Resist composition and pattern forming method using same

Abstract

Provided are a resist composition and a pattern forming method using the same. The resist composition includes a first organometallic compound represented by one of Formulae 1-1 to 1-4 and a second organometallic compound represented by Formula 2: wherein M11, M21, L11 to L14, L21 to L24, a11 to a14, a21 to a24, R11 to R14, R21 to R24, b11 to b14, b21 to b24, Y11 to Y13, and X11 to X13 in Formulae 1-1 to 1-4 and 2 are as described in the specification. # imgabs 0 # formula 2 # imgabs 1 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0151935 filed on November 6, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. Technical Field

[0003] The present disclosure relates to a resist composition and a pattern forming method using the same. Background Art

[0004] During the manufacture of semiconductors, resists whose physical properties change in response to light are used to form fine patterns. Among these resists, chemically amplified resists have been widely used. In the case of chemically amplified resists, an acid formed by a reaction between light and a photoacid generator reacts again with a base resin to change the solubility of the base resin to a developer, thereby enabling patterning.

[0005] However, in the case of chemically amplified resists, diffusion of the formed acid into unexposed areas can lead to poor pattern uniformity and increased surface roughness. With increasingly miniaturized semiconductor processes, it is not easy to control the diffusion of the acid, resulting in the need to develop new types of resists.

[0006] Recently, in order to overcome the limitations of chemically amplified resists, attempts have been made to develop materials whose physical properties change due to exposure. However, the dose required for exposure is still high. Summary of the invention

[0007] Provided are a resist composition having improved storage stability, the properties of which are changed even under low-dose exposure, and which provides a pattern with improved resolution, and a pattern forming method using the same.

[0008] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0009] According to example embodiments of the present disclosure, the resist composition may include a first organometallic compound represented by one of Formulae 1-1 to 1-4, and

[0010] The second organometallic compound represented by Formula 2, wherein

[0011] The first organometallic compound and the second organometallic compound may be different from each other:

[0012]

[0013] Wherein, in Formulas 1-1 to 1-4 and 2,

[0014] M 11 and M 21 can be independently selected from indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po),

[0015] L 11 To L 14 and L 21 To L 24 Each independently may be a single bond or a linear, branched or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0016] a11 to a14 and a21 to a24 may each independently be an integer of 1 to 4,

[0017] R 11 To R 14 and R 21 To R 24 Each independently may be a polymerizable group, a substituted or unsubstituted C 1 -C 30 Alkyl, substituted or unsubstituted C 3 -C 30 Cycloalkyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl, substituted or unsubstituted C 2 -C 30 Alkenyl, substituted or unsubstituted C 3 -C 30 Cycloalkenyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl, substituted or unsubstituted C 2 -C 30 Alkynyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 7 -C 30 Arylalkyl, substituted or unsubstituted C 1 -C 30 heteroaryl, or substituted or unsubstituted C 2 -C 30 Heteroarylalkyl,

[0018] R 21 To R 24 At least one of may be a polymerizable group,

[0019] R 11 To R 14and R 21 To R 24 Two adjacent ones of may optionally be bonded to each other to form a ring,

[0020] b11 to b14 and b21 to b24 may each independently be an integer of 1 to 4,

[0021] Y 11 To Y 13 can be independently O, OC (= O), S, SC (= O), NX 14 , or NX 14 C(=O), and

[0022] X 11 To X 14 are each independently hydrogen, deuterium, or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 A monovalent hydrocarbon group.

[0023] According to example embodiments of the present disclosure, a pattern forming method may include forming a resist film by applying the resist composition to a substrate, exposing at least a portion of the resist film to high-energy rays to provide an exposed resist film, and developing the exposed resist film using a developer. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The above and other aspects, features, and advantages of some embodiments will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0025] Figure 1 is a flow chart showing a pattern forming method according to an embodiment;

[0026] Figures 2A to 2C is a side cross-sectional view showing a pattern forming method according to an embodiment;

[0027] Figures 3A to 3E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment; and

[0028] Figures 4A to 4E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION

[0029] Embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings, wherein the same reference numerals always refer to the same elements. In this regard, the present embodiment may have different forms and should not be construed as being limited to the description set forth herein. Therefore, embodiments are described below with reference to the accompanying drawings to illustrate aspects of the present specification. As used herein, the term "and / or" includes any and all combinations of one or more of the related enumerated items. Statements such as "at least one (kind) of ... ", when before or after the list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, "at least one (kind) of A, B, and C" and similar language (e.g., "selected from at least one (kind) of A, B, and C", "at least one (kind) of A, B, or C") can be interpreted as only A, only B, only C, or any combination of two or more of A, B, and C, such as ABC, AB, BC, and AC.

[0030] When the term "about" or "substantially" is used in conjunction with a numerical value in this specification, it is intended that the associated numerical value includes a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value. In addition, when the words "substantially" and "substantially" are used in conjunction with a geometric shape, it is intended that the accuracy of the geometric shape is not required, but that the tolerance for the shape is within the scope of the present disclosure. In addition, regardless of whether a numerical value or shape is modified as "about" or "substantially", it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operating tolerances around the stated numerical value or shape (e.g., ±10%). When a range is specified, the range includes all values ​​therebetween, such as increments of 0.1%.

[0031] Since the present disclosure can be applied to a variety of transformations and has a variety of embodiments, the specific embodiments will be shown in the drawings and described in detail in the specific embodiments. However, it should be understood that this is not intended to limit the present disclosure to specific embodiments, but to include all transformations, equivalents and substitutes included in the spirit and scope of the present disclosure. When describing the present disclosure, when it is determined that the specific description of known related art unnecessarily obscures the subject matter of the present disclosure, its detailed description will be omitted.

[0032] It will be understood that although the terms "first", "second", and "third" may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element and are not used to limit the order or type of the elements.

[0033] In this specification, when a part of a layer, film, region, plate, etc. is described as being "on" or "over" another part, it may include not only the meaning of "directly on / below / left / right of..." in a contacting manner, but also the meaning of "on / below / left / right of..." in a non-contacting manner.

[0034] Expressions used in the singular encompass expressions in the plural, unless they have clearly different meanings in the context. Hereinafter, unless explicitly described to the contrary, it will be understood that terms such as "include", "have", and "comprise" are intended to indicate the presence of features, numbers, steps, actions, components (parts), parts, ingredients, materials, or combinations thereof disclosed in this specification, and are not intended to exclude the possibility that one or more other features, numbers, steps, actions, components (parts), parts, ingredients, materials, or combinations thereof may exist or may be added.

[0035] Whenever a range of values ​​is listed, the range includes all values ​​falling within the range, as if expressly written, and the range further includes the boundaries of the range. Thus, a range of "X to Y" includes all values ​​between X and Y and also includes X and Y.

[0036] The expression “C x -C y " refers to the case where the number of carbon atoms constituting the substituent is within the range of x to y. For example, the expression "C 1 -C 6 " refers to the case where the number of carbon atoms constituting the substituent is within the range of 1 to 6, and the expression "C 6 -C 20 ” refers to the case where the number of carbon atoms constituting the substituent is within the range of 6 to 20.

[0037] The term "monovalent hydrocarbon group" as used herein refers to a monovalent residue derived from an organic compound including carbon and hydrogen or a derivative thereof, and specific examples thereof include a linear or branched alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); a monovalent saturated alicyclic hydrocarbon group (cycloalkyl group) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecyl, In some embodiments, the monovalent hydrocarbon groups of the present invention include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxyl-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl, or a combination thereof. In some embodiments, some of the hydrogen in these groups may be replaced by a portion including heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, or halogen atoms, or some of the carbon in these groups may be replaced by a portion including heteroatoms such as oxygen, sulfur, nitrogen, or phosphorus. Thus, these groups can include cyano groups, nitro groups, hydroxyl groups, thiol groups, amino groups, carboxylate groups, ether moieties, thioether moieties, carbonyl moieties, ester moieties, phosphonate moieties, sulfonate moieties, carbonate moieties, amide moieties, lactone moieties, sultone moieties, carboxylic anhydride moieties, and the like.

[0038] The term "divalent hydrocarbon group" as used herein is a divalent residue and refers to a system in which any one hydrogen atom of a 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 cycloalkenylene group, an arylene group, a group in which some of its carbon atoms are replaced by heteroatoms, and the like.

[0039] The term "alkyl" as used herein refers to a linear or branched saturated aliphatic monovalent hydrocarbon group, and examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. The term "alkylene" as used herein refers to a linear or branched saturated aliphatic divalent hydrocarbon group, and examples thereof may include methylene, ethylene, propylene, butylene, and isobutylene.

[0040] The term "haloalkyl" as used herein refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom, and examples thereof include CF 3 In this regard, the halogen atom is F, Cl, Br, or I.

[0041] As used herein, the term "alkoxy" refers to a group having the formula -OA 101 A monovalent group, where A 101 Specific examples thereof include methoxy, ethoxy, isopropoxy and the like.

[0042] As used herein, the term "alkylthio" refers to a group having the formula -SA 101 A monovalent group, where A 101 It is an alkyl group.

[0043] The term "haloalkoxy" as used herein refers to a group in which one or more hydrogen atoms of an alkoxy group are replaced by a halogen atom, and specific examples thereof include -OCF 3 wait.

[0044] The term "haloalkylthio group" as used herein refers to a group in which one or more hydrogen atoms of an alkylthio group are replaced by a halogen atom, and specific examples thereof include -SCF 3 wait.

[0045] The term "cycloalkyl" as used herein refers to a monovalent saturated hydrocarbon cyclic group, and specific examples thereof include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and polycyclic condensed cyclic groups such as norbornyl and adamantyl. The term "cycloalkylene" as used herein refers to a divalent saturated hydrocarbon cyclic group, and specific examples thereof include cyclopentylene, cyclohexylene, adamantylene, adamantylene methyl, norbornylene, norbornylene methyl, tricyclodecylene, tetracyclododecylene, tetracyclododecylene methyl, dicyclohexylene methyl, etc.

[0046] As used herein, the term "cycloalkoxy" refers to a cycloalkyl group having the formula -OA 102 A monovalent group, where A 102 Specific examples thereof include cyclopropyloxy, cyclobutyloxy and the like.

[0047] As used herein, the term "cycloalkylthio" refers to a group having the formula -SA 102 A monovalent group, where A 102 It is a cycloalkyl group.

[0048] The term "heterocycloalkyl" as used in this article can be a group in which some carbon atoms of cycloalkyl are replaced by parts including heteroatoms such as oxygen, sulphur or nitrogen. The heterocycloalkyl can include ether bonds (connections), ester bonds (connections), sulfonate bonds (connections), carbonate bonds (connections), lactone rings, sultone rings or carboxylic anhydride moieties. The term "heterocycloalkylene" as used in this article refers to a group in which some carbon atoms of cycloalkylene are replaced by parts including heteroatoms such as oxygen, sulphur or nitrogen.

[0049] As used herein, the term "heterocycloalkoxy" refers to a heterocycloalkoxy group having the formula -OA 103 A monovalent group, where A 103 It is a heterocycloalkyl group.

[0050] As used herein, the term "heterocycloalkylthio" refers to a group having the formula -SA 103 A monovalent group, where A 103 It may be a heterocycloalkyl group.

[0051] As used herein, the term "alkenyl" refers to a linear or branched unsaturated aliphatic hydrocarbon monovalent group including one or more carbon-carbon double bonds. As used herein, the term "alkenylene" refers to a linear or branched unsaturated aliphatic hydrocarbon divalent group including one or more carbon-carbon double bonds.

[0052] The term "cycloalkenyl" as used herein refers to a monovalent unsaturated hydrocarbon cyclic group including one or more carbon-carbon double bonds and not having aromaticity. The term "cycloalkenylene" as used herein refers to a divalent unsaturated hydrocarbon cyclic group including one or more carbon-carbon double bonds and not having aromaticity.

[0053] The term "heterocycloalkenyl" as used herein refers to a group in which some of the carbon atoms of a cycloalkenyl group are replaced by a moiety comprising heteroatoms such as oxygen, sulfur, or nitrogen. The term "heterocycloalkenylene" as used herein refers to a group in which some of the carbon atoms of a cycloalkenyl group are replaced by a moiety comprising heteroatoms such as oxygen, sulfur, or nitrogen.

[0054] The term "alkynyl" as used herein refers to a straight-chain or branched unsaturated aliphatic hydrocarbon monovalent group including one or more carbon-carbon triple bonds.

[0055] The term "aryl" as used herein refers to a monovalent group having a carbocyclic aromatic system, and examples thereof include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, and The term "arylene" as used herein refers to a divalent group having a carbocyclic aromatic system.

[0056] As used herein, the term "aryloxy" refers to a 104 A is a monovalent group represented by 104It is an aromatic group.

[0057] As used herein, the term "arylthio" refers to a 104 A is a monovalent group represented by 104 It is an aromatic group.

[0058] The term "heteroaryl" as used herein refers to a monovalent group having a heterocyclic aromatic system, and specific examples thereof include pyridyl, pyrimidinyl, pyrazinyl, etc. The term "heteroarylene" as used herein refers to a divalent group having a heterocyclic aromatic system.

[0059] As used herein, the term "heteroaryloxy" refers to a 105 A is a monovalent group represented by 105 It is a heteroaryl group.

[0060] As used herein, the term "heteroarylthio" refers to a 105 A is a monovalent group represented by 105 It is a heteroaryl group.

[0061] The term "arylalkyl" as used herein refers to a group in which an alkyl group is substituted with a monovalent group having a carbocyclic aromatic system, and specific examples include benzyl, diphenylmethyl and the like.

[0062] The term "heteroarylalkyl" as used herein refers to a group in which an alkyl group is substituted with a monovalent group having a heterocyclic aromatic system.

[0063] The term "heterocyclic group" as used herein refers to a monocyclic or polycyclic group having 1 to 60 carbon atoms including at least one heteroatom, and is a group including a monovalent group, a divalent group, and a trivalent group.

[0064] The term "substituent" as used herein includes deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylate 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 anhydride moiety, a C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, or C 1 -C 20 heteroarylthio;

[0065] Each of C is substituted by 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, and C 1 -C 20 Heteroarylthio group: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1-C 20 Alkylthio, C 1 -C 20 Haloalkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof; and combinations thereof.

[0066] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings, wherein the same reference numerals denote substantially the same or corresponding components throughout the accompanying drawings, and redundant descriptions thereof will be omitted. In the accompanying drawings, the thicknesses of layers and regions are exaggerated for clarity. In addition, in the accompanying drawings, the thicknesses of some layers and regions are exaggerated for ease of description. Meanwhile, the embodiments described herein are merely examples, and various changes may be made therein.

[0067] [Resist composition]

[0068] The resist composition according to an embodiment includes a first organic metal compound represented by one of Formulae 1-1 to 1-4 and a second organic metal compound represented by Formula 2:

[0069]

[0070]

[0071] and a second organometallic compound represented by Formula 2:

[0072]

[0073] Wherein, in Formulas 1-1 to 1-4 and 2,

[0074] M 11 and M 21 can be independently selected from indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po),

[0075] L 11 To L 14 and L 21 To L 24 Each independently may be a single bond or a linear, branched or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0076] a11 to a14 and a21 to a24 may each independently be an integer of 1 to 4,

[0077] R 11 To R 14 and R 21 To R 24 Each independently may be a polymerizable group, a substituted or unsubstituted C 1 -C 30 Alkyl, substituted or unsubstituted C 3 -C 30 Cycloalkyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl, substituted or unsubstituted C 2 -C 30 Alkenyl, substituted or unsubstituted C 3 -C 30 Cycloalkenyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl, substituted or unsubstituted C 2 -C 30 Alkynyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 7 -C 30 Arylalkyl, substituted or unsubstituted C 1 -C 30 heteroaryl, or substituted or unsubstituted C 2 -C 30 Heteroarylalkyl,

[0078] R 21 To R 24 At least one of may be a polymerizable group,

[0079] R 11 To R 14 and R 21 To R 24 Two adjacent ones of may optionally be bonded to each other to form a ring,

[0080] b11 to b14 and b21 to b24 may each independently be an integer of 1 to 4,

[0081] Y 11To Y 13 can be independently O, OC (= O), S, SC (= O), NX 14 , or NX 14 C(=O), and

[0082] X 11 To X 14 may be independently hydrogen, deuterium, or a linear, branched or cyclic C 1 -C 30 A monovalent hydrocarbon group.

[0083] The first organometallic compound and the second organometallic compound may be different from each other.

[0084] The molecular weight of the first organometallic compound may be 3000 g / mol or less. In some embodiments, the molecular weight of the first organometallic compound may be 2000 g / mol or less.

[0085] For example, M in Formulas 1-1 to 1-4 and 2 11 and M 21 In some embodiments, M in Formulas 1-1 to 1-4 and 2 11 and M 21 They may each independently be Sn.

[0086] For example, L in Formulas 1-1 to 1-4 and 2 11 To L 14 and L 21 To L 24 can be independently a single bond, a substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 3 -C 30 Cycloalkylene, substituted or unsubstituted C 3 -C 30 Heterocycloalkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 3 -C 30 Cycloalkenylene, substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene, substituted or unsubstituted C 6 -C 30 Arylene, or substituted or unsubstituted C 1 -C 30 Heteroarylene.

[0087] In some embodiments, L in Formulas 1-1 to 1-4 and 2 11 To L14 and L 21 To L 24 may be independently selected from: a single bond; C 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Heterocycloalkylene, C 2 -C 30 Alkenylene, C 3 -C 30 Cycloalkenylene, C 3 -C 30 Heterocycloalkenylene, C 6 -C 30 Arylene, and / or C 1 -C 30 Heteroarylene group: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0088] In some embodiments, L in Formulas 1-1 to 1-4 and 2 11 To L14 and L 21 To L 24 may be independently selected from: a single bond; and / or C 1 -C 30 Alkylene: deuterium, halogen atoms, hydroxyl, cyano, C 1 -C 20 Alkyl, C 1 -C 20 haloalkyl, or a combination thereof.

[0089] For example, a11 to a14 and a21 to a24 in Formulae 1-1 to 1-4 and 2 may each independently be an integer of 1 or 2.

[0090] For example, R in Formulas 1-1 to 1-4 and 2 11 To R 14 and R 21 To R 24 may be independently selected from: a polymerizable group; and C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 3 -C 30 Heterocycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, and C 2 -C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20Haloalkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof, and

[0091] R 21 To R 24 At least one of may be a polymerizable group.

[0092] In some embodiments, R in Formulas 1-1 to 1-4 and 2 11 To R 14 and R 21 To R 24 may be independently selected from: a polymerizable group; and C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, and / or C 7 -C 30 Arylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20Alkylthio, C 1 -C 20 Haloalkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof, and

[0093] R 21 To R 24 At least one of may be a polymerizable group.

[0094] In some embodiments, in Formulas 1-1 to 1-4 and 2, R 11 To R 14 and R 21 To R 24 Each may be independently selected from a polymerizable group and / or one of Formulas 3-1 to 3-15:

[0095]

[0096] Among them, in formulas 3-1 to 3-15,

[0097] At least one hydrogen may be optionally replaced by deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkoxy, C 1 -C 20 It can be replaced by a haloalkylthio group, or a combination thereof.

[0098] In an embodiment, R in Formula 2 21 To R 24Each may independently be a polymerizable group.

[0099] In an embodiment, R in Formulas 1-1 to 1-4 11 To R 14 is not a polymerizable group, and R in Formula 2 21 To R 24 Each may independently be a polymerizable group.

[0100] The polymerizable group may be selected from: an azide group; an isocyanate group; and an epoxy group, an oxetane group, a C 2 -C 30 Alkenyl, and C 2 -C 30 Alkynyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0101] In some embodiments, the polymerizable group may be selected from: an azide group; an isocyanate group; and an epoxy group, an oxetane group, a vinyl group, and an acetylene group, each of which is unsubstituted or substituted with: a deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylate 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 anhydride moiety, a C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0102] b11 to b14 and b21 to b24 in Formulae 1-1 to 1-4 and 2 refer to substituents R 11 The number of substituents R 14 The number and substituents R 21 The number of substituents R 24 The number of, and for example, b11 to b14 and b21 to b24 in Formulae 1-1 to 1-4 and 2 may each independently be 1 or 2.

[0103] R 11 To R 14 and R 21 To R 24 Adjacent two of may optionally be bonded to each other to form a ring.

[0104] For example, multiple R 11Two adjacent R 12 Two adjacent R 13 Two adjacent R 14 Two adjacent ones of the rings may selectively bind to each other to form a ring.

[0105] In some embodiments, multiple R 21 Two adjacent R 22 Two adjacent R 23 Two adjacent R 24 Two adjacent ones of the rings may selectively bind to each other to form a ring.

[0106] R 11 To R 14 Two adjacent ones of R may selectively combine with each other to form a ring, and R 21 To R 24 Two adjacent ones of the rings may selectively bind to each other to form a ring.

[0107] For example, Y in Formulas 1-1 to 1-4 11 To Y 13 They may each independently be O, OC(═O), S, or SC(═O).

[0108] For example, X in Formulas 1-1 to 1-4 11 To X 14 may be independently selected from: hydrogen; deuterium; and C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 1 -C 30 Alkoxy, C 1 -C 30 Alkylthio, C 1 -C 30 Haloalkoxy, C 1 -C 30 Halogenated alkylthio, C 3 -C 30 Cycloalkyl, C 3 -C 30 Cycloalkoxy, C 3 -C 30 Cycloalkylthio, C 3 -C 30 Heterocycloalkyl, C 2 -C 30 Alkenyl, C3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 6 -C 30 Aryloxy, C 6 -C 30 Arylthio, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, C 1 -C 30 Heteroaryloxy, C 1 -C 30 Heteroarylthio, and C 2 -C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Haloalkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0109] In some embodiments, X in Formulas 1-1 to 1-4 11 To X 14 may be independently selected from: hydrogen; deuterium; and C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, and C 2 -C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 aryl, or a combination thereof.

[0110] In some embodiments, X in Formulas 1-1 to 1-4 11 To X 14 may be independently selected from: hydrogen; deuterium; and C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 2 -C 30 Alkynyl, and C 6 -C 30 Aryl: deuterium, a halogen atom, or a combination thereof.

[0111] In some embodiments, X in Formulas 1-1 to 1-4 11 To X 14 Each independently may be: hydrogen; deuterium; and methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl, each of which is unsubstituted or substituted with: deuterium, a halogen atom, methyl, ethyl, phenyl, naphthyl, or a combination thereof.

[0112] In an embodiment, the first organometallic compound may be represented by one of Formulae 1-1 to 1-3.

[0113] In an embodiment, the first organometallic compound represented by one of Formulae 1-1 to 1-4 may be selected from Group I:

[0114]

[0115]

[0116] n in group I can be an integer from 1 to 4.

[0117] For example, n in group I may be 2.

[0118] In an embodiment, the second organometallic compound represented by Formula 2 may be selected from Group II: Group II

[0119]

[0120] Although not limited to a particular theory, free radicals may be formed from the first organometallic compound and the second organometallic compound by heat and / or high-energy rays. Specifically, free radicals may be formed from the M of the first organometallic compound and the second organometallic compound. 11 -Carbon bond and M 21 -carbon bond formation, and optionally in an atmosphere in which water is present, the free radicals are reacted to form a chemical bond between the first organometallic compound and / or the second organometallic compound. As a result, the physical properties of the first organometallic compound and / or the second organometallic compound, such as its solubility in a developer, can be changed.

[0121] In particular, due to the inclusion of one or more polymerizable groups, the second organic metal compound can react with free radicals generated by the first organic metal compound to form crosslinks. Therefore, the resist composition further including the second organic metal compound has improved photosensitivity compared to the resist composition not including the second organic metal compound.

[0122] The first organometallic compound may be one type of Formulae 1-1 to 1-4, or a mixture of two or more types thereof.

[0123] Likewise, the second organometallic compound may be one type represented by Formula 2, or a mixture of two or more types thereof.

[0124] Based on 100 parts by weight of the resist composition, the amount of the first organometallic compound in the resist composition can be from about 0.01 parts by weight to about 99.99 parts by weight, for example, 0.2 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, or 1.5 parts by weight or more and 90 parts by weight or less, or 80 parts by weight or less. Within these ranges, chemical bonds between the organometallic compounds are formed, for example, sufficiently formed, while side reactions are suppressed or otherwise reduced in likelihood, thereby providing a resist composition with improved sensitivity and / or resolution.

[0125] Based on 100 parts by weight of the resist composition, the amount of the second organometallic compound in the resist composition can be from about 0.01 parts by weight to about 99.99 parts by weight, for example, 0.2 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, or 1.5 parts by weight or more and 90 parts by weight or less, or 80 parts by weight or less. Within these ranges, chemical bonds between the organometallic compounds are formed, for example, sufficiently formed, while side reactions are suppressed or otherwise reduced in likelihood, thereby providing a resist composition with improved sensitivity and / or resolution.

[0126] The amount of the second organometallic compound in the resist composition may be from about 0.1 parts by weight to about 100,000 parts by weight based on 100 parts by weight of the first organometallic compound. In some embodiments, the second organometallic compound may be included in an amount from about 5 parts by weight to about 100 parts by weight, for example, from about 10 parts by weight to about 20 parts by weight, based on 100 parts by weight of the first organometallic compound. Within these ranges, the photosensitivity of the resist composition may be improved.

[0127] The solubility of the resist composition to the developer is changed by exposure to high-energy rays. The resist composition may be a negative resist composition. That is, the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern.

[0128] In addition, the resist composition according to the embodiment may be used in an alkaline development process using an alkaline developer for development when forming a resist pattern, or in a solvent development process using a developer including an organic solvent (hereinafter, also referred to as an organic developer).

[0129] The resist composition may be non-chemically amplified, in which case, it may substantially exclude a photoacid generator.

[0130] Since physical properties of the first and second organometallic compounds are changed by exposure, the resist composition may substantially exclude compounds having a molecular weight of 1,000 or more, except for the first and second organometallic compounds.

[0131] The first organometallic compound and the second organometallic compound may be prepared by any appropriate method, or commercially available products may be used.

[0132] The structure (composition) of the first organometallic compound can be determined by Fourier transform infrared (FT-IR) analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, ultraviolet (UV) analysis, single crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC), size exclusion chromatography (SEC) analysis, thermal analysis, etc. The detailed confirmation method is described in the following examples.

[0133] <Organic Solvents>

[0134] The resist composition may further include an organic solvent.

[0135] The organic solvent included in the resist composition is not particularly limited as long as the first organometallic compound and the second organometallic compound and the optional components included therein as required can be dissolved or dispersed therein. As the organic solvent, one type of organic solvent can be used, or two or more different types of organic solvents can be used in combination.

[0136] In an embodiment, the organic solvent may include a protic organic solvent, an aprotic organic solvent, or a combination thereof.

[0137] In some embodiments, the organic solvent may be a mixture including an aprotic organic solvent and a protic organic solvent.

[0138] Since the resist composition may not substantially include water, the organic solvent may not include water. In an embodiment, the resist composition may include no more than 3 wt % of water, and the organic solvent may include no more than 3 wt % of water.

[0139] Examples of the organic solvent are alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, hydrocarbon-based solvents, and / or the like.

[0140] Examples of the alcohol-based solvent are monohydric alcohol-based solvents such as 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-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc.; polyol solvents such as ethylene glycol, 1,2-propylene glycol, 1, 3-Butanediol, 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; and ether solvents including polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono Phenyl 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, dipropylene glycol monopropyl ether and / or the like.

[0141] Examples of the ether-based solvent are: diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether; dialkyl ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, etc.; cyclic ether-based solvents such as tetrahydrofuran, tetrahydropyran, etc.; and ether-based solvents including an aromatic ring such as diphenyl ether, anisole and / or the like.

[0142] Examples of the ketone-based solvent are chain ketone-based solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, or trimethylnonanone, cyclic ketone-based solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, or methylcyclohexanone, 2,4-pentanedione, acetonylacetone, and / or acetophenone.

[0143] Examples of the amide-based solvent are cyclic amide-based solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone, and chain amide-based solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, or N-methylpropionamide.

[0144] Examples of the ester-based solvent are: an acetate-based solvent such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, and / or n-nonyl acetate; a solvent based on ether carboxylates including polyhydric alcohols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and / or dipropylene glycol monoethyl ether acetate; lactone solvents, such as γ-butyrolactone and / or δ-valerolactone; carbonate-based solvents, such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and / or propylene carbonate; and lactate-based solvents, such as methyl lactate, ethyl lactate, n-butyl lactate, and / or n-amyl lactate; ethylene glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate, and / or diethyl phthalate.

[0145] Examples of the sulfoxide-based solvent are dimethyl sulfoxide and / or diethyl sulfoxide.

[0146] Examples of the hydrocarbon-based solvent are aliphatic or alicyclic hydrocarbon-based solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, or methylcyclohexane; and / or aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, or n-pentylnaphthalene.

[0147] In some embodiments, the organic solvent may be selected from alcohol-based solvents, ketone-based solvents, ester-based solvents, and any combination thereof. In some embodiments, the organic solvent may be selected from 4-methyl-2-pentanol (MIBC), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and / or a combination thereof.

[0148] Based on 100 parts by weight of the resist composition, the organic solvent can be used in an amount of about 0 parts by weight to about 99.9 parts by weight, such as 0.1 parts by weight or more, 1 part by weight or more, 5 parts by weight or more, or 10 parts by weight or more, and 99 parts by weight or less, 98 parts by weight or less, or 95 parts by weight or less. The organic solvent can be used alone, or any mixture of two or more different solvents can also be used.

[0149] <Optional Components>

[0150] As required, the resist composition may further include a surfactant, a crosslinking agent, a leveling agent, a colorant, or a combination thereof.

[0151] The resist composition may further include a surfactant to improve coating properties, developability, etc. The example of the surfactant may 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 or polyethylene glycol distearate. As the surfactant, any commercially available product or synthetic product can be used. The example of the commercially available product of the surfactant is KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75 and Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., LTD.), Eftop EF301, Eftop 303 and Eftop 352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE TM F171、MEGAFACE TM F173, R-40, R-41, and R-43 (products manufactured by DIC Corporation), Fluorad TM FC430 and Fluorad TM FC431 (manufactured by Sumitomo 3M, Ltd.), Asahi Guard TMAG710 (manufactured by AGC Seimi Chemical Co., Ltd.), and Surflon TM S-382, Surflon TM SC-101, Surflon TM SC-102, Surflon TM SC-103, Surflon TM SC-104, Surflon TM SC-105, and / or Surflon TM SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0152] The resist composition may include the surfactant in an amount ranging from about 0 parts by weight to about 20 parts by weight based on 100 parts by weight of the resist composition. As the surfactant, one type of surfactant may be used, or two or more different types of surfactants may be mixed and used.

[0153] The method for preparing the resist composition is not particularly limited, and the resist composition can be prepared by, for example, mixing the organometallic compound and optional components added as needed. The temperature or time during mixing is not particularly limited. If necessary, filtering can be performed after mixing.

[0154] [Pattern Formation Method]

[0155] In the following, reference will be made to Figure 1 and 2A 2C describe the pattern forming method according to the embodiment in more detail. Figure 1 is a flowchart showing a pattern forming method according to an embodiment, and Figures 2A to 2C Each is a side cross-sectional view illustrating a pattern forming method according to an embodiment. Hereinafter, a pattern forming method using a negative resist composition will be described as an example, but the embodiment is not limited thereto.

[0156] Reference Figure 1 , the pattern forming method may include: an operation S101 of applying a resist composition to form a resist film, an operation S102 of exposing at least a portion of the resist film to high-energy rays, and an operation S103 of developing the exposed resist film using a developer. If necessary, such operations may be omitted or may be performed in a different order.

[0157] First, a substrate 100 may be prepared. The substrate 100 may include, for example, a semiconductor substrate such as a silicon substrate or a germanium substrate, glass, quartz, ceramic, or copper. In some embodiments, the substrate 100 may include a group III-group V compound such as GaP, GaAs, GaSb, etc.

[0158] The resist composition can be applied to the substrate 100 to a desired thickness by, for example, coating to form a resist film 110. If necessary, the resist film 110 can be heated (pre-baked, PB) to remove the organic solvent remaining therein. In some embodiments, by heating the resist film 110, free radicals can be generated, and then by exposure, the free radicals can be chemically combined to form crosslinks.

[0159] As coating method, spin coating, dipping, roller coating or other common coating methods can be used. In these coating methods, in particular, spin coating can be used, and the viscosity, concentration and / or rotation speed of the resist composition can be adjusted to form a resist film 110 with a desired thickness. In some embodiments, the resist film 110 can have a thickness of about 10nm to about 300nm. In some embodiments, the resist film 110 can have a thickness of about 30nm to about 200nm.

[0160] The lower limit of the temperature of PB may be 60° C. or higher, or 80° C. or higher. In some embodiments, the upper limit of the temperature of PB may be 150° C. or lower, or 140° C. or lower. The lower limit of the time of PB may be 5 seconds or more, or 10 seconds or more. The upper limit of the time of PB may be 600 seconds or less, or 300 seconds or less.

[0161] Before the resist composition is applied to the substrate 100, an etching target film (not shown) may be further formed on the substrate 100. The etching target film may refer to a layer to which an image is transferred from a resist pattern and converted into a certain pattern. In an embodiment, the etching target film may be formed to include, for example, an insulating material such as silicon oxide, silicon nitride, and silicon oxynitride. In some embodiments, the etching target film may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicon nitride. In some embodiments, the etching target film may be formed to include a semiconductor material such as polysilicon.

[0162] In an embodiment, an anti-reflection film may be further formed on the substrate 100 to maximize the efficiency of the resist. The anti-reflection film may be an organic or inorganic anti-reflection film.

[0163] In an embodiment, a protective film may be further provided on the resist film 110 to reduce the influence of alkaline impurities etc. included during the process. When immersion exposure is performed, for example, a protective film for immersion may also be formed on the resist film 110 to avoid direct contact between the immersion medium and the resist film 110.

[0164] Next, at least a portion of the resist film 110 may be exposed to high energy rays. For example, high energy rays may be irradiated onto at least a portion of the resist film 110 through the mask 120. Thus, the resist film 110 may have an exposed portion 111 and an unexposed portion 112.

[0165] Although not limited to a particular theory, free radicals are generated in the exposed portion 111 by exposure, and chemical bonds are formed between the free radicals, which may change the physical properties of the resist composition.

[0166] In some cases, exposure can be performed by irradiating high-energy rays through a mask having a certain pattern using a liquid such as water as a medium. Examples of the high-energy rays may include electromagnetic waves such as ultraviolet rays, deep ultraviolet rays, extreme ultraviolet (EUV) rays (wavelength of 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams (EB) and alpha particle beams. Irradiation with high-energy rays may be collectively referred to as "exposure".

[0167] A variety of light sources can be used for exposure. For example, a light source emitting a laser beam in the UV range, such as a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), and an F2 excimer laser (wavelength of 157 nm), a light source (YAG or semiconductor laser) emitting a harmonic laser beam in the far ultraviolet or vacuum ultraviolet range by converting the wavelength of a laser beam received from a solid laser light source, and / or a light source emitting EB or EUV can be used. During exposure, exposure can usually be performed through a mask corresponding to a desired pattern, but when the exposure light is EB, exposure can be performed by direct writing without using a mask.

[0168] When extreme ultraviolet rays are used as high-energy rays, the integrated dose of the high-energy rays may be 2000 mJ / cm 2 or less, or 500mJ / cm 2 Or less. In addition, when EB is used as high-energy ray, the integrated dose can be 5000μC / cm 2 or less, or 1000μC / cm 2 or less.

[0169] In addition, a post-exposure bake (PEB) may be performed after exposure. The lower limit of the temperature of the PEB may be 50° C. or higher, or 80° C. or higher. The upper limit of the temperature of the PEB may be 250° C. or lower, or 200° C. or lower. The lower limit of the time of the PEB may be 5 seconds or more, or 10 seconds or more. The upper limit of the time of the PEB may be 600 seconds or less, or 300 seconds or less.

[0170] Next, the exposed resist film 110 may be developed using a developer. The unexposed region 112 may be removed by being washed away by the developer, and the exposed portion 111 remains without being washed away by the developer.

[0171] Examples of the developer are alkaline developers and / or developers including organic solvents (hereinafter also referred to as "organic developers"). Examples of the developing method are dipping, spinning immersion, spraying, dynamic injection, etc. The developing temperature may be, for example, 5° C. or higher and 60° C. or lower, and the developing time may be, for example, 5 seconds or more and 300 seconds or less.

[0172] The alkaline developer may include, for example, an alkaline aqueous solution in which one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, TMAH (tetramethylammonium hydroxide), 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 include a surfactant.

[0173] The lower limit of the amount of the alkaline compound included in the alkaline developer may be 0.1 wt % or more, or 0.5 wt % or more, or 1 wt % or more. In an embodiment, the upper limit of the amount of the alkaline compound included in the alkaline developer may be 20 wt % or less, or 10 wt % or less, or 5 wt % or less.

[0174] Examples of the organic solvent included in the organic developer may include the same organic solvents as those in the section of <Organic Solvent> of [Resist Composition]. In an embodiment, the organic developer may be n-butyl acetate (nBA), propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), γ-butyrolactone (GBL), isopropyl alcohol (IPA), etc. The organic developer may further include an organic acid such as acetic acid, formic acid, citric acid, etc.

[0175] Regarding the organic developer, the lower limit of the amount of the organic solvent may be 80 wt % or more, 90 wt % or more, 95 wt % or more, or 99 wt % or more.

[0176] The organic developer may further include a surfactant. In addition, the organic developer may include a trace amount of water. In some embodiments, during development, development may be stopped by replacing (displacing) with a solvent of a different type than the organic developer.

[0177] The resist pattern after development may be further cleaned. Ultrapure water, a cleaning solution, etc. may be used as a cleaning solution. The cleaning solution is not particularly limited as long as the cleaning solution does not dissolve the resist pattern, and a solution including a common organic solvent may be used. For example, the cleaning solution may be an alcohol-based solvent or an ester-based solvent. After cleaning, the cleaning solution remaining on the substrate 100 and the resist pattern may be removed. In addition, when ultrapure water is used, water remaining on the substrate 100 and the resist pattern may be removed.

[0178] Furthermore, the developers may be used alone or in combination of two or more.

[0179] After forming the resist pattern as described above, a pattern interconnect substrate can be obtained by etching. The etching can be performed by a known method including dry etching using plasma gas and wet etching using an alkaline solution, a copper (II) chloride solution, an iron (II) chloride solution, etc.

[0180] After the resist pattern is formed, plating may be performed. The plating is not particularly limited, and examples thereof may include copper plating, solder plating, nickel plating, gold plating, and the like.

[0181] The resist pattern remaining after etching can be stripped with an organic solvent. One or more embodiments are not limited thereto, but examples of such organic solvents may include PGMEA, PGME, ethyl lactate (EL), etc. The stripping method is not particularly limited, but examples thereof may include immersion, spraying, etc. In addition, the interconnect substrate on which the resist pattern is formed may be a multilayer interconnect substrate, or may have a small diameter through hole.

[0182] In an embodiment, the interconnect substrate may be formed by forming a resist pattern, depositing a metal in a vacuum, and then melting the resist pattern using a solution (ie, a lift-off method).

[0183] The present disclosure will be described in more detail using the following examples and comparative examples, but the technical scope of the present disclosure is not limited to the following examples.

[0184] [Example]

[0185] Synthesis Example 1: Synthesis of SM1

[0186]

[0187] 8.2g (69.2mmol) of Sn powder and 120ml of dry toluene were added to a 250ml three-necked flask, and the temperature was raised to 90°C. About 1.0ml of DI water was added thereto, and then 10.0g (69.2mmol) of 4-fluorobenzyl chloride was added dropwise for 10 minutes. Heating, reflux, and stirring were performed at 130°C for 4 hours, and then the unreacted Sn powder was filtered using a Buchner funnel. Meanwhile, as the filtered solution cooled, 6.5g of white crystals (SM1 precursor) as a product were obtained (36% yield).

[0188]

[0189] 1.5 g (3.7 mmol) of SM1 precursor and 21.0 ml of dry acetone were added to a 50 ml single-necked flask, and the temperature was lowered to 0° C. 0.6 g (7.4 mmol) of sodium acetate was added, and then stirred for about 12 hours. The NaCl salt produced in the solution was filtered using a 0.45 μm filter, and the resulting solution was rotary evaporated and dried under vacuum to obtain SM1 (1.6 g) with a yield of 74%.

[0190] 1 H-NMR (500 MHz, DMSO-d 6 ): δ~6.9(8H),~2.6(4H),~1.6(6H)

[0191] Evaluation Example 1: Evaluation of Thin Film Development

[0192] (1) Terminology

[0193] E th refers to the exposure dose at the time point when the film begins to cure, and E 1 It refers to the exposure dose at the saturation point where the thickness of the film does not become increased. γ is a contrast curve, and is a value calculated by the following Equation 1.

[0194] Equation 1

[0195]

[0196] (2) Evaluation of the influence of PEB temperature

[0197] Casting solution A-1 was prepared by dissolving 2 wt % of SM1 obtained in Synthesis Example 1 in ethyl lactate. The first solution was prepared by dissolving 2 wt % of tetraallyltin (TAT) in ethyl lactate. Casting solution A-2 was prepared by mixing casting solution AI and the first solution in a weight ratio of 8:1. An 8-inch diameter silicon wafer coated with HMDS (hexamethyldisilazane) was cut into four equal parts and washed with O 2 Plasma treatment for 30 minutes, spin coating with casting solution A-1 and casting solution A-2 at 1500 rpm for 1 minute each, and then drying (PAB) at 90°C for 1 minute, thereby producing a film with an initial thickness of 33.5 nm. Then, a 3.5 mm thick mask (4 cm x 4 cm) with rectangular holes (1 cm x 1 cm) was placed thereon, and each hole was irradiated with 0 mJ / cm 2 Up to 60mJ / cm 2 The film was exposed to DUV at a wavelength of 254 nm at a dose of 1000 nm, and the resulting structure was dried (PEB) for 1 minute at the PEB temperature shown in Table 1. The dried film was immersed in a PGMEA solution containing 2 wt % acetic acid as a developer and then immersed at 25° C. for 60 seconds. The thickness of the remaining film was measured and shown in Table 1.

[0198] [Table 1]

[0199]

[0200] Referring to Table 1, the E of the resist composition of Comparative Example 1-1 is th 、E 1 , and / or γ significantly vary depending on the PEB temperature, whereas the resist composition of Example 1-1 is relatively less affected by the PEB temperature.

[0201] Furthermore, it was confirmed that, under the same PEB temperature conditions, when the resist composition of Example 1-1 was used, E th and E 1 The results show that the resist composition of Example 1-1 has improved photosensitivity compared to the resist composition of Comparative Example 1-1. In addition, as the PEB temperature increases, the effect of improving photosensitivity tends to increase.

[0202] (3) Evaluation based on the content of the second organometallic compound

[0203] Casting solution A-1 was prepared by dissolving 2 wt % of SM1 obtained in Synthesis Example 1 in ethyl lactate. The first solution was prepared by dissolving 2 wt % of tetraallyltin (TAT) in ethyl lactate. Casting solutions B-2, B-3, and B-4 were prepared by mixing casting solution A-1 and the first solution in a weight ratio of 10:1, 8:1, and 7:1, respectively. An 8-inch diameter silicon wafer coated with HMDS was cut into four equal parts and washed with O 2 Plasma treatment was performed for 30 minutes, and casting solutions B-2 to B-4 were spin-coated at 1500 rpm for 1 minute each, followed by drying (PAB) at 90° C. for 1 minute, thereby producing films having the initial thicknesses shown in Table 2. Then, a 3.5 mm thick mask (4 cm x 4 cm) having rectangular holes (1 cm x 1 cm) was placed thereon, and each hole was irradiated with 0 mJ / cm 2 Up to 60mJ / cm 2 The film was exposed to DUV at a wavelength of 254 nm at a dose of 1000 nm, and the resulting structure was dried (PEB) at 200° C. for 1 minute. The dried film was immersed in a PGMEA solution containing 2 wt % acetic acid as a developer and then immersed at 25° C. for 60 seconds. The thickness of the remaining film was measured and shown in Table 2.

[0204] [Table 2]

[0205]

[0206] Referring to Table 2, it is confirmed that the E th The change in E is not significant, and 1 It is about 10 mJ to about 20 mJ. In addition, γ in Example 2-1 was confirmed to be the largest.

[0207] Figures 3A to 3E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment.

[0208] Reference Figure 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 be a multilayer structure. The material of the material layer 130 may be different from the material of the substrate 100. The resist film 110 may include a resist composition according to an example embodiment, and may have a thickness of about 10 nm to about 300 nm, or about 30 nm to about 200 nm.

[0209] Reference Figure 3B, the resist film 110 may be exposed to high energy rays through the mask 120 , after which the resist film 110 may include an exposed region 111 and an unexposed region 112 .

[0210] Reference Figure 3C The exposed resist film 110 may be developed using a developer (eg, a developing solution). The exposed portion 111 may remain without being washed away by the developing solution, while the unexposed portion 112 may be washed away by the developing solution.

[0211] Reference Figure 3D , the exposed region 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 .

[0212] Reference Figure 3E , the resist pattern 110 may be removed.

[0213] Figures 4A to 4E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment.

[0214] Reference Figure 4A , a gate dielectric 505 (eg, silicon oxide) may be formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (eg, doped polysilicon) may be formed on the gate dielectric 505. A hard mask layer 520 may be formed on the gate layer 515.

[0215] Reference Figure 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 example embodiments. The resist pattern 540b may be formed of a resist composition including an organic solvent and optionally a surfactant, a crosslinking agent, a leveling agent, a colorant, or a combination thereof as needed.

[0216] Reference Figure 4C , the hard mask layer 520, 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.

[0217] Reference Figure 4D , the hard mask pattern 520a may be optionally removed, and 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 forming the spacers 535a, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0218] Reference Figure 4E , an interlayer insulating layer 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 may be formed in the interlayer insulating layer 560 to connect to the gate electrode 515a and the S / D region. The electrical contacts may be formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating layer 560 and the electrical contacts 570a, 570b, and 570c. Although Figures 4A to 4E An example of forming a transistor is shown, but the inventive concept is not limited thereto.

[0219] The resist composition according to one or more embodiments may be used in a patterning process to form other types of semiconductor devices.

[0220] According to an embodiment, a resist composition having improved storage stability and improved sensitivity and providing a pattern with increased resolution may be provided.

[0221] It should be understood that the embodiments described herein should be considered in a descriptive sense only and not for limiting purposes. The description of features or aspects within each embodiment should typically be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope as defined by the appended claims.

Claims

1. A resist composition comprising: A first organometallic compound represented by one of Formulae 1-1 to 1-4; and The second organometallic compound represented by Formula 2, wherein The first organometallic compound and the second organometallic compound are different from each other: Wherein, in Formulas 1-1 to 1-4 and 2, M 11 and M 21 Each is independently selected from indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), L 11 To L 14 and L 21 To L 24 Each independently is a single bond or a linear, branched or cyclic C1-C 30 Divalent hydrocarbon groups, a11 to a14 and a21 to a24 are each independently an integer of 1 to 4, R 11 To R 14 and R 21 To R 24 Each independently represents a polymerizable group, a substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Heterocycloalkyl, substituted or unsubstituted C2-C 30 Alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocycloalkenyl, substituted or unsubstituted C2-C 30 Alkynyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C7-C 30 Arylalkyl, substituted or unsubstituted C1-C 30 heteroaryl, or substituted or unsubstituted C2-C 30 Heteroarylalkyl, R 21 To R 24 at least one of which is a polymerizable group, R 11 To R 14 and R 21 To R 24 Adjacent two of are optionally bonded to each other to form a ring, b11 to b14 and b21 to b24 are each independently an integer of 1 to 4, Y 11 To Y 13 Each independently represents O, OC(=O), S, SC(=O), NX 14 , or NX 14 C(=O), and X 11 To X 14 are each independently hydrogen, deuterium, or a linear, branched or cyclic C1-C 30 A monovalent hydrocarbon group.

2. The resist composition according to claim 1, wherein M 11 and M 21 Each independently represents In, Sn, or Sb.

3. The resist composition according to claim 1, wherein L 11 To L 14 and L 21 To L 24 are each independently a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, substituted or unsubstituted C3-C 30 Heterocycloalkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Heterocycloalkenylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C1-C 30 Heteroarylene.

4. The resist composition according to claim 1, wherein R 11 To R 14 and R 21 To R 24 Each independently selected from: a polymerizable group; and C1-C 30 Alkyl, C3-C 30 Cycloalkyl, C3-C 30 Heterocycloalkyl, C2-C 30 Alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocycloalkenyl, C2-C 30 Alkynyl, C6-C 30 Aryl, C7-C 30 Arylalkyl, C1-C 30 Heteroaryl, and C2-C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy, C1-C 20 Halogenated alkylthio, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 Heteroaryl, C6-C 20 Aryloxy, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroarylthio, or a combination thereof, and R 21 To R 24 At least one of the groups is a polymerizable group.

5. The resist composition according to claim 1, wherein R 21 To R 24 Each is independently a polymerizable group.

6. The resist composition according to claim 1, wherein R 11 To R 14 are each independently not a polymerizable group, and R 21 To R 24 Each is independently a polymerizable group.

7. The resist composition according to claim 1, wherein The polymerizable group is selected from: an azide group; an isocyanate group; and an epoxy group, an oxetane group, a C2-C 30 Alkenyl and C2-C 30 Alkynyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy, C1-C 20 Halogenated alkylthio, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 Heteroaryl, C6-C 20 Aryloxy, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroarylthio, or a combination thereof.

8. The resist composition according to claim 1, wherein The polymerizable group is selected from: an azide group; an isocyanate group; and an epoxy group, an oxetane group, a vinyl group and an acetylene group, each of which is unsubstituted or substituted with: a deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylate 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 anhydride moiety, a C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy, C1-C 20 Halogenated alkylthio, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 Heteroaryl, C6-C 20 Aryloxy, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroarylthio, or a combination thereof.

9. The resist composition according to claim 1, wherein The first organometallic compound is represented by one of Formulas 1-1 to 1-3, and Y 11 To Y 13 Each is independently O, OC(═O), S, or SC(═O).

10. The resist composition according to claim 1, wherein X 11 To X 14 are each independently selected from: hydrogen; deuterium; and C1-C 30 Alkyl, C1-C 30 Halogenated alkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy, C1-C 30 Halogenated alkylthio, C3-C 30 Cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocycloalkyl, C2-C 30 Alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocycloalkenyl, C2-C 30 Alkynyl, C6-C 30 Aryl, C6-C 30 Aryloxy, C6-C 30 Arylthio, C7-C 30 Arylalkyl, C1-C 30 Heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 Heteroarylthio, and C2-C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate 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, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy, C1-C 20 Halogenated alkylthio, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 Heteroaryl, C6-C 20 Aryloxy, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroarylthio, or a combination thereof.

11. The resist composition according to claim 1, wherein The first organometallic compound is represented by one of Formulae 1-1 to 1-3.

12. The resist composition according to claim 1, wherein The first organometallic compound represented by one of Formulae 1-1 to 1-4 is selected from Group I: Group I Wherein n in group I is an integer from 1 to 4.

13. The resist composition according to claim 1, wherein The second organometallic compound represented by Formula 2 is selected from Group II: Group II 14. The resist composition according to claim 1, wherein The second organometallic compound is included in an amount of about 0.1 parts by weight to about 100,000 parts by weight based on 100 parts by weight of the first organometallic compound.

15. The resist composition according to claim 1, wherein The resist composition substantially excludes a photoacid generator.

16. The resist composition according to claim 1, wherein The resist composition substantially does not include a compound having a molecular weight of 1,000 or more.

17. A pattern forming method comprising: forming a resist film by applying the resist composition according to any one of claims 1 to 16 to a substrate; exposing at least a portion of the resist film to high energy radiation to provide an exposed resist film; as well as The exposed resist film is developed using a developer.

18. The pattern forming method according to claim 17, wherein Exposing at least a portion of the resist film is performed by irradiating the resist film with at least one of deep ultraviolet (DUV) rays, extreme ultraviolet (EUV) rays, or electron beams (EB).

19. The pattern forming method according to claim 17, wherein During exposure of at least a portion of the resist film to light, the first organometallic compound and the second organometallic compound undergo a cross-linking reaction.

20. The pattern forming method according to claim 17, wherein The exposed resist film includes an exposed portion and an unexposed portion, and In the development, the unexposed portion is removed.

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