The resist composition according to claim 15, wherein the organic solvent is a polar aprotic solvent.

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

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

20. the exposed resist film includes an exposed portion and a non-exposed portion, 18. The pattern formation method according to claim 17, wherein a difference between a water contact angle of the non-exposed portion and a water contact angle of the exposed portion is 25° or more.

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