Organometal compound, resist composition including the same, and pattern forming method using the resist composition

Abstract

Provided are an organometallic compound represented by one of formulae 1-1 to 1-4 in which M11, Q11 to Q14, b11 to b14, R11 to R14, Y11 to Y13, and X11 to X13 are as described in the specification, a resist composition including the same, and a pattern forming method using the resist composition. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0128482 filed on September 25, 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 an organometallic compound, a resist composition including the same, and a pattern forming method using the resist composition. Background Art

[0004] In the manufacture of semiconductors, resists that undergo changes in physical properties in response to light are used to form micropatterns. Among these resists, chemically amplified resists are widely used. In the case of chemically amplified resists, the acid formed by the reaction between light and a photoacid generator (photoacid generator) reacts again with a base resin to change the solubility of the base resin in 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. In embodiments, for 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, to overcome the limitations of chemically amplified resists, attempts have been made to develop materials whose physical properties change as a result of exposure to light. However, the dose required for exposure is still high. Summary of the invention

[0007] Provided are a resist composition whose properties are changed even with 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, the organometallic compound may be represented by one of Formulae 1-1 to 1-4:

[0010]

[0011] In formulas 1-1 to 1-4,

[0012] M 11It may be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi) or polonium (Po),

[0013] Q 11 To Q 14 may be independently 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, or substituted or unsubstituted C 1 -C 30 Heteroaryl,

[0014] b11 can be 2 or 3,

[0015] b12 to b14 may each independently be an integer from 0 to 3,

[0016] R 11 To R 14 can be independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, carboxylic acid group, 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, or substituted or unsubstituted C 1 -C 30 Heteroaryl,

[0017] Q 11 To Q 14 and R 11 To R 14 Adjacent two of may be optionally bonded to each other to form a ring (eg, a fused ring),

[0018] Y 11 To Y 13 can be independently O, O(C=O), S, S(C=O), NX 14 or NX 14 (C=O), and

[0019] X 11 To X 14 may be independently: hydrogen; deuterium; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 30 A monovalent hydrocarbon group.

[0020] According to example embodiments, a resist composition may include the organometallic compound.

[0021] According to example embodiments, a pattern forming method may include forming a resist film by applying the resist composition on 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

[0022] The above and other aspects, features, and advantages of some embodiments of the present disclosure will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0023] Figure 1 FIG. 1 is a flow chart showing a pattern forming method according to an embodiment.

[0024] FIG. 2A to FIG. 2C is a side cross-sectional view showing a pattern forming method according to an embodiment;

[0025] Figures 3A to 3C To display A-2 1 H-NMR data, 13 C-NMR data and 119 Plots of Sn-NMR data;

[0026] Figures 4A to 4C To display A-1 1 H-NMR data, 13 C-NMR data and 119 Plots of Sn-NMR data;

[0027] Figures 5A to 5C To display the OM-A 1 H-NMR data, 13 C-NMR data and 119 Plots of Sn-NMR data;

[0028] Figures 6A to 6CTo show B-2 1 H-NMR data, 13 C-NMR data and 119 Plots of Sn-NMR data;

[0029] Figures 7A to 7C To display B-1 1 H-NMR data, 13 C-NMR data and 119 Plots of Sn-NMR data;

[0030] Figures 8A to 8C To display the OM-B 1 H-NMR data, 13 C-NMR data and 119 Plots of Sn-NMR data;

[0031] Figures 9A to 9E are graphs showing changes in film thickness (THK) after development depending on the dose of Examples 1-1 to 1-5, respectively;

[0032] Fig.10 is a graph showing changes in film thickness after development depending on the dose of Example 2-1;

[0033] Figures 11A to 11C Graphs showing changes in film thickness after development depending on the dose for Comparative Examples 1 to 3, respectively.

[0034] Figures 12A to 12E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment; and

[0035] Figures 13A to 13E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION

[0036] Embodiment will now be introduced in detail, and its example is 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, the embodiment is described below with reference to the accompanying drawings to illustrate aspects. 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 of A, B and C" and similar language (e.g., "selected from at least one of A, B and C", "at least one 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.

[0037] When the term "about" or "substantially" is used in this specification with respect to a numerical value, 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 with respect to a geometric shape, it is intended that the accuracy of the geometric shape is not required, but tolerance for the shape is within the scope of the present disclosure. In addition, regardless of whether a numerical value or shape is modified with "about" or "substantially", it will be understood that these values ​​and shapes should be interpreted as including a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value or shape.

[0038] Since the following disclosure allows for various changes and many embodiments, specific embodiments will be shown in the drawings and described in detail in the written description. However, this is not intended to limit the present disclosure to a specific mode of practice, and it will be understood that all modifications, equivalents, and substitutes that do not depart from the spirit and technical scope of the present disclosure are included in the present disclosure. In the following description of the present disclosure, when the introduction of a detailed description of known functions and configurations (configurations) herein may obscure the subject matter of the present disclosure, it will be omitted.

[0039] Although the terms “first,” “second,” “third,” etc. may be used herein to describe various elements, these terms are only used to distinguish one element from another, and the order, type, etc. of the elements are not limited thereby.

[0040] Throughout the specification, it will be understood that when an element such as a layer, film, region, or plate is referred to as being “on” another element, it can be in direct contact with the other element or intervening elements may be present therebetween.

[0041] Expressions used in the singular encompass expressions in the plural, unless it has a clearly different meaning in the context. In this specification, it will be understood that terms such as "including" or "having" are intended to indicate the presence of features, numbers, operations, elements, parts, components, materials, or combinations thereof disclosed in this specification, and are not intended to exclude the possibility that one or more other features, numbers, operations, elements, parts, components, materials, or combinations thereof may exist or may be added, unless otherwise stated.

[0042] Whenever a range of values ​​is recited, the range includes all values ​​corresponding to the range, as if explicitly recited, and also includes the boundaries of the range. Thus, the range "X to Y" includes all values ​​between X and Y, including X and Y.

[0043] As used herein, the term "C x -C y" means that the number of carbon atoms constituting a substituent or group is in the range of x to y. For example, the term "C 1 -C 6 " means that the number of carbon atoms constituting the substituent or group is in the range of 1 to 6, and the term "C 6 -C 20 " means that the number of carbon atoms constituting the substituent or group is in the range of 6 to 20.

[0044] The term "monovalent hydrocarbon group" as used herein refers to a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and examples thereof include: a straight-chain 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, tricyclodecyl, tetracyclododecyl); yl, tetracyclododecylmethyl and dicyclohexylmethyl); monovalent unsaturated aliphatic hydrocarbon groups (alkenyl and alkynyl) (e.g., allyl); monovalent unsaturated alicyclic hydrocarbon groups (cycloalkenyl) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl, 1-naphthyl and 2-naphthyl); aralkyl groups (e.g., benzyl and diphenylmethyl); monovalent hydrocarbon groups containing heteroatoms (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl and 3-oxocyclohexyl); or combinations thereof. In an embodiment, since in these groups, some hydrogen atoms may be replaced by a moiety including a heteroatom such as oxygen, sulfur, nitrogen or a halogen atom, or some carbon atoms may be replaced by a moiety including a heteroatom such as oxygen, sulfur or nitrogen, the group may include a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond (linker), an ester bond (linker), a sulfonate bond (linker), a carbonate bond (linker), a lactone ring, a sultone ring, a carboxylic anhydride moiety, or a halogenated alkyl moiety.

[0045] The term "divalent hydrocarbon group" as used herein is a divalent residue and means that any one hydrogen of the monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. The divalent hydrocarbon group may include, for example, linear or branched alkylene, cycloalkylene, alkenylene, alkynylene, cycloalkylene, arylene, and those in which some carbon atoms are replaced by heteroatoms.

[0046] As used herein, the term "alkyl" refers to a straight or branched saturated aliphatic monovalent hydrocarbon group, and non-limiting examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl. As used herein, the term "alkylene" refers to a straight or branched saturated aliphatic divalent hydrocarbon group, and non-limiting examples thereof may include methylene, ethylene, propylene, butylene and isobutylene.

[0047] The term "haloalkyl" as used herein refers to a group in which at least one hydrogen of an alkyl group is replaced by a halogen, and non-limiting examples thereof may include CF 3 In this regard, the halogen atom is F, Cl, Br or I.

[0048] As used herein, the term "alkoxy" refers to a group having the formula -OA 101 A monovalent group, where A 101 is an alkyl group. Examples thereof include methoxy, ethoxy and isopropoxy.

[0049] As used herein, the term "alkylthio" refers to a group having the formula -SA 101 A monovalent group, where A 101 It may be an alkyl group.

[0050] The term "haloalkoxy" as used herein refers to a group in which at least one hydrogen of an alkoxy group is replaced by a halogen, and non-limiting examples thereof include -OCF 3 .

[0051] The term "haloalkylthio" as used herein refers to a group in which at least one hydrogen of an alkylthio group is replaced by a halogen, and non-limiting examples thereof may include -SCF 3 .

[0052] The term "cycloalkyl" as used herein refers to a cyclic saturated monovalent hydrocarbon group, and examples thereof may include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, and polycyclic condensed groups such as norbornyl and adamantyl. The term "cycloalkylene" as used herein refers to a cyclic saturated divalent hydrocarbon group, and non-limiting examples thereof may include cyclopentylene, cyclohexylene, adamantylene, adamantylene methyl, norbornylene, norbornylene methyl, tricyclodecylene, tetracyclododecylene, tetracyclododecylene methyl and dicyclohexylene methyl.

[0053] The term "cycloalkoxy" refers to a cycloalkyloxy group having the formula -OA 102 A monovalent group, where A 102 It may be a cycloalkyl group. Examples thereof include cyclopropyloxy and cyclobutyloxy.

[0054] As used herein, the term "cycloalkylthio" refers to a group having the formula -SA102 A monovalent group, where A 102 It may be a cycloalkyl group.

[0055] As used herein, the term "heterocycloalkyl" may refer to a group in which some of the carbon atoms of a cycloalkyl group may be replaced by a portion containing a heteroatom such as oxygen, sulfur or nitrogen, and the heterocycloalkyl group may contain, for example, an ether bond, an ester bond, a sulfonate bond, a carbonate, a lactone ring, a sultone ring or a carboxylic anhydride portion. As used herein, the term "heterocycloalkylene" may be a group in which some of the carbon atoms of a cycloalkylene group are replaced by a portion containing a heteroatom such as oxygen, sulfur or nitrogen.

[0056] As used herein, the term "heterocycloalkoxy" refers to a 103 A monovalent group, where A 103 It may be a heterocycloalkyl group.

[0057] As used herein, the term "alkenyl" refers to a linear or branched unsaturated aliphatic monovalent hydrocarbon group containing at least one carbon-carbon double bond. As used herein, the term "alkenylene" refers to a linear or branched unsaturated aliphatic divalent hydrocarbon group containing at least one carbon-carbon double bond.

[0058] The term "cycloalkenyl" as used herein refers to a cyclic unsaturated monovalent hydrocarbon group containing at least one carbon-carbon double bond. The term "cycloalkenylene" as used herein refers to a cyclic unsaturated divalent hydrocarbon group containing at least one carbon-carbon double bond.

[0059] The term "heterocycloalkenyl" as used herein may be a group in which some of the carbon atoms of a cycloalkenylene group are replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen. The term "heterocycloalkenyl" as used herein may be a group in which some of the carbon atoms of a cycloalkenylene group are replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen.

[0060] The term "alkynyl" as used herein refers to a straight-chain or branched unsaturated aliphatic monovalent hydrocarbon group containing at least one carbon-carbon triple bond.

[0061] The term "aryl" as used herein refers to a monovalent group having a carbocyclic aromatic system, and non-limiting examples thereof may include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, and The term "arylene" as used herein refers to a divalent group having a carbocyclic aromatic system.

[0062] The term "heteroaryl" as used herein refers to a monovalent group having a heterocyclic aromatic system, and non-limiting examples thereof may include pyridyl, pyrimidyl and pyrazinyl. The term "heteroarylene" as used herein refers to a divalent group having a heterocyclic aromatic system.

[0063] As used herein, the "substituent" may be: deuterium, halogen, hydroxyl, cyano, nitro, carbonyl, carboxylic acid group, amino, ether moiety, ester 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, or C 1 -C 20 heteroarylthio;

[0064] C is unsubstituted or substituted as follows 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, C6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, and C 1 -C 20 Heteroarylthio group: deuterium, halogen atom, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether moiety, ester 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, and combinations thereof.

[0065] Hereinafter, the embodiments will be described in detail with reference to the accompanying drawings. In the accompanying drawings, similar reference numerals represent similar elements or components having substantially the same functions, and repeated descriptions will be omitted. In the accompanying drawings, for the convenience of explanation, the thickness of some layers and regions is exaggerated for clarity. At the same time, it should be understood that the embodiments described hereinafter are for illustrative purposes only, and various changes in form may be made by the embodiments.

[0066] [Organometallic compounds]

[0067] The organometallic compound according to the embodiment may be represented by any one of Formulae 1-1 to 1-4:

[0068]

[0069] Among them, in formulas 1-1 to 1-4,

[0070] M 11 It may be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po),

[0071] Q 11 To Q 14 may be independently 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, or substituted or unsubstituted C 1 -C 30 Heteroaryl,

[0072] b11 can be 2 or 3,

[0073] b12 to b14 may each independently be an integer from 0 to 3,

[0074] R 11 To R 14 can be independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, carboxylic acid group, 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, or substituted or unsubstituted C 1 -C 30 Heteroaryl,

[0075] Q11 To Q 14 and R 11 To R 14 Two adjacent ones of may be optionally (e.g., via a single bond or a linking group such as O, S, C 1 -C 10 Alkylene or C 2 -C 10 alkenylene) are bonded to each other to form a ring (e.g., a fused ring),

[0076] Y 11 To Y 13 can be independently O, O(C=O), S, S(C=O), NX 14 or NX 14 (C=O), and

[0077] X 11 To X 14 may be independently: hydrogen; deuterium; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 30 A monovalent hydrocarbon group.

[0078] The molecular weight of the organometallic compound may be 3000 g / mol or less. In an embodiment, the molecular weight of the organometallic compound may be 2000 g / mol or less, such as 1000 g / mol or less, such as 900 g / mol or less, such as 800 g / mol or less, and 200 g / mol or more, such as 300 g / mol or more, or 400 g / mol or more.

[0079] In the organometallic compound, M 11 The bond dissociation energy (calculated value) of the bond between Q and C may be 30 kcal / mol or less. Although not limited to a particular theory, the b11 Q bonded to C 11 Can be used when M 11 The free radical generated when the bond between C and C is broken is stable. 11 The bond dissociation energy of the bond between Q and C can be reduced. In particular, due to 11 The double or triple bonds contained in the 11 The carbon (C) connected to the 11 When the bond between Q and C is broken, the free radical generated can 11 The resonance is stable.

[0080] For example, M in Formulas 1-1 to 1-4 11In, Sn or Sb. In the embodiment, M in Formulas 1-1 to 1-4 11 It can be Sn.

[0081] For example, Q in Formulas 1-1 to 1-4 11 To Q 14 may be independently selected from 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, and C 1 -C 30 Heteroaryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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.

[0082] In an embodiment, Q in Formulas 1-1 to 1-4 11 To Q 14 may be independently selected from C2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 2 -C 30 Alkynyl, and C 6 -C 30 Aryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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.

[0083] In an embodiment, Q in Formulas 1-1 to 1-4 11 To Q 14 may be each independently selected from vinyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl, each of which is unsubstituted or substituted with deuterium, halogen, hydroxyl, cyano, nitro, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, C 1 -C 10Haloalkoxy, C 1 -C 10 Halogenated alkylthio, C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy, C 3 -C 10 cycloalkylthio, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, or a combination thereof.

[0084] For example, in Formulae 1-1 to 1-4, b11 may be 2 or 3; b12 may be 2 or 3; b13 may be 2 or 3; or b14 may be 2 or 3. In some embodiments, b11 to b14 in Formulae 1-1 to 1-4 may each independently be 2 or 3.

[0085] For example, R in Formulas 1-1 to 1-4 11 To R 14 may be independently selected from: hydrogen; deuterium; halogen; hydroxyl; cyano; nitro; carboxylic acid 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, and C 1 -C 30 Heteroaryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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, C3 -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.

[0086] In an embodiment, R in Formulas 1-1 to 1-4 11 To R 14 may be independently selected from: hydrogen; deuterium; halogen; hydroxyl; cyano; nitro; carboxylic acid group; and C 1 -C 30 (For example, C 1 -C 20 , C 1 -C 10 , or C 1 -C 6 ) alkyl, C 3 -C 30 (For example, C 3 -C 10 or C 3 -C 6 ) cycloalkyl, C 2 -C 30 (For example, C 2 -C 20 , C 2 -C 10 , or C 2 -C 6 ) alkenyl, C 3 -C 30 (For example, C 3 -C 10 or C 3 -C 6 )cycloalkenyl, C 2 -C 30 (For example, C 2 -C 10 or C 2 -C 6 ) alkynyl, and C 6 -C 30 (For example, C 6 -C 12 or C6 -C 10 ) Aryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 (For example, C 1 -C 10 or C 1 -C 6 ) alkyl, C 1 -C 20 (For example, C 1 -C 10 or C 1 -C 6 ) haloalkyl, C 1 -C 20 (For example, C 1 -C 10 or C 1 -C 6 ) alkoxy, C 1 -C 20 (For example, C 1 -C 10 or C 1 -C 6 ) alkylthio, C 1 -C 20 (For example, C 1 -C 10 or C 1 -C 6 ) haloalkoxy, C 1 -C 20 (For example, C 1 -C 10 or C 1 -C 6 ) haloalkylthio, 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.

[0087] In some embodiments, R in Formulas 1-1 to 1-4 11 To R 14 may each independently be: hydrogen; deuterium; halogen; hydroxyl; cyano; nitro; a carboxylic acid group; and methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl, each of which is unsubstituted or substituted with: deuterium, halogen, hydroxyl, cyano, nitro, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkoxy, C 1 -C 10 Halogenated alkylthio, C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy, C 3 -C 10 cycloalkylthio, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, or a combination thereof.

[0088] In an embodiment, b11 in Formulae 1-1 to 1-4 may be 2. In some embodiments, b11 to b14 in Formulae 1-1 to 1-4 may each independently be 2.

[0089] In an embodiment, with respect to Formulae 1-1 to 1-4, *-C(Q 11 )b 11 (R 11 ) (3-b11) It can be represented by one of the formulas 2-11 to 2-14; *-C(Q 12 )b 12 (R 12 ) (3-b12) It can be represented by one of the formulas 2-21 to 2-30; *-C(Q 13 ) b13 (R 13 ) (3-b13) It can be represented by one of the formulas 2-31 to 2-40; and *-C(Q 14 ) b14 (R 14 ) (3-b14) It can be expressed by one of the formulas 2-41 to 2-50:

[0090]

[0091]

[0092] Regarding formulas 2-11 to 2-14 and 2-21 to 2-50,

[0093] Q 11a To Q 11f , Q 12a To Q 12f , Q 13a To Q 13f , and Q 14a To Q 14f Each of the formulas 1-1 to 1-4 can be referred to by referring to Q 11 The description provided is to understand,

[0094] R 11c , R 11d , R 12a To R 12f , R 13a To R 13f , and R 14a To R 14f Each can be referred to by referring to R in Formulae 1-1 to 1-4 11 It should be understood that for Q 11a To Q 11f , Q 12a To Q 12f , Q 13a To Q 13f , Q 14a To Q 14f , R 11c , R 11d , R 12a To R 12f , R 13a To R 13f , and R 14a To R 14f , when they are not in a ring, they are monovalent groups, and when they are in a ring, they are divalent groups.

[0095] L 11 To L 14 Can be independently a single bond, O, S, C 1 -C 10 Alkylene, or C 2 -C 10 alkenylene, a11 to a14 may each independently be an integer of 1 to 3, and

[0096] * is the binding site with the adjacent atom.

[0097] For example, L in Formulas 2-11, 2-12, 2-21 to 2-26, 2-31 to 2-36, and 2-41 to 2-46 11 To L 14 They may each independently be a single bond or O.

[0098] For example, a11 to a14 in Formulae 2-11, 2-12, 2-21 to 2-26, 2-31 to 2-36, and 2-41 to 2-46 may each independently be 1.

[0099] For example, Q in Formulas 2-11 to 2-14 and 2-21 to 2-50 11a , Q 11b , Q 12a , Q 12b , Q 13a , Q 13b , Q 14a , Q 14b , R 12a , R 12b , R 13a , R 13b , R 14a , and R 14b may be independently substituted or unsubstituted C 3 -C 30 Cycloalkenyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl, substituted or unsubstituted C 6 -C 30 Aryl, or substituted or unsubstituted C 1 -C 30 Heteroaryl.

[0100] In an embodiment, *-C(Q 11 ) b11 (R 11 ) (3-b11) It can be represented by one of the formulas 3-11 to 3-14; *-C(Q 12 ) b12 (R 12 ) (3-b12) It can be represented by one of the formulas 3-21 to 3-24; *-C(Q 13 ) b13 (R 13 ) (3-b13) It can be represented by one of the formulas 3-31 to 3-34; and *-C(Q 14 ) b14 (R 14 ) (3-b14) It can be expressed by one of the formulas 3-41 to 3-44:

[0101]

[0102]

[0103] In Formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44,

[0104] Q 11c , Q 11f , Q 12c , Q 12f , Q 13c , Q 13f , Q 14c and Q 14f Each of the formulas 1-1 to 1-4 can be referred to by referring to Q 11 Description provided to understand.

[0105] R 11c , R 11d , R 12c , R 12f , R 13c , R 13f , R 14c and R 14f Each can be referred to by referring to R in Formulae 1-1 to 1-4 11 Description provided to understand.

[0106] L 11 To L 14 Can be independently a single bond, O, S, C 1 -C 10 Alkylene, or C 2 -C 10 Alkenylene,

[0107] a11 to a14 can each independently be an integer from 1 to 3,

[0108] A 31 and A 32 Can be independently C 3 -C 20 Cycloalkenyl, C 3 -C 20 Heterocycloalkenyl, C 6 -C 20 Aryl, or C 1 -C 20 Heteroaryl,

[0109] R 31 To R 36 can each independently be hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkoxy, C 1 -C 10 Halogenated alkylthio, C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy, C 3 -C 10 Cycloalkylthio, C 6 -C 10 Aryl, C 1 -C 10 Heteroaryl, C 6 -C 10 Aryloxy, C 6 -C 10 Arylthio, C 1 -C 10 Heteroaryloxy, or C 1 -C 10 Heteroarylthio,

[0110] b31 and b32 may each independently be an integer from 1 to 8, and

[0111] * is the binding site with the adjacent atom.

[0112] For example, L in Formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44 11 To L 14 They may each independently be a single bond or O.

[0113] For example, a11 to a14 in Formulae 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44 may each independently be 1.

[0114] For example, A in Formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44 31 and A 32 Each independently may be cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, phenyl, or naphthyl.

[0115] For example, Y in Formulas 1-1 to 1-4 11 To Y 13Each independently may be O, O(C═O), S, or S(C═O).

[0116] For example, X in Formulas 1-1 to 1-4 11 To X 14 may be each independently: hydrogen; deuterium; and C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 3 -C 20 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 20 Aryl, and C 1 -C 20 Heteroaryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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, or a combination thereof.

[0117] In an embodiment, X in Formulas 1-1 to 1-4 11 To X 14 may be each independently: hydrogen; deuterium; and C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 3-C 20 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 20 Aryl, and C 1 -C 20 Heteroaryl: deuterium, halogen, hydroxyl, amino, carboxylic acid group, ether moiety, ester 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.

[0118] In an embodiment, X in Formulas 1-1 to 1-4 11 To X 14 may be each independently: hydrogen; deuterium; and C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 2 -C 30 Alkynyl, and C 6 -C 20 Aryl: deuterium, halogen, methyl, ethyl, phenyl, naphthyl, or a combination thereof.

[0119] 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, halogen, methyl, ethyl, phenyl, naphthyl, or a combination thereof.

[0120] In an embodiment, the organometallic compound may be represented by Formula 1-2, 11 ) b11 (R11 ) (3-b11) It can be represented by one of the formulas 3-11 and 3-13; and *-C(Q 12 ) b12 (R 12 ) (3-b12) It can be expressed by one of formulas 3-21 and 3-23.

[0121] In an embodiment, the organometallic compound represented by one of Formulae 1-1 to 1-4 may be selected from Group I:

[0122]

[0123]

[0124] Although not limited to any particular theory, the organometallic compound may be capable of forming free radicals through heat and / or high energy radiation. 11 -carbon bonds form free radicals, and optionally in an atmosphere in which water is present, the free radicals can react to form chemical bonds between the organometallic compounds. As a result, the physical properties of the organometallic compound, such as its solubility in the developer, can be altered.

[0125] In particular, the organometallic compound represented by one of Formulae 1-1 to 1-4 must include at least two Q 11 , so that the radical (group) stability can be improved, and therefore, M 11 - The bond dissociation energy of the carbon bond can be reduced, and its sensitivity to energy rays such as EUV can be improved.

[0126] For some of the organometallic compounds represented by one of Formulas 1-1 to 1-4, density functional theory (DFT) calculations were used to calculate the enthalpy change values ​​of the equilibrium homolysis of the Sn-C bond. Based on the results obtained, the bond dissociation energy of the Sn-C bond was defined and listed in Table 1 below.

[0127] Table 1

[0128]

[0129] The organometallic compound may be prepared by any suitable method.

[0130] The structure (composition) of the organometallic compound can be determined by 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 as described in the examples.

[0131] [Resist composition]

[0132] According to one aspect of the present disclosure, a resist composition includes the organic metal compound. The resist composition may have improved photosensitivity and / or storage stability properties.

[0133] Exposure to high energy rays changes the solubility of the resist composition in the developer. 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.

[0134] In an embodiment, when forming a resist pattern, the resist composition can be used for an alkaline development process using an alkaline developer for development treatment; or for a solvent development process using a developer containing an organic solvent (hereinafter, also referred to as an organic developer) for development treatment.

[0135] The resist composition may be non-chemically amplified. In this case, a photoacid generator may be substantially excluded.

[0136] Since physical properties of the organometallic compound are changed by exposure, the resist composition may substantially exclude a compound having a molecular weight of 1,000 g / mol or more other than the organometallic compound.

[0137] The amount of the organometallic compound in the resist composition may be about 0.1 to about 100 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 2 parts by weight or more, and 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of the resist composition. Within these ranges, chemical bonds between the organometallic compounds are sufficiently formed while side reactions are suppressed, thereby providing a resist composition with improved sensitivity and / or resolution.

[0138] <Organic Solvents>

[0139] The resist composition may further include an organic solvent.

[0140] The organic solvent included in the resist composition is not particularly limited as long as the organometallic compound and any component included therein when necessary can be dissolved or dispersed therein. The organic solvent may be used alone or in any combination of two or more different organic solvents.

[0141] In an embodiment, the organic solvent may include a protic organic solvent, an aprotic organic solvent, or a combination thereof.

[0142] In some embodiments, the organic solvent may be a mixture including an aprotic organic solvent and a protic organic solvent.

[0143] 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.

[0144] Examples of the organic solvent may include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent, a sulfoxide-based solvent, and a hydrocarbon-based solvent.

[0145] In some embodiments, examples of the alcohol-based solvent may include: 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, tert-pentanol, 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 and diacetone alcohol; solvents based on polyols 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-containing polyol-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl The following are the ingredients of the present invention: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene 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.

[0146] Examples of the ether-based solvent include dialkyl ether-based 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-based solvents such as diphenyl ether and anisole.

[0147] Examples of the ketone-based solvent may include: chain ketone-based solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone and trimethylnonanone; cyclic ketone-based solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone; and 2,4-pentanedione, acetonylacetone and acetophenone.

[0148] Examples of the amide-based solvent may include: 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 and N-methylpropionamide.

[0149] Examples of the ester-based solvent include acetate-based solvents 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 n-nonyl acetate; polyol-containing ether carboxylate-based solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGE) and propylene glycol monomethyl ether acetate. The present invention relates to solvents based on the invention, for example, 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-based solvents such as γ-butyrolactone and δ-valerolactone; carbonate-based solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate; lactate-based solvents such as methyl lactate, ethyl lactate, n-butyl lactate and n-amyl lactate; and glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate and diethyl phthalate.

[0150] Examples of the sulfoxide-based solvent may include dimethyl sulfoxide and diethyl sulfoxide.

[0151] Examples of the hydrocarbon-based solvent include: aliphatic hydrocarbon-based 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-based solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene and n-pentylnaphthalene.

[0152] 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 combinations thereof.

[0153] <Other components>

[0154] If necessary, the resist composition may further include a surfactant, a crosslinking agent, a leveling agent, a colorant, or a combination thereof.

[0155] The resist composition may further include a surfactant to improve coating properties, developability, etc. Examples 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, and polyethylene glycol distearate. Any commercially available product or synthetic product may be used as the surfactant. Examples of commercially available products may include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75 and Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Eftop EF301, Eftop EF303, and Eftop 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, Fluorad FC431 (manufactured by 3MC Co., Ltd.), AsahiGuard AG710 (manufactured by AGC Co., Ltd.), and Surflon (registered trademark) S-382, Surflon SC-101, Surflon Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105 and Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0156] The surfactant may be included in an amount ranging from about 0 parts by weight to about 20 parts by weight based on 100 parts by weight of the organic metal compound. The surfactant may be used alone or any mixture of two or more different surfactants may also be used.

[0157] 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 the optional components added when necessary. The temperature or time during mixing is not particularly limited. If necessary, filtering can be performed after mixing.

[0158] [Pattern Formation Method]

[0159] 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 flow chart showing a pattern forming method according to an embodiment, and Figures 2A to 2C 2 is a side cross-sectional view showing 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.

[0160] Reference Figure 1 The pattern forming method includes: forming a resist film by applying a resist composition (S101), exposing at least a portion of the resist film to high-energy rays (S102) to provide an exposed resist film, and developing the exposed resist film using a developer (S103).

[0161] First, prepare a substrate 100. The substrate 100 may be a semiconductor substrate such as a silicon substrate and a germanium substrate, or may include glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 may include a III-V group compound such as GaP, GaAs, and GaSb.

[0162] The resist film 110 may be formed on the substrate 100 by applying the resist composition thereto to a desired thickness using a coating method. If necessary, the resist film 110 may be heated (pre-baked, PB) to remove the organic solvent remaining therein. In some embodiments, by heating the resist film 110, free radicals may be generated, and then by exposure, the free radicals may be chemically combined to form crosslinks.

[0163] As coating method, spin coating, dipping, roller coating or other common coating methods can be used. Among them, spin coating can be used in particular. By adjusting the viscosity, concentration and / or the rotation speed of the resist composition, a resist film 110 with a desired thickness can be formed. In an embodiment, the resist film 110 can have a thickness of about 10nm to about 300nm. In an embodiment, the resist film 110 can have a thickness of about 30nm to about 200nm.

[0164] The lower limit of the pre-bake temperature may be 60°C or higher, or 80°C or higher. In an embodiment, the upper limit of the pre-bake temperature may be 150°C or lower, or 140°C or lower. The lower limit of the pre-bake time may be 5 seconds or more, or 10 seconds or more. The upper limit of the pre-bake time may be 600 seconds or less, or 300 seconds or less.

[0165] Before the resist composition is applied to the substrate 100, a film to be etched (not shown) may be formed on the substrate 100. The film to be etched may refer to a film to which an image is transferred from a resist pattern and converted into a pattern. In an embodiment, the film to be etched may be formed to include, for example, an insulating material such as silicon oxide, silicon nitride, and silicon oxynitride. In some embodiments, the film to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, and a metal silicon nitride. In some embodiments, the film to be etched may be formed to include a semiconductor material such as polysilicon.

[0166] 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.

[0167] In an embodiment, a protective film may be further formed on the resist film 110 to reduce the influence of alkaline impurities included during the process. In an embodiment, in the case of performing immersion lithography, a protective film for immersion lithography may be formed on the resist film to avoid direct contact between the immersion medium and the resist film 110.

[0168] Subsequently, at least a portion of the resist film 110 may be exposed to high-energy rays. For example, high-energy rays passing through the mask 120 may reach at least a portion of the resist film 110. Therefore, the resist film 110 may have an exposed region 111 and an unexposed region 112.

[0169] 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.

[0170] If necessary, exposure is performed by irradiating high-energy rays through a mask having a specific pattern using a liquid such as water as a medium. Examples of high-energy rays may include electromagnetic waves such as ultraviolet rays, deep ultraviolet rays, extreme ultraviolet rays (EUV) (wavelength of 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams and alpha particle beams. Irradiation of these high-energy rays may be collectively referred to as "exposure".

[0171] Various 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 a F 2Excimer laser (wavelength of 157nm); a light source that emits 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 (YAG or semiconductor laser); and a light source that emits an electron beam or EUV. During exposure, a mask corresponding to a desired pattern is generally used. However, in the case of using an electron beam as a light source for exposure, exposure can be performed directly without using a mask.

[0172] In the case of using extreme ultraviolet rays as high-energy rays, the total dose of the high-energy rays may be 2000 mJ / cm 2 or less or 500mJ / cm 2 In an embodiment, when an electron beam is used as the high-energy ray, the total dose may be 5000 μC / cm 2 or less or 1000μC / cm 2 or smaller.

[0173] In an embodiment, a post-exposure bake (PEB) may be performed after exposure. The lower limit of the PEB temperature may be 50° C. or higher, or 80° C. or higher. The upper limit of the PEB temperature may be 250° C. or lower, or 200° C. or lower. The lower limit of the PEB time may be 5 seconds or more, or 10 seconds or more. The upper limit of the PEB time may be 600 seconds or less, or 300 seconds or less.

[0174] The exposed resist film 110 may be developed using a developer. The unexposed region 112 may be removed by washing with the developer, and the exposed portion 111 remains without being washed with the developer.

[0175] Examples of the developer may include an alkaline developer and a developer including an organic solvent (hereinafter, also referred to as an "organic developer"). The developing method may be dipping, puddling, spraying, a dynamic method, etc. The developing temperature may be, for example, about 5° C. to about 60° C., and the developing time may be, for example, about 5 seconds to about 300 seconds.

[0176] Examples of the alkaline developer may include an alkaline aqueous solution containing at least one alkaline compound dissolved therein, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 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 include a surfactant.

[0177] The lower limit of the amount of the alkaline compound contained 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 contained in the alkaline developer may be 20 wt % or less, or 10 wt % or less, or 5 wt % or less.

[0178] For example, the organic solvent contained in the organic developer may be the same as those described in the <Organic Solvent> section of the [Resist Composition] above. In an embodiment, the organic developer may include or 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.

[0179] Regarding the organic developer, a 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.

[0180] The organic developer may include a surfactant. In embodiments, the organic developer may include trace amounts of moisture. In embodiments, during development, development may be stopped by replacing the organic developer with a different type of solvent.

[0181] The resist pattern can be further washed after development. Ultrapure water, cleaning solution, etc. can be used during washing. The cleaning solution is not particularly limited as long as the resist pattern is not dissolved therein, and any solution including common organic solvents can be used. For example, the cleaning solution can be an alcohol-based solvent or an ester-based solvent. After washing, the cleaning solution remaining on the substrate and the pattern can be removed. In an embodiment, when ultrapure water is used, the water remaining on the substrate and the pattern can be removed.

[0182] In embodiments, the developer may be used alone, or any combination of two or more different developers may be used.

[0183] After forming the resist pattern as described above, a patterned wiring substrate can be obtained by etching. Any etching method known in the art such as dry etching using plasma gas and wet etching using an alkaline solution, a copper (II) chloride solution or a ferric chloride solution can be used.

[0184] After the resist pattern is formed, plating may be performed. The plating method is not particularly limited, and for example, copper plating, solder plating, nickel plating, and gold plating may be used.

[0185] The resist pattern remaining after etching can be stripped using an organic solvent. Examples of the organic solvent may be, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and ethyl lactate (EL). The stripping method is not particularly limited, but may be, for example, dipping and spraying. In an embodiment, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate or may have a small diameter through hole.

[0186] In an embodiment, the wiring substrate may be formed by a method including forming a resist pattern, depositing a metal in a vacuum, and dissolving the resist pattern using a solution, ie, a lift-off method.

[0187] Hereinafter, the present disclosure will be described in more detail with reference to the following examples and comparative examples. However, the following examples are presented only as non-limiting examples of the present disclosure, and the scope of the present disclosure is not limited thereto.

[0188] Example

[0189] Synthesis Example 1: Synthesis of OM-A

[0190]

[0191] (1) Synthesis of A-2

[0192] Diphenylmethane (4.89 g, 29.1 mmol) was added to the N 2 A 2-necked round-bottom flask was replaced and diluted with THF (30 ml). n-BuLi (2.5 M in hexane, 29.1 mmol) was added dropwise thereto at -78 ° C, and then stirred at 0 ° C for 0.5 hours. Dichlorodiphenyltin alkane (5 g, 14.5 mmol) was added to a vial and diluted with THF (28 ml, total THF (58 ml, 0.25 M)). The solution in the vial was added dropwise to a round-bottom flask at -78 ° C, stirred for 0.5 hours, then heated to room temperature and stirred again for 0.5 hours. After confirming that the reaction was complete, the solvent was removed, filtered with silica / diatomaceous earth, and purified by column chromatography (ethyl acetate (EA): n-hexane (EA5 volume %)) to obtain A-2 (6.8 g, 77%).

[0193] Figures 3A to 3C To display A-2 1 H-NMR data, 13 C-NMR data and 119 Plot of Sn-NMR data.

[0194] (2) Synthesis of A-1

[0195] A-2 (6.2 g, 10.2 mmol) was placed in a round-bottom flask and the atmosphere in the round-bottom flask was replaced with N 2 After dilution with dichloromethane (DCM) (102 ml, 0.1 M), the mixture was stirred at 4 °C for 2 h. 2 2M HCl solution (15.3 ml, 30.67 mmol) in 0 was added dropwise thereto at -78°C. After stirring at -78°C for 1 hour, the temperature was raised to room temperature, and then stirred for 12 hours of reaction. The solvent was removed therefrom, and a precipitate was obtained by washing with methyl tert-butyl ether: n-hexane (5 ml: 100 ml), and then dried under vacuum to obtain A-1 (4.3 g, 80%).

[0196] Figures 4A to 4C To display A-1 1 H-NMR data, 13 C-NMR data and 119 Plot of Sn-NMR data.

[0197] (3) Synthesis of OM-A

[0198] A-1 (1.0 g, 1.91 mmol) was placed in a round-bottom flask and the atmosphere in the round-bottom flask was replaced with N 2 After dilution with dry acetone (19 ml, 0.1 M), sodium acetate (0.31 g, 3.82 mmol) was added thereto at 0°C. After reaction at 0°C for 16 hours, diatomaceous earth was used for filtration. The solvent was removed, followed by recrystallization (methyl tert-butyl ether: n-hexane = 3 ml: 30 ml). After filtration, the precipitate was dried under vacuum to obtain OM-A (0.54 g, 50%).

[0199] Figures 5A to 5C To display the OM-A 1 H-NMR data, 13 C-NMR data and 119 Plot of Sn-NMR data.

[0200] Synthesis Example 2: Synthesis of OM-B

[0201]

[0202] (1) Synthesis of B-2

[0203] Fluorene (8.31 g, 50.0 mmol) was added to the 2In a 2-necked round-bottom flask replaced with THF (50ml). n-BuLi (2.5M in hexane, 20ml, 50mmol) is added dropwise thereto at -78°C, and then stirred at 0°C for 0.5 hours. Dichlorodiphenyltin alkane (8.60g, 25.0mmol) is added to a vial, and diluted with THF (50ml, total THF 100ml (0.25M)). The solution in the vial is added dropwise to a round-bottom flask at -78°C, stirred for 0.5 hours, then heated to room temperature and stirred again for 0.5 hours. After confirming that the reaction is complete, the solvent is removed, filtered with silica / diatomaceous earth, and purified by column chromatography (dichloromethane (DCM): n-hexane (DCM 10 volume %)) to obtain B-2 (12.1g, 80%).

[0204] Figures 6A to 6C To show B-2 1 H-NMR data, 13 C-NMR data and 119 Plot of Sn-NMR data.

[0205] (2) Synthesis of B-1

[0206] B-2 (12.0 g, 20.0 mmol) was placed in a round-bottom flask and the atmosphere in the round-bottom flask was replaced with N 2 After dilution with dichloromethane (200 ml, 0.1 M), the 2 A 2M HCl solution (30 ml, 60 mmol) in 0 was added dropwise thereto at -78°C. After stirring at -78°C for 1 hour, the temperature was raised to room temperature, and then stirred for 12 hours of reaction. The solvent was removed, washed with n-hexane to obtain a precipitate, and the precipitate was dried under vacuum to obtain B-1 (8.8 g, 85%).

[0207] Figures 7A to 7C To display B-1 1 H-NMR data, 13 C-NMR data and 119 Plot of Sn-NMR data.

[0208] (3) Synthesis of OM-B

[0209] B-1 (1.5 g, 2.88 mmol) was placed in a round-bottom flask and the atmosphere in the round-bottom flask was replaced with N 2Replacement. After dilution with dry acetone (29 ml, 0.1 M), sodium propionate (0.55 g, 5.77 mmol) was added thereto at 0°C. After reaction at 0°C for 16 hours, diatomaceous earth was used for filtration. The solvent was removed and then recrystallized (dichloromethane: n-hexane = 5 ml: 100 ml). After filtration and drying under vacuum, OM-B (1.30 g, 76%) was obtained.

[0210] Figures 8A to 8C To display the OM-B 1 H-NMR data, 13 C-NMR data and 119 Plot of Sn-NMR data.

[0211] Evaluation Example: Thin Film Development Evaluation

[0212] The organometallic compound synthesized in each of Synthesis Examples 1 and 2 was dissolved in a casting solvent listed in Table 1 below in an amount of 2 wt % based on the total weight of the casting solution to obtain a casting solution. A silicon wafer having a diameter of 4 inches was 2 The films were plasma treated for 30 minutes, spin coated with the casting solution at 1200 rpm for 1 minute, and then prebaked (PB) at 120°C for 1 minute to produce films with the initial thickness shown in Table 1 below. Then, a 3.5 mm thick mask (4 cm x 4 cm) with a plurality of rectangular holes (1 cm x 1 cm) was placed thereon, and each hole was irradiated with 0 mJ / cm 2 Up to 50mJ / cm 2 Or 0mJ / cm 2 Up to 100mJ / cm 2 The film was exposed to DUV at a wavelength of 254 nm and post-exposure baking (PEB) was performed at 120° C. to 160° C. for 1 minute. The resulting 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 is shown in Table 2 below and Figures 9A to 9E , 10 and 11A to 11C. Figures 9A to 9E , 10 and 11A to 11C, "as applied" is reference data of a sample not treated with a developer, and "after development" is data of a sample treated with a developer. In an embodiment, in order to compare the effects of the ligand, Eth and E1 of Examples 1-3, 2-1, and Comparative Examples 1 to 3 are compared and shown in Tables 3 and 4 below.

[0213] Table 2

[0214]

[0215]

[0216] Table 3

[0217] serial number Example Comparative Example <![CDATA[E of the embodiment th > <![CDATA[E of the comparative example th > Rate of change Comparison 1 Examples 1-3 Comparative Example 1 3 23 87% reduction Comparison 2 Examples 1-3 Comparative Example 2 3 23 87% reduction Comparison 3 Example 2-1 Comparative Example 3 18 28 36% reduction

[0218] Table 4

[0219] serial number Example Comparative Example <![CDATA[E of the embodiment 1 > <![CDATA[E of the comparative example 1 > Rate of change Comparison 4 Examples 1-3 Comparative Example 1 5 40 88% reduction Comparison 5 Examples 1-3 Comparative Example 2 5 35 86% reduction Comparison 6 Example 2-1 Comparative Example 3 33 40 18% reduction

[0220] In Tables 2 to 4, E th refers to the exposure at the point when the film begins to harden, and E 1 It refers to the exposure at the saturation point where the thickness of the film no longer increases.

[0221] Referring to Table 2, it can be seen that Examples 1-1 and 1-2 show the same contrast level as Examples 1-4 and 1-5. That is, it can be seen that the resist composition including the organometallic compound according to an embodiment of the present disclosure may be advantageous in that the temperature of the pattern forming process is suitably controlled as desired.

[0222] Referring to Table 2, it can be seen that the E th and E 1 Less than E of Comparative Examples 1 to 3 th and E 1 The results show that the resist compositions of Examples 1-1 to 1-5 and 2-1 have improved photosensitivity compared to the resist compositions of Comparative Examples 1 to 3.

[0223] Referring to Tables 3 and 4, since the organometallic compound according to an embodiment of the present disclosure is composed of *-C(Q 11 ) b11 (R 11 ) (3-b11) ,*-C(Q 12 ) b12 (R 12 ) (3-b12) 、*-C(Q 13 ) b13 (R 13 ) (3-b13) and / or *-C(Q 14 ) b14 (R 14 ) (3-b14) The structure of the ligand, E th and E 1 Changes / Improvements. In particular, it can be seen that compared with Comparative Examples 1 and 2, the use of 2 or more Q 11 Examples 1-3 of the organometallic compounds exhibit significantly reduced E th and E 1, and similarly, Example 2-1 also showed a significantly reduced E compared to Comparative Example 3. th and E 1 .

[0224] Figures 12A to 12E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment.

[0225] Reference Fig. 12A , before forming the resist film 110 on the substrate 100, a material layer 130 may be formed on the substrate 100. The resist film 110 may be formed on 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.

[0226] Reference Fig. 12B , the resist film 110 may be exposed to light with high energy rays through the mask 120 , after which the resist film 110 may include an exposed region 111 and an unexposed region 112 .

[0227] Reference Fig. 12C , 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 developer, while the unexposed portion 112 may be washed away by the developer.

[0228] Reference Fig.12D , 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 .

[0229] Reference Fig.12E , the resist pattern 110 can be removed.

[0230] Figures 13A to 13E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment.

[0231] Reference Fig.13A , a gate dielectric 505 (e.g., 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 (e.g., doped polysilicon) may be formed on the gate dielectric 505. A hard mask layer 520 may be formed on the gate layer 515.

[0232] Reference Fig. 13B, a resist pattern 540b may be formed on the hard mask layer 520. The resist pattern 540b may be formed using a resist composition according to example embodiments. The resist pattern 540b may be formed of a resist composition according to example embodiments.

[0233] Reference Fig. 13C , the hard mask layer 520, the gate layer 515, and the gate dielectric 505 may be etched by using the resist pattern 540b as a mask to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a. Then, the resist pattern 540b and the hard mask pattern 520a may be removed. Fig.13D , a spacer layer may be formed over 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 a spacer 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After forming the spacer 535a, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0234] Reference Fig.13E , 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 source / drain impurity regions S / D. 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 13A to 13E An example of forming a transistor is shown, but the inventive concept is not limited thereto.

[0235] The resist composition according to one or more embodiments may be used in a patterning process to form other types of semiconductor devices.

[0236] According to embodiments, a resist composition having improved sensitivity and providing a pattern with increased resolution may be provided.

[0237] It should be understood that the example embodiments described herein should be considered in a descriptive sense only and not for limiting purposes. The description of features or aspects in 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. An organometallic compound represented by one of formulas 1-1 to 1-4: in, In formulas 1-1 to 1-4, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi) or polonium (Po), Q 11 To Q 14 are each independently 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, or substituted or unsubstituted C1-C 30 Heteroaryl, b11 is 2 or 3, b12 to b14 are each independently an integer from 0 to 3, R 11 To R 14 are each independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, a carboxylic acid 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, or substituted or unsubstituted C1-C 30 Heteroaryl, Q 11 To Q 14 and R 11 To R 14 Adjacent two of are optionally bonded to each other to form a ring, Y 11 To Y 13 are independently O, O(C=O), S, S(C=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 organometallic compound according to claim 1, wherein In the organometallic compound, M 11 The bond dissociation energy of the bond between C is 30 kcal / mol or less.

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

4. The organometallic compound according to claim 1, wherein Q11 to Q14 are each independently selected from C2-C 30 Alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocycloalkenyl, C2-C 30 Alkynyl, C6-C 30 Aryl and C1-C 30 Heteroaryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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 11 To R 14 each independently selected from: hydrogen; deuterium; halogen; hydroxyl; cyano; nitro; carboxylic acid 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 and C1-C 30 Heteroaryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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.

5. The organometallic compound according to claim 1, wherein b12 is 2 or 3; b13 is 2 or 3; or b14 is 2 or 3.

6. The organometallic compound according to claim 1, wherein *-C(Q 11 ) b11 (R 11 ) (3-b11 ) is represented by one of Formulas 2-11 to 2-14, *-C(Q 12 ) b12 (R 12 ) (3-b12) It is represented by one of Formulas 2-21 to 2-30, *-C(Q 13 ) b13 (R 13 ) (3-b13) is represented by one of Formulas 2-31 to 2-40, and *-C(Q 14 ) b14 (R 14 ) (3-b14) It is represented by one of the formulas 2-41 to 2-50: in, In formulas 2-11 to 2-14 and 2-21 to 2-50, Q 11a To Q 11f , Q 12a To Q 12f , Q 13a To Q 13f , and Q 14a To Q 14f Having the same Q as in Formulas 1-1 to 1-4 11 The same definition, R 11c , R 11d , R 12a To R 12f , R 13a To R 13f , and R 14a To R 14f Having the same R as in Formulas 1-1 to 1-4 11 The same definition, L 11 To L 14 Each independently represents a single bond, O, S, C1-C 10 Alkylene or C2-C 10 Alkenylene, a11 to a14 are each independently an integer of 1 to 3, and * is the binding site with the adjacent atom.

7. The organometallic compound according to claim 6, wherein Q 11a , Q 11b , Q 12a , Q 12b , Q 13a , Q 13b , Q 14a , Q 14b , R 12a , R 12b , R 13a , R 13b , R 14a , and R 14b are each independently substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, or substituted or unsubstituted C1-C 30 Heteroaryl.

8. The organometallic compound according to claim 1, wherein *-C(Q 11 ) b11 (R 11 ) (3-b11) It is represented by one of Formulas 3-11 to 3-14, *-C(Q 12 ) b12 (R 12 ) (3-b12) It is represented by one of Formulas 3-21 to 3-24, *-C(Q 13 ) b13 (R 13 ) (3-b13) It is represented by one of Formulas 3-31 to 3-34, and *-C(Q 14 ) b14 (R 14 ) (3-b14) It is represented by one of Formulas 3-41 to 3-44: in, In Formulas 3-11 to 3-14, 3-21 to 3-24, 3-31 to 3-34, and 3-41 to 3-44, Q 11c , Q 11f , Q 12c , Q 12f , Q 13c , Q 13f , Q 14c and Q 14f Having the same Q as in Formulas 1-1 to 1-4 11 The same definition, R 11c , R 11d , R 12c , R 12f , R 13c , R 13f , R 14c and R 14f Having the same R as in Formulas 1-1 to 1-4 11 The same definition, L 11 To L 14 Each independently represents a single bond, O, S, C1-C 10 Alkylene or C2-C 10 Alkenylene, a11 to a14 are each independently an integer of 1 to 3, and A 31 and A 32 Each independently is C3-C 20 Cycloalkenyl, C3-C 20 Heterocycloalkenyl, C6-C 20 Aryl, or C1-C 20 Heteroaryl, R 31 To R 36 are each independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C1-C 10 Halogenated alkoxy, C1-C 10 Halogenated alkylthio, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, C3-C 10 Cycloalkylthio, C6-C 10 Aryl, C1-C 10 Heteroaryl, C6-C 10 Aryloxy, C6-C 10 Arylthio, C1-C 10 Heteroaryloxy, or C1-C 10 Heteroarylthio, b31 and b32 are each independently an integer from 1 to 8, and * is the binding site with the adjacent atom.

9. The organometallic compound according to claim 1, wherein X 11 To X 14 are each independently selected from: hydrogen; deuterium; and C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C3-C 20 Cycloalkyl, C2-C 30 Alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocycloalkenyl, C2-C 30 Alkynyl, C6-C 20 Aryl and C1-C 20 Heteroaryl: deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester 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, or a combination thereof.

10. The organometallic compound according to claim 1, wherein The organic metal compound represented by one of Formulae 1-1 to 1-4 is represented by Formula 1-2, *-C(Q 11 ) b11 (R 11 ) (3-b11) It is represented by one of Formulas 3-11 and 3-13, and *-C(Q 12 ) b12 (R 12 ) (3-b12) It is expressed by one of the formulas 3-21 and 3-23: in, In formulas 3-11, 3-13, 3-21 and 3-23, R 11c , R 11d , R 12c , and R 12f Each has the same R as in Formulas 1-1 to 1-4 11 The same definition, L 11 and L 12 Each independently represents a single bond, O, S, C1-C 10 Alkylene or C2-C 10 Alkenylene, a11 to a12 are each independently an integer of 1 to 3, and A 31 and A 32 Each independently is C3-C 20 Cycloalkenyl, C3-C 20 Heterocycloalkenyl, C6-C 20 Aryl, or C1-C 20 Heteroaryl, R 31 To R 36 are each independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxylic acid group, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C1-C 10 Halogenated alkoxy, C1-C 10 Halogenated alkylthio, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, C3-C 10 Cycloalkylthio, C6-C 10 Aryl, C1-C 10 Heteroaryl, C6-C 10 Aryloxy, C6-C 10 Arylthio, C1-C 10 Heteroaryloxy or C1-C 10 Heteroarylthio, b31 and b32 are each independently an integer from 1 to 8, and * is the binding site with the adjacent atom.

11. The organometallic compound according to claim 1, wherein The organometallic compound represented by one of Formulae 1-1 to 1-4 is selected from Group I: <Group I> 12. A resist composition comprising: The organometallic compound according to any one of claims 1 to 11.

13. The resist composition according to claim 12, wherein The resist composition substantially excludes a photoacid generator.

14. The resist composition according to claim 12, wherein The resist composition substantially does not include a compound having a molecular weight of 1,000 g / mol or more.

15. The resist composition according to claim 12, further comprising: Organic solvents.

16. The resist composition according to claim 15, wherein The organic solvent includes a protic organic solvent, an aprotic organic solvent, or a combination thereof.

17. A pattern forming method comprising: Forming a resist film by applying the resist composition according to any one of claims 12 to 16 on a substrate; exposing at least a portion of the resist film to high energy radiation to provide an exposed resist film; and The exposed resist film is developed using a developer.

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

19. The pattern forming method according to claim 17, wherein A chemical bond is formed between molecules of the organic metal compound by exposing at least the portion of the resist film to light.

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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