Resist composition and pattern forming method using same

Abstract

Provided are a resist composition including an organometallic compound represented by Formula 1 and an additive represented by Formula 2, and a pattern forming method using the same. The description of M11, Rx, Ry, n, m, X2, Y2, Z2, L2, a2, b2 and c2 in Formulae 1 and 2 is provided in the specification.

Description

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application No. 10-2024-0119557, filed on September 3, 2024, with the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to resist compositions and methods for patterning using the same. Background Technology

[0004] In semiconductor manufacturing, photoresists with physical properties that change in response to light are used to form fine patterns. Among these photoresists, chemically amplified photoresists have been widely used. In the case of chemically amplified photoresists, patterning is achieved by reacting an acid formed through the reaction between light (e.g., incident light with a specific intensity and / or wavelength) and a photoacid generator, which then reacts with a base resin to alter the solubility of the base resin in a developer. Summary of the Invention

[0005] Some exemplary embodiments provide resist compositions with improved storage stability, wherein the resist composition is configured to alter one or more properties even under low-dose exposure to incident light (e.g., exposure to light of small amounts and / or intensities), and wherein the resist composition is configured to provide a pattern with improved resolution. Some exemplary embodiments provide a patterning method using said resist composition. Such resist compositions may have compositions possessing improved storage stability, wherein the resist composition is configured to alter one or more physical properties even by exposure to incident light (e.g., high-energy rays) to overcome the limitations of chemically amplified resists that can cause the formed acid to diffuse into unexposed areas, such that the resist composition reduces, minimizes, or prevents the possibility of a decrease in pattern uniformity or an increase in surface roughness based on avoiding such acid diffusion, while providing improved chemical stability of the resist composition (and thus a reduced, minimized, or prevented risk of chemical degradation) and / or altering physical properties even by exposure to small amounts (e.g., low-intensity) of incident light (e.g., high-energy rays) in normal use at room temperature.

[0006] Other 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 means of embodiments of the inventive concept presented.

[0007] According to some exemplary embodiments of the present invention, the resist composition comprises an organometallic compound represented by Formula 1 and an additive represented by Formula 2:

[0008] Formula 1

[0009] M 11 (R x ) n (R y ) (m-n)

[0010] Formula 2

[0011] (X2) c2 -(L2) a2 -[Y2-Z2] b2

[0012] In Equations 1 and 2,

[0013] M 11 It can be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po).

[0014] R x It can be *-X1-Y1,

[0015] R y It can be *-(L1) a1 -(R1) b1 ,

[0016] n can be an integer from 1 to 6.

[0017] m can be an integer from 1 to 6.

[0018] mn can be 0 or greater.

[0019] Equation 1 may optionally include multiple R values ​​based on n greater than 1. x The plurality of R x Whether they are the same or different,

[0020] Equation 1 may optionally include multiple R values ​​based on mn being greater than 1. y The plurality of R y Whether they are the same or different,

[0021] X1 can be O, OC(=O), C(=O)O, OS(=O), S(=O)O, OS(=O)2, S(=O)2O, S, SC(=O) or C(=O)S,

[0022] Y1 can be hydrogen, deuterium, or optionally a straight-chain, branched, or cyclic C1-C chain including heteroatoms. 30 Monovalent hydrocarbon groups,

[0023] L1 can be a single bond, or optionally a straight chain, branched chain, or cyclic C1-C chain including heteroatoms. 30 Divalent hydrocarbon groups,

[0024] a1 can be an integer from 0 to 4.

[0025] R1 can be a straight-chain, branched, or cyclic C1-C chain that optionally includes heteroatoms. 30 Monovalent hydrocarbon groups,

[0026] b1 can be an integer from 1 to 4, wherein formula 1 may optionally include a plurality of R1s based on b1 being greater than 1, wherein two adjacent groups of the plurality of R1s may optionally be bonded to each other to form a ring.

[0027] X2 can be OH, SH, C(=O)OH, S(=O)OH, S(=O)2OH, or P(=O)(OH)2.

[0028] c2 can be an integer from 1 to 4.

[0029] Each L2 can independently be a straight-chain, branched, or cyclic C1-C, optionally including heteroatoms. 30 Divalent hydrocarbon groups,

[0030] a2 can be an integer from 0 to 4.

[0031] Y2-Z2 can be a photoreactive unit.

[0032] b2 can be an integer from 1 to 4, and

[0033] * indicates a binding site with an adjacent atom.

[0034] In Equation 1, M 11 It can be Sn, Sb, Te or Bi.

[0035] In Equation 1, X1 can be O, OC (=O), C (=O)O, S, SC (=O), or C (=O)S, and Y1 can be selected from: hydrogen, deuterium, Cl-C 30 Alkyl, C1-C 30 Haloalkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy groups, C1-C 30 Haloalkylthio group, C3-C 30 cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C6-C 30 Aryloxy group, C6-C30 Arylthio, C7-C 30 arylalkyl, C1-C 30 heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 heteroaryl thiols and C2-C 30 Heteroarylalkyl. C1-C 30 Alkyl, C1-C 30 Haloalkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy groups, C1-C 30 Haloalkylthio group, C3-C 30 cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C6-C 30 Aryloxy group, C6-C 30 Arylthio, C7-C 30 arylalkyl, C1-C 30 heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 heteroaryl thiols and C2-C 30 Each of the heteroaryl alkyl groups may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C20 Heteroaryl thiols or any combination thereof.

[0036] In Equation 1, L1 can be a single bond, a substituted or unsubstituted C1-C bond. 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl or substituted or unsubstituted C1-C 30 The heteroaryl group, where a1 can be 0, 1, or 2, and R1 can be selected from C1-C1. 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Each of the heteroaryl alkyl groups may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

[0037] The organometallic compounds represented by Formula 1 can be selected from Group I:

[0038] <Group I>

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] In group I, n is an integer from 0 to 3.

[0048] In Equation 2, X2 can be OH or C(=O)OH.

[0049] In Equation 2, (L2) a2 It can be expressed by any one of equations 5-1 to 5-7:

[0050]

[0051] In equations 5-1 to 5-7, R 51 To R 53 Each can be independently hydrogen, deuterium, halogen, hydroxyl, cyano, C1-C4 alkyl or C1-C4 haloalkyl, b51 can be an integer from 1 to 4, n51 can be an integer from 1 to 4 or from 1 to 3, and * and *' each indicate the binding site with the adjacent atom of Formula 2.

[0052] In Equation 2, Y2 can be OC(=O), C(=O)O, OS(=O)2, or S(=O)2O, Z2 can be *-C(R2)(R3)(R4), *-C(R2)=N(R3), *-N=C(R2)(R3), or *-N(R2)(R3), and R2 to R4 can each independently be hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, -C(=O)R5, -C(R5)=NR6, -OR5, -S(=O)R5, -S(=O)2R5, -S(=O)2OR5, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C1-C 30 Halogenated alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C 30 Halogenated alkoxy, substituted or unsubstituted C1-C 30 Haloalkylthio, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkoxy, substituted or unsubstituted C3-C 30 Cyclothio, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkoxy, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 Alkenyl group, substituted or unsubstituted C2-C 30 Thiolated, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyloxy, substituted or unsubstituted C3-C 30 Cycloalkenyl thio, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C3-C 30 Heterocyclic olefins, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C2-C 30 Acryloxy group, substituted or unsubstituted C2-C 30 Acrylylthio, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 aryloxy, substituted or unsubstituted C6-C 30 Arylthio, substituted or unsubstituted C1-C 30 heteroaryl, substituted or unsubstituted C1-C30 Heteroaryl groups or substituted or unsubstituted C1-C 30 The heteroaryl thio group, R2 and R3 optionally bond to each other to form a ring, and R5 and R6 can each be independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1-C. 30 Alkyl, substituted or unsubstituted C1-C 30 Halogenated alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C 30 Halogenated alkoxy, substituted or unsubstituted C1-C 30 Haloalkylthio, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkoxy, substituted or unsubstituted C3-C 30 Cyclothio, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkoxy, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 Alkenyl group, substituted or unsubstituted C2-C 30 Thiolated, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyloxy, substituted or unsubstituted C3-C 30 Cycloalkenyl thio, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C3-C 30 Heterocyclic olefins, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C2-C 30 Acryloxy group, substituted or unsubstituted C2-C 30 Acrylylthio, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 aryloxy, substituted or unsubstituted C6-C 30 Arylthio, substituted or unsubstituted C1-C 30 heteroaryl, substituted or unsubstituted C1-C 30 Heteroaryl groups or substituted or unsubstituted C1-C 30 The heteroaryl thio group, and * is the binding site with the adjacent atom of formula 2.

[0053] The additive represented by Equation 2 can be selected from self-assembly II:

[0054] Group II

[0055]

[0056]

[0057]

[0058]

[0059] =

[0060]

[0061]

[0062]

[0063] Ph in group II is phenyl.

[0064] Based on 100 parts by weight of the organometallic compound, the additive may be included in the resist composition in an amount from about 0.1 parts by weight to about 100,000 parts by weight.

[0065] The resist composition may further include a solvent.

[0066] The solvent can be a polar aprotic solvent.

[0067] The solvent can be selected from ketone-based solvents, ester-based solvents, and any combination thereof.

[0068] The solvent can be selected from chain ketone solvents, cyclic ketone solvents, ether carboxylic acid ester solvents containing polyols, lactone solvents, acetate solvents, and any combination thereof.

[0069] The solvent may be methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, n-butyl acetate, or any combination thereof.

[0070] According to some exemplary embodiments, the 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 form an exposed resist film; and developing the exposed resist film using a developer.

[0071] Exposure can be based on irradiation 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.

[0072] Based on exposing at least a portion of the photoresist film, the exposed photoresist film may include an exposed portion and an unexposed portion. The difference between the water contact angle of the unexposed portion and the water contact angle of the exposed portion may be 25° or greater.

[0073] Based on exposing at least a portion of the photoresist film, the exposed photoresist film may include exposed and unexposed portions. The developer may include distilled water, an alkaline developer, or any combination thereof. Developing the exposed photoresist film may include removing the exposed portions.

[0074] Based on exposing at least a portion of the photoresist film, the exposed photoresist film may include exposed portions and unexposed portions. The developer may include an organic solvent. Developing the exposed photoresist film may include removing the unexposed portions. Attached Figure Description

[0075] The above and other aspects, features, and advantages of some exemplary embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, wherein:

[0076] Figure 1 This is a flowchart illustrating a pattern forming method according to some example implementations;

[0077] Figure 2A , 2B 2C and 2C are side cross-sectional views illustrating a pattern forming method according to some exemplary embodiments;

[0078] Figure 3A , 3B 3C, 3D, and 3E are side cross-sectional views illustrating a method for forming a patterned structure according to some exemplary embodiments;

[0079] Figure 4A , 4B 4C, 4D, and 4E are side cross-sectional views illustrating a method for forming a semiconductor device according to some exemplary embodiments;

[0080] Figure 5 The results of Fourier transform infrared spectroscopy (FT-IR) analysis of compounds M1, A1, mixtures of compounds M1 and A1, and compound X1 are shown; and

[0081] Figure 6A , 6B 6C and 6D and Figure 7 The changes in film thickness after development according to dosage are shown for Examples 1-1, 1-2, 2-1 and Comparative Examples 1-1 and 1-2, respectively. Detailed Implementation

[0082] Some exemplary embodiments will now be described in detail, some of which are shown in the accompanying drawings, wherein the same reference numerals always denote the same elements. In this respect, some exemplary embodiments may take different forms and should not be construed as limited to the description set forth herein. Therefore, only some exemplary embodiments are described below with reference to the accompanying drawings to explain aspects thereof. As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of…” modify the entire list of elements when preceding or following it and do not modify individual elements of the list.

[0083] The inventive concept can have various modifications and can be embodied in several different forms. Specific examples and embodiments will be shown in the accompanying drawings and described in detail in the specification. However, it should be understood that this is not intended to limit the inventive concept to the specific forms disclosed, but rather, it is intended to cover all modifications, equivalents, and substitutions falling within the spirit and scope of the inventive concept. In describing the inventive concept, detailed descriptions of known related art will be omitted where it is determined that such detailed descriptions unnecessarily obscure the gist of the inventive concept.

[0084] The term "the (said)" and similar indicative words may correspond to both the singular and plural. The operations constituting the method may be performed in any suitable order unless otherwise stated herein or clearly contradicted by the context, and are not necessarily limited to the stated order.

[0085] All illustrative or explanatory terms used in some exemplary embodiments are merely for the purpose of describing the technical ideas in detail, and the scope of the inventive concept is not limited by the illustrative or explanatory terms unless they are limited by the claims.

[0086] Regardless of whether the element and / or its properties are modified to be “substantially”, it will be understood that such element and / or its properties should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) surrounding the element and / or its properties.

[0087] When the terms “about” or “substantially” are used in conjunction with numerical values ​​in this specification, it is intended that the relevant numerical value includes manufacturing or operational tolerances (e.g., ±10%) around the stated value. Furthermore, when the terms “about” and “substantially” are used in conjunction with geometry, it is intended that the precision of the geometry is not required, but rather the tolerance of the shape is within the scope of this disclosure. Moreover, 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 manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape. When a range is specified, the range includes all values ​​within that range, for example, increments of 0.1%.

[0088] As described herein, when an operation is described as being performed “by” or “via” additional operations, or when an effect such as a structure is described as being established “by” or “via” additional operations, it will be understood that the operation may be performed “based on” the additional operations and / or the effect / structure may be established “based on” the additional operations, which may include performing the additional operations alone or in combination with other further additional operations.

[0089] Although the terms “first,” “second,” “third,” etc., may be used in this document 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 by them.

[0090] In this specification, when a part of a layer, film, region, plate, etc. is described as being "on" or "above" another part, it can include not only the meaning of "in contact with... on / below / left / right" but also the meaning of "in non-contact with... on / below / left / right".

[0091] A singular expression covers a plural expression unless it has a distinct meaning in the context. Unless explicitly stated otherwise, it will be understood that terms such as “comprising” and “having” are intended to indicate the presence of features, figures, steps, actions, components, parts, ingredients, materials or combinations thereof disclosed in the specification, and are not intended to exclude the possibility that one or more other features, figures, steps, actions, components, parts, ingredients, materials or combinations thereof may be present or added.

[0092] Whenever a range of values ​​is described, the range includes all values ​​falling within the range, as explicitly stated, and the range further includes the boundaries of the range. Therefore, the range “X to Y” includes all values ​​between X and Y, and also includes X and Y.

[0093] As used in this article, “C” x -C y "C1-C6" or "C1-C6" means that the number (e.g., quantity) of carbons constituting the group is x to y, where x and y can each be any natural number. For example, "C1-C6" and "C1-C6" mean that the number of carbons constituting the group is 1 to 6, and "C6-C" means that the number of carbons constituting the group is 1 to 6. 20 "C6-C20" means that the number of carbons constituting the group is 6 to 20.

[0094] As used herein, the term "monovalent hydrocarbon group" refers to a monovalent residue derived from an organic compound or its derivatives comprising carbon and hydrogen, and specific examples include straight-chain or branched alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); monovalent saturated alicyclic hydrocarbon groups (cycloalkyl) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornel, norbornelmethyl, tricyclodecyl, tetracyclododecyl, etc.). Tetracyclododecylmethyl and dicyclohexylmethyl); monovalent unsaturated aliphatic hydrocarbon groups (alkenyl or ynyl) (e.g., allyl); monovalent unsaturated alicyclic hydrocarbon groups (cycloalkenyl) (e.g., 3-cyclohexenyl); aryl (e.g., phenyl, 1-naphthyl and 2-naphthyl); arylalkyl (e.g., benzyl and diphenylmethyl); monovalent hydrocarbon groups including heteroatoms (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetaminomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl and 3-oxocyclohexyl) or combinations thereof. Additionally, some of the hydrogen atoms in these groups may be replaced by portions including heteroatoms (e.g., one or more heteroatoms) such as oxygen, sulfur, nitrogen, phosphorus, or halogen atoms, or some of the carbon atoms in these groups may be replaced by portions including heteroatoms (e.g., one or more heteroatoms) such as oxygen, sulfur, nitrogen, or phosphorus. Therefore, these groups may include cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulcinolone moiety, carboxylic anhydride moiety, etc.

[0095] As used herein, the term "divalent hydrocarbon group" refers to a divalent residue and means a system in which any hydrogen atom of a monovalent hydrocarbon group is replaced by a binding site with an adjacent atom. Divalent hydrocarbon groups may include, for example, straight-chain or branched alkylene groups, cycloalkylene groups, alkenyl groups, ynylene groups, cycloalkenyl groups, aryl groups, and groups in which some of their carbon atoms are replaced by heteroatoms.

[0096] As used herein, the term "alkyl" refers to a straight-chain or branched saturated aliphatic monovalent hydrocarbon group, and examples of such groups are methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. As used herein, the term "alkylene" refers to a straight-chain or branched saturated aliphatic divalent hydrocarbon group, and examples of such groups may include methylene, ethylene, propylene, butylene, and isobutylene.

[0097] As used herein, the term "haloalkyl" refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom, and examples include CF3. In this respect, the halogen atom may be F, Cl, Br, or I.

[0098] As used in this article, the term "alkoxy" refers to a compound of the formula -OA. 101 The monovalent group represents A. 101 It is an alkyl group. Examples include methoxy, ethoxy, and isopropoxy.

[0099] As used in this article, the term "alkylthio" refers to a group derived from the formula -SA. 101 The monovalent group represents A. 101 It is an alkyl group.

[0100] As used herein, the term "haloalkoxy" refers to a group in which one or more hydrogen atoms of an alkoxy group are replaced by halogen atoms, and specific examples include -OCF3, etc.

[0101] As used herein, the term "haloalkylthio" refers to a group in which one or more hydrogen atoms of an alkylthio group are replaced by halogen atoms, and specific examples include -SCF3, etc.

[0102] As used herein, the term "cycloalkyl" refers to a monovalent saturated hydrocarbon cyclic group, and specific examples include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, as well as polycyclic fused-ring groups such as norcamphenyl and adamantyl. As used herein, the term "cycloalkylene" refers to a divalent saturated hydrocarbon cyclic group, and specific examples include cyclopentylene, cyclohexylene, adamantylene, adamantylmethylene, norcamphenylene, norcamphenylmethylene, tricyclodecylene, tetracyclododecylmethylene, tetracyclododecylmethylene, dicyclohexylmethylene, etc.

[0103] As used in this article, the term "cycloalkoxy" refers to a compound of the formula -OA. 102 The monovalent group represents A. 102 It is a cycloalkyl group. Examples include cyclopropoxy and cyclobutoxy.

[0104] As used in this article, the term "cycloalkylthio" refers to a compound derived from the formula -SA. 102 The monovalent group represents A. 102 It is a cycloalkyl group.

[0105] As used herein, the term "heterocyclic alkyl" refers to a cycloalkyl group in which some of its carbon atoms are partially replaced by a heteroatom, such as oxygen, sulfur, or nitrogen, and a heterocyclic alkyl group may include, for example, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, or carboxylic anhydride moieties. As used herein, the term "hemieloalkylene" refers to a group in which some of its carbon atoms are partially replaced by a heteroatom, such as oxygen, sulfur, or nitrogen.

[0106] As used in this article, the term "heterocyclic alkoxy" refers to a compound of the formula -OA. 103 The monovalent group represents A. 103 It is a heterocyclic alkyl group.

[0107] As used in this article, the term "heterocyclic alkylthio" refers to a compound of the formula -SA 103 The monovalent group represents A. 103 It is a heterocyclic alkyl group.

[0108] As used herein, the term "alkenyl" refers to a straight-chain or branched unsaturated aliphatic hydrocarbon monovalent group comprising one or more carbon-carbon double bonds. As used herein, the term "alkenyl" refers to a straight-chain or branched unsaturated aliphatic hydrocarbon divalent group comprising one or more carbon-carbon double bonds.

[0109] As used in this article, the term "olefinic group" refers to a group having the formula -OA. 104 The monovalent group, of which A 104 It is an alkenyl group.

[0110] As used herein, the term "cycloalkenyl" refers to a monovalent unsaturated hydrocarbon cyclic group that comprises at least one carbon-carbon double bond and is non-aromatic. As used herein, the term "cycloalkenylene" refers to a divalent unsaturated hydrocarbon cyclic group that comprises at least one carbon-carbon double bond and is non-aromatic.

[0111] As used in this article, the term "cycloolefin" refers to a compound with the formula -OA. 105 The monovalent group, of which A 105 It is a cycloalkenyl group.

[0112] As used herein, the term "heterocyclic alkenyl" refers to a group in which some carbon atoms of the cycloalkenyl group are partially replaced by heteroatoms (e.g., one or more heteroatoms) such as oxygen, sulfur, or nitrogen. As used herein, the term "hemiecyclic alkenyl" refers to a cycloalkenyl group in which some carbon atoms are partially replaced by heteroatoms (e.g., one or more heteroatoms) such as oxygen, sulfur, or nitrogen.

[0113] As used in this article, the term "heterocyclic olefin" refers to a compound with the formula -OA. 106 The monovalent group, of which A 106 It is a heterocyclic alkenyl group.

[0114] As used herein, the term "alkynyl" refers to a straight-chain or branched monovalent unsaturated aliphatic hydrocarbon group comprising one or more carbon-carbon triple bonds.

[0115] As used in this article, the term "alkynyloxy group" refers to a group with -OA. 107 The monovalent group of the formula, wherein A 107 It is an acetylinyl group.

[0116] As used herein, the term "aryl" refers to a monovalent group comprising a carbocyclic aromatic system, and examples of such groups include phenyl, naphthyl, anthraceneyl, phenanthryl, pyreneyl, and trefyl. As used herein, the term "arylene" refers to a divalent group comprising a carbocyclic aromatic system.

[0117] As used in this article, the term "aryloxy group" refers to the group formed by the formula -OA 104 The monovalent group represents A. 104 It is an aryl group.

[0118] As used in this article, the term "arylthio" refers to a group derived from the formula -SA 104 The monovalent group represents A. 104 It is an aryl group.

[0119] As used herein, the term "heteroaryl" refers to a monovalent group comprising a heterocyclic aromatic system, and examples of such groups include pyridyl, pyrimidinyl, and pyrazinyl. As used herein, the term "hybridaryl" refers to a divalent group comprising a heterocyclic aromatic system.

[0120] As used in this article, the term "heteroaryloxy" refers to a compound derived from the formula -OA. 105 The monovalent group represents A. 105 It is a heteroaryl group.

[0121] As used in this article, the term "heteroaryl thio" refers to a compound derived from the formula -SA. 105 The monovalent group represents A. 105 It is a heteroaryl group.

[0122] As used herein, the term "arylalkyl" refers to an alkyl group substituted with a monovalent group having a carbocyclic aromatic system, and specific examples include benzyl, diphenylmethyl, etc.

[0123] As used herein, the term "heteroarylalkyl" refers to a group in which the alkyl group is replaced by a monovalent group having a heterocyclic aromatic system.

[0124] As used herein, the term "heterocyclic group" refers to a monocyclic or polycyclic group having 1 to 60 carbon atoms, including at least one heteroatom, and is a group that includes monovalent, divalent, and trivalent groups.

[0125] As used herein, the term "substituent" includes deuterium, halogen atom, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 heteroaryl, C1-C 20 Heteroaryloxy or C1-C 20 heteroaryl thiols;

[0126] Each of the following C1-C is replaced: 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 heteroaryl, C1-C 20 Heteroaryloxyl and C1-C 20 Heteroaryl thiols: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 heteroaryl, C1-C 20 Heteroaryloxy, C1-C 20 A heteroaryl thio group or any combination thereof; or any combination thereof.

[0127] As used herein, unless otherwise defined, "aromatic ring" refers to a functional group in which all atoms of the cyclic functional group have p-orbitals and where these p-orbitals are conjugated.

[0128] In the following description, some exemplary embodiments will be described in detail with reference to the accompanying drawings, wherein the same reference numerals throughout the drawings denote substantially the same or corresponding components, and redundant descriptions will be omitted. In the drawings, the thickness of layers and regions is exaggerated for clarity. Furthermore, in the drawings, the thickness of some layers and regions is exaggerated for ease of description. At the same time, the exemplary embodiments described herein are merely examples and various modifications can be made therein.

[0129] [Resistant Composition]

[0130] The resist composition according to some exemplary embodiments comprises an organometallic compound represented by Formula 1 and an additive represented by Formula 2:

[0131] Formula 1

[0132] M 11 (R x ) n (R y ) (m-n)

[0133] Formula 2

[0134] (X2) c2 -(L2) a2 -[Y2-Z2] b2

[0135] In Equations 1 and 2,

[0136] M 11 It can be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po).

[0137] R x It can be *-X1-Y1,

[0138] Ry It can be *-(L1) a1 -(R1) b1 ,

[0139] n can be an integer from 1 to 6 (inclusive).

[0140] m can be an integer from 1 to 6 (inclusive).

[0141] mn is 0 or greater

[0142] Where n>1 such that Equation 1 includes multiple R x In example implementations, multiple R x They may be the same or different from each other (for example, Equation 1 may optionally include multiple R based on n greater than 1). x Multiple R x (Whether they are the same or different)

[0143] Where (mn)>1, Equation 1 includes multiple R y In example implementations, multiple R y They may be the same or different from each other (for example, Equation 1 may optionally include multiple R values ​​based on mn being greater than 1). y Multiple R y (Whether they are the same or different)

[0144] X1 can be O, OC(=O), C(=O)O, OS(=O), S(=O)O, OS(=O)2, S(=O)2O, S, SC(=O) or C(=O)S,

[0145] Y1 may be hydrogen, deuterium, or optionally include a straight-chain, branched, or cyclic C1-C chain containing heteroatoms (e.g., one or more heteroatoms). 30 Monovalent hydrocarbon groups,

[0146] L1 can be a single bond, or optionally a straight chain, branched chain, or cyclic C1-C chain including heteroatoms (e.g., one or more heteroatoms). 30 Divalent hydrocarbon groups,

[0147] a1 can be an integer from 0 to 4 (inclusive).

[0148] R1 can be a straight-chain, branched, or cyclic C1-C chain that optionally contains heteroatoms (e.g., one or more heteroatoms). 30 A monovalent hydrocarbon group, wherein (b1) > 1 such that formula R y In example embodiments including multiple R1s, two adjacent groups among the multiple R1s may optionally combine with each other to form a ring (e.g., Formula 1 optionally includes multiple R1s based on b1 being greater than 1, where two adjacent groups among the multiple R1s may optionally combine with each other to form a ring).

[0149] b1 can be an integer from 1 to 4 (inclusive).

[0150] X2 can be OH, SH, C(=O)OH, S(=O)OH, S(=O)2OH, or P(=O)(OH)2.

[0151] c2 can be an integer from 1 to 4 (inclusive).

[0152] Each L2 can independently be a straight-chain, branched, or cyclic C1-C that optionally contains heteroatoms (e.g., one or more heteroatoms). 30 Divalent hydrocarbon groups,

[0153] a2 can be an integer from 0 to 4 (inclusive).

[0154] Y2-Z2 can be a photoreactive unit.

[0155] b2 can be an integer from 1 to 4 (inclusive of the endpoints), and

[0156] * indicates the binding site with the adjacent atom of Formula 1.

[0157] The molecular weight of the organometallic compound may be about 3000 g / mol or lower. In some exemplary embodiments, the molecular weight of the organometallic compound may be about 2000 g / mol or lower.

[0158] In some example implementations, M in Equation 1 11 It can be Sn, Sb, Te, or Bi. In some example implementations, in Equation 1, M... 11 It can be Sn.

[0159] In Equation 1, m refers to M 11 The valence of the compound.

[0160] In some implementation examples, n in Equation 1 can be an integer from 1 to 4.

[0161] In some implementation examples, m in Equation 1 can be an integer from 1 to 4.

[0162] In some implementation examples, in Equation 1, n can be an integer from 1 to 4, m can be an integer from 1 to 4, and M 11 It can be Sn.

[0163] In some example implementations, in Equation 1, M 11 and R x The key between them can be M 11 -Oxygen single bond or M 11 -Sulfur single bond. In some exemplary embodiments, in Equation 1, M 11 With R xThe key between them can be M 11 -Oxygen single bond.

[0164] In some example implementations, in Equation 1, M 11 With R y The key between them can be M 11 - Carbon single bond.

[0165] In some implementation examples, X1 in Equation 1 can be O, OC (=O), C (=O)O, S, SC (=O) or C (=O)S.

[0166] In some implementation examples, Y1 in Formula 1 can be independently selected from: hydrogen, deuterium, Cl-C 30 Alkyl, C1-C 30 Haloalkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy groups, C1-C 30 Haloalkylthio group, C3-C 30 cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C6-C 30 Aryloxy group, C6-C 30 Arylthio, C7-C 30 arylalkyl, C1-C 30 heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 heteroaryl thiols and C2-C 30 Heteroarylalkyl. C1-C 30 Alkyl, C1-C 30 Haloalkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy groups, C1-C 30 Haloalkylthio group, C3-C 30 cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C6-C 30 Aryloxy group, C6-C 30 Arylthio, C7-C 30 arylalkyl, C1-C 30 heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 heteroaryl thiols and C2-C 30 Each of the heteroaryl alkyl groups may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

[0167] In some exemplary embodiments, Y1 may be independently selected from: hydrogen; deuterium; and each of the following C1-C that is not substituted or is substituted with: 30 Alkyl, C1-C 30 Haloalkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C1-C 20Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl or any combination thereof.

[0168] In some exemplary embodiments, Y1 in Formula 1 may be selected from: hydrogen; deuterium; and C1-C, which are either unsubstituted or substituted with the following: 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl and C6-C 30 Aryl: deuterium, halogen, or any combination thereof.

[0169] Specifically, Y1 in Formula 1 may be selected from: 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: deuterium, halogen, methyl, ethyl, phenyl, naphthyl or any combination thereof.

[0170] In some implementation examples, L1 in Formula 1 can be a single bond, a substituted or unsubstituted C1-C bond. 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl or substituted or unsubstituted C1-C 30 Hybrid aryl.

[0171] In some implementation examples, L1 in Equation 1 can be selected from: single bonds, and C1-C 30 Alkylene, C3-C 30 Cycloalkylene, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkylene, C3-C 30 Heterocyclic alkenyl, C6-C 30 aryl and C1-C 30 Hybrid aryl. C1-C 30 Alkylene, C3-C 30 Cycloalkylene, C3-C 30Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkylene, C3-C 30 Heterocyclic alkenyl, C6-C 30 aryl and C1-C 30 Each heteroaryl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

[0172] In some example implementations, L1 in Formula 1 may be selected from a single bond; and C1-C, each of which is not substituted or is substituted by the following: 30 Alkylene and C6-C 30 Aryl groups: deuterium, halogen, hydroxyl, cyano, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl groups or any combination thereof.

[0173] In some implementation examples, a1 in Equation 1 can be 0, 1, or 2.

[0174] In some example implementations, R1 in Equation 1 can be selected from C1-C 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C30 heteroaryl and C2-C 30 Heteroarylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Each of the heteroaryl alkyl groups may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

[0175] In some example implementations, R1 in Equation 1 can be selected from C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30Aryl and C7-C 30 Each aryl alkyl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

[0176] In some example implementations, R1 in Equation 1 can be selected from any one of Equations 3-1 to 3-21:

[0177] .

[0178] In equations 3-1 to 3-21,

[0179] At least one hydrogen atom may be present or optionally replaced by: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 heteroaryl or any combination thereof, and

[0180] * indicates the binding site with the adjacent atom of Formula 1.

[0181] In Equation 1, b1 indicates the number of R1 substituents, and for example, b1 in Equation 1 can be 1 or 2.

[0182] Two adjacent R1s may optionally be combined with each other to form a loop (e.g., in an example implementation where b1 is 2 or greater).

[0183] In some implementation examples, in Equation 1, b1 can be 2 or greater, and R1 can be selected from C2-C.30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl and C6-C 30 Aryl. C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl and C6-C 30 Each aryl group can be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C. 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 heteroaryl groups or any combination thereof.

[0184] In some exemplary embodiments, the organometallic compound represented by Formula 1 may be represented by one of Formulas 1-1 to 1-4:

[0185] Equation 1-1 Equation 1-2

[0186]

[0187] Equation 1-3 Equation 1-4

[0188]

[0189] Among them, in equations 1-1 to 1-4,

[0190] M 11 As described in reference equation 1 above, such that M 11 It can be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po).

[0191] L 11 To L 13 Each independently as described with respect to L1 in Equation 1, such that L 11 To L 13 Each can be independently a straight-chain, branched, or cyclic C1-C chain that optionally includes heteroatoms (e.g., one or more heteroatoms). 30 Divalent hydrocarbon groups,

[0192] a11 to a13 are each independently described as in relation to a1 in Equation 1, such that a11 to a13 can each be an integer from 0 to 4 independently.

[0193] R 11 To R 13 Each independently as described with respect to R1 in Equation 1, such that R 11 To R13 Each is independently a straight-chain, branched, or cyclic C1-C structure that optionally includes heteroatoms (e.g., one or more heteroatoms). 30 Monovalent hydrocarbon groups,

[0194] b11 to b13 are each independently described as in relation to b1 in Equation 1, such that b11 to b13 are each independently an integer from 1 to 4, where based on b11 being greater than 1, multiple R 11 Two adjacent groups in the ring may optionally combine with each other to form a ring, based on b12 being greater than 1, and multiple R groups. 12 Two adjacent groups in the ring may optionally combine with each other to form a ring, and based on b13 being greater than 1, multiple R groups may be involved. 13 Two adjacent groups in the ring may optionally combine with each other to form a ring.

[0195] X 11 To X 14 Each independently as described with respect to X1 in Equation 1, such that X 11 To X 14 Each can be independently O, OC (=O), C (=O)O, OS (=O), S (=O)O, OS (=O)2, S (=O)2O, S, SC (=O) or C (=O)S, and

[0196] Y 11 To Y 13 Each independently as described with respect to Y1 in Equation 1, such that Y 11 To Y 13 Each is a straight-chain, branched, or cyclic C1-C atom, independently of hydrogen, deuterium, or optionally including one or more heteroatoms. 30 Monovalent hydrocarbon group.

[0197] In some exemplary embodiments, the organometallic compound represented by Formula 1 may be selected from Group I:

[0198] <Group I>

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] In group I, n is an integer from 0 to 3 (inclusive).

[0208] In some implementation examples, n in group I can be 2.

[0209] Any type of organometallic compound can be used, or a combination of two or more types of organometallic compounds can be used.

[0210] In some implementation examples, X2 in Formula 2 can be OH or C(=O)OH.

[0211] In some implementation examples, c2 in Equation 2 can be 1.

[0212] In Equation 2, L2 can be as described with respect to L1, such that L2 can be a straight-chain, branched, or cyclic C1-C chain optionally comprising one or more heteroatoms. 30 Divalent hydrocarbon groups.

[0213] In some implementation examples, a2 in Equation 2 can be 1 or 2.

[0214] In some example implementations, (L2) in Equation 2 a2 It can be expressed by one of equations 5-1 to 5-7:

[0215] .

[0216] In equations 5-1 to 5-7,

[0217] R 51 To R 53 Each can be independently hydrogen, deuterium, halogen, hydroxyl, cyano, C1-C4 alkyl, or C1-C4 haloalkyl.

[0218] b51 can be an integer from 1 to 4 (inclusive of the endpoints).

[0219] n51 can be an integer from 1 to 4 (inclusive), and

[0220] * and *' each represent the binding site with the adjacent atom in Formula 2.

[0221] In some implementation examples, Y2 in Equation 2 can be OC (=O), C (=O)O, OS (=O)2 or S (=O)2O.

[0222] In some example implementations, Z2 in Formula 2 can be *-C(R2)(R3)(R4), *-C(R2)=N(R3), *-N=C(R2)(R3) or *-N(R2)(R3), where * is the binding site of the adjacent atom in Formula 2.

[0223] In some exemplary embodiments, in Formula 2, R2 to R4 can each independently be hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, -C(=O)R5, -C(R5)=NR6, -OR5, -S(=O)R5, -S(=O)2R5, -S(=O)2OR5, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C1-C 30 Halogenated alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C 30 Halogenated alkoxy, substituted or unsubstituted C1-C 30 Haloalkylthio, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkoxy, substituted or unsubstituted C3-C 30 Cyclothio, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkoxy, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 Alkenyl group, substituted or unsubstituted C2-C 30 Thiolated, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyloxy, substituted or unsubstituted C3-C 30 Cycloalkenyl thio, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C3-C 30 Heterocyclic olefins, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C2-C 30 Acryloxy group, substituted or unsubstituted C2-C 30 Acrylylthio, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 aryloxy, substituted or unsubstituted C6-C 30 Arylthio, substituted or unsubstituted C1-C 30 heteroaryl, substituted or unsubstituted C1-C 30 Heteroaryl groups or substituted or unsubstituted C1-C 30 Heteroaryl thiols, R2 and R3 optionally combine with each other to form a ring, and

[0224] R5 and R6 can each be independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1-C. 30 Alkyl, substituted or unsubstituted C1-C 30 Halogenated alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C 30 Halogenated alkoxy, substituted or unsubstituted C1-C 30 Haloalkylthio, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkoxy, substituted or unsubstituted C3-C 30 Cyclothio, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkoxy, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 Alkenyl group, substituted or unsubstituted C2-C 30 Thiolated, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyloxy, substituted or unsubstituted C3-C 30 Cycloalkenyl thio, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C3-C 30 Heterocyclic olefins, substituted or unsubstituted C3-C 30 Heterocyclic thiols, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C2-C 30 Acryloxy group, substituted or unsubstituted C2-C 30 Acrylylthio, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 aryloxy, substituted or unsubstituted C6-C 30 Arylthio, substituted or unsubstituted C1-C 30 heteroaryl, substituted or unsubstituted C1-C 30 Heteroaryl groups or substituted or unsubstituted C1-C 30 heteroaryl thiols.

[0225] In some exemplary embodiments, in Formula 2, R2 to R4 can each be independently selected from: hydrogen; deuterium; halogen; cyano; nitro; hydroxyl; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Each aryl alkyl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heterooxygen group, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or any combination thereof, and

[0226] R5 and R6 can each independently be: hydrogen; deuterium; hydroxyl group; and each of their own unsubstituted or substituted C1-C groups as follows: 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30Arylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heterooxygen group, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

[0227] In some exemplary embodiments, in Formula 2, R2 to R4 can each be independently selected from: hydrogen; deuterium; halogen; cyano; nitro; hydroxyl; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Each aryl alkyl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C. 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 Heteroaryl or any combination thereof, and

[0228] R5 and R6 can be independently selected from: hydrogen; deuterium; hydroxyl group; and each of the following C1-C groups, either unsubstituted or substituted: 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl groups: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 heteroaryl groups or any combination thereof.

[0229] In some exemplary embodiments, in Formula 2, R2 to R4 may each be independently selected from: hydrogen; deuterium; halogen; cyano; nitro; hydroxyl; -C(=O)R5; -C(R5)=NR6; -S(=O)2R5; and one of Formulas 3-1 to 3-21, and

[0230] R5 and R6 can be independently selected from: hydrogen; deuterium; hydroxyl group; and one of formulas 3-1 to 3-21:

[0231] .

[0232] In equations 3-1 to 3-21,

[0233] At least one hydrogen atom may be present or optionally replaced by deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 Substitution of heteroaryl groups or any combination thereof, and

[0234] * indicates the binding site with the adjacent atom in Formula 2.

[0235] In some example implementations, Z2 in Equation 2 can be represented by one of Equations 4-1 to 4-9:

[0236] .

[0237] In equations 4-1 to 4-9,

[0238] R2 to R4 can be independently selected from: hydrogen; deuterium; halogen; cyano; nitro, hydroxyl, C1-C 30 Alkyl, C3-C 30cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Each aryl alkyl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C. 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 heteroaryl or any combination thereof

[0239] R5, R 5a R 5b R6 and R6 can be independently selected from: hydrogen, deuterium, C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Each aryl alkyl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C. 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 heteroaryl or any combination thereof

[0240] R2 to R5, R 5a and R 5b Two adjacent groups in the ring can optionally combine with each other to form a ring.

[0241] A 41 and A 42 Each can be independently a C1-C that optionally includes one or more heteroatoms. 30 Cycloalkyl groups or C1-C groups optionally including one or more heteroatoms 30 Aryl,

[0242] R 41 and R 42 Each can be independently hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl or C1-C 20 Mixed aromatics,

[0243] b41 and b42 can each be an integer from 1 to 10 (inclusive), and

[0244] * indicates the binding site with the adjacent atom in Formula 2.

[0245] In some example implementations, Z2 in Equation 2 can be represented by one of Equations 4-11 to 4-50:

[0246]

[0247]

[0248]

[0249] .

[0250] In equations 4-11 to 4-50,

[0251] * indicates the binding site with the adjacent atom in Formula 2.

[0252] In some exemplary embodiments, at least one of Z2 in Formula 2 may include an electron-withdrawing group.

[0253] In some exemplary embodiments, in Formula 2, at least one of R2 to R4 may be an electron-withdrawing group.

[0254] In some exemplary embodiments, at least one of R2 to R4 in Formula 2 may be selected from: halogen, cyano, nitro, -C(=O)R5, -C(R5)=NR6, -S(=O)2R5, Cl-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Aryl alkyl groups can be converted to halogens, cyano groups, nitro groups, C1-C groups, etc. 20 Halogenated alkyl groups or any combination thereof are substituted.

[0255] R5 and R6 can be independently selected from: hydrogen, deuterium, C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl. C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Each aryl alkyl group may be unsubstituted or substituted with: deuterium, halogen, cyano, nitro, carbonyl moiety, C1-C. 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C1-C 20 heteroaryl groups or any combination thereof.

[0256] In some implementation examples, b2 in Equation 2 can be 1.

[0257] In some implementation examples, the additive represented by Formula 2 may be a self-assembly II:

[0258] Group II

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266] .

[0267] Regarding group II, Ph is phenyl.

[0268] The additive may be any compound represented by Formula 2, or a mixture of two or more such compounds may be used.

[0269] The additive can improve the chemical stability of the organometallic compound represented by Formula 1 by ligand exchange with the organometallic compound.

[0270] In the resist composition, based on 100 parts by weight of the resist composition, the organometallic compound may 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, 1.5 parts by weight or more, 90 parts by weight or less, or 80 parts by weight or less. When these ranges are met, sufficient chemical bonds are formed between the organometallic compounds and side reactions are suppressed, thereby providing a resist composition with improved sensitivity and / or resolution.

[0271] In the resist composition, based on 100 parts by weight of the resist composition, the additive may 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, 1.5 parts by weight or more, 90 parts by weight or less, or 80 parts by weight or less. When these ranges are met, sufficient chemical bonds are formed between the organometallic compounds and side reactions are suppressed, thereby providing a resist composition with improved sensitivity and / or resolution.

[0272] In the resist composition, the additive may be included in an amount from about 0.1 parts by weight to about 100,000 parts by weight based on 100 parts by weight of the organometallic compound. In some exemplary embodiments, the additive may be included in an amount from about 10 parts by weight to about 1,000 parts by weight based on 100 parts by weight of the organometallic compound. When these ranges are met, the resist composition can significantly improve storage stability while maintaining photosensitivity at the level of an additive-free resist composition.

[0273] In view of at least the above, the resist composition may have a composition with improved storage stability and / or the resist composition may be configured to alter one or more physical properties, even by exposure to incident light (e.g., high-energy rays), to overcome the limitations of chemically amplified resists that can cause the formed acid to diffuse into unexposed areas. As a result, the resist composition may be configured to reduce, minimize, or prevent the possibility of reduced pattern uniformity and / or increased surface roughness when the resist composition is used in a patterning method, based on avoiding such acid diffusion, while providing improved chemical stability of the resist composition in normal use at room temperature (and thus reduced, minimized, or prevented risk of chemical degradation) and / or alter physical properties even by exposure to small amounts (e.g., low intensity) of incident light (e.g., high-energy rays).

[0274] Since the resist composition is non-chemically scaled up, it may substantially exclude photoacid generators.

[0275] Because the physical properties of the organometallic compound change upon exposure to light, the resist composition may not include or substantially exclude compounds having a molecular weight of about 1,000 or greater, other than the organometallic compound.

[0276] Exposure to high-energy radiation alters the solubility of the resist composition in a developer. The resist composition may be a negative resist composition in which the unexposed portions of the resist film are dissolved and removed to form a negative resist pattern, or a positive resist composition in which the exposed portions of the resist film are dissolved and removed to form a positive resist pattern. The resist composition can be modified in various ways, such as negative or positive, depending on the exposure intensity and / or the type of developer.

[0277] Additionally, the resist composition can be used in a distilled water development process when developing with distilled water (DI), an alkaline development process when developing with an alkaline developer, or a solvent development process when developing with a developer containing an organic solvent (hereinafter also referred to as an organic developer). In some exemplary embodiments, the resist composition can be used in a distilled water development process or a solvent development process.

[0278] In some embodiments, when distilled water, an alkaline developer, or any combination thereof are used as the developer, the exposed portions can be washed away and removed by the developer, while the unexposed portions remain unremoved by the developer. As a result, the properties of a positive resist composition are obtained. Simultaneously, when an organic solvent is used as the developer, the unexposed portions can be washed away and removed by the developer, while the exposed portions remain unremoved by the developer. As a result, the properties of a negative resist composition are obtained. That is, the resist composition can be a negative resist composition or a positive resist composition, depending on the polarity of the developer.

[0279] Not limited to a specific theory, the organometallic compound can react with additives, such that the ligands of the organometallic compound (e.g., R...) x The ligand is replaced by the additive. Subsequently, the organometallic compound in which the ligand is replaced by the additive may undergo a change in polarity due to the dissociation of specific bonds (e.g., bonds within a photoreactive unit) by high-energy radiation.

[0280] In some exemplary embodiments, organometallic compounds having ligands substituted with additives can generate free radicals from photoreactive units via high-energy radiation, and optionally, in an atmosphere in which water is present, the free radicals can react to generate polar functional groups. Therefore, the physical properties of the organometallic compound, particularly its solubility in developer, can be altered by high-energy radiation.

[0281] The organometallic compound and the additive can be prepared by any suitable method, or commercially available products can be used for this purpose.

[0282] The structure (composition) of the organometallic compound and the additive can be confirmed by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), X-ray fluorescence (XRF), mass spectrometry, ultraviolet (UV) spectroscopy, single-crystal X-ray structure analysis, powder X-ray diffraction (PXRD), liquid chromatography, size exclusion chromatography (SEC), and thermal analysis. Detailed confirmation methods are described in the following examples.

[0283] Solvent

[0284] The resist composition may further include a solvent.

[0285] The solvents included in the resist composition are not particularly limited, as long as they are capable of dissolving or dispersing the organometallic compound, additives, and optional components as needed. The solvents may be used alone or in combination of two or more different types.

[0286] The solvent may include nonpolar solvents, polar aprotic solvents, or combinations thereof.

[0287] In some implementation examples, the solvent may be a polar aprotic solvent.

[0288] Nonpolar solvents may include ether-based solvents, hydrocarbon-based solvents, and combinations thereof.

[0289] Polar aprotic solvents may include ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and combinations thereof.

[0290] Examples of ether-based solvents are diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether; dialkyl ether solvents such as diethyl ether, dipropyl ether and dibutyl ether; cyclic ether solvents such as 1,4-dioxane, tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0291] Examples of ketone-based solvents are chain ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-pentyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; and other ketone solvents such as 2,4-pentanedione, acetone-acetone, and acetophenone.

[0292] Examples of amide-based solvents are cyclic amide solvents such as N,N'-dimethylimidazolium ketone and N-methyl-2-pyrrolidone; and linear amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide and N-methylpropionamide.

[0293] Examples of ester-based solvents include acetate solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isoamyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, and n-nonyl acetate; and polyol-containing ether carboxylic acid ester 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, etc. 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 dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate; and other solvents such as ethylene glycol diacetate, methoxytriethylene glycol 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.

[0294] Examples of sulfoxide-based solvents are dimethyl sulfoxide and diethyl sulfoxide.

[0295] Examples of hydrocarbon-based solvents are aliphatic or alicyclic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentylnaphthalene.

[0296] In some implementations, the solvent may be selected from ketone-based solvents, ester-based solvents, and combinations thereof.

[0297] In some embodiments, the solvent may be selected from chain ketone solvents, cyclic ketone solvents, polyol-containing ether carboxylic acid ester solvents, lactone solvents, acetate solvents, and combinations thereof.

[0298] In some exemplary embodiments, the solvent may be selected from methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, n-butyl acetate, and combinations thereof.

[0299] The resist composition may be anhydrous or substantially anhydrous, and therefore the solvent may also be anhydrous. In some exemplary embodiments, the resist composition may contain 3% by weight or less water (e.g., 0.01% by weight to 3% by weight, 0.1% by weight to 3% by weight, 1% by weight to 3% by weight, etc.), and the solvent may contain 3% by weight or less water (e.g., 0.01% by weight to 3% by weight, 0.1% by weight to 3% by weight, 1% by weight to 3% by weight, etc.).

[0300] Based on 100 parts by weight of the resist composition, the solvent can be used in amounts from about 0 parts by weight to about 99.9 parts by weight (e.g., from about 0.01 parts by weight to about 99.9 parts by weight, from about 0.1 parts by weight to about 99.9 parts by weight, from about 1 part by weight to about 99.9 parts by weight, etc.). The solvent can be used alone or in combination of two or more different types.

[0301] <Optional Ingredients>

[0302] As needed, the resist composition may further include surfactants, crosslinking agents, leveling agents, colorants, or combinations thereof.

[0303] The resist composition may further include a surfactant to improve properties such as coating and developing. Examples of surfactants are nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. The surfactant may be commercially available or synthetically manufactured. Examples of commercially available surfactants include KP341 (a product of Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75 and Polyflow No. 95 (products of Kyoisha Chemical Co., Ltd.), F-Top EF301, F-Top EF303 and F-Top EF352 (products of Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE® F171, MEGAFACE® F173, R40, R41, R43 (products of DIC Corporation), Fluorad® FC430 and Fluorad® FC431 (products of 3M), Asahiguard AG710 (product of AGC Inc.), and Surflon® S-382, Surflon® SC-101, Surflon® SC-102, Surflon® SC-103, and Surflon® SC-104, Surflon® SC-105 and Surflon® SC-106 (products of AGC Seimi Chemical Co., Ltd.).

[0304] Based on 100 parts by weight of the resist composition, a surfactant may be included in an amount from about 0 parts by weight to about 20 parts by weight. The surfactant may be used alone or in combination of two or more different types.

[0305] The method for preparing the resist composition is not particularly limited and may include, for example, mixing the organometallic compound, the additive, and any optional components in an organic solvent. There are no particular limitations on the temperature and duration of mixing. Filtration may be performed after mixing if necessary.

[0306] [Pattern Formation Method]

[0307] In the following text, reference will be made to Figure 1 and 2A The pattern forming method according to the exemplary embodiment is described in more detail in section 2C. Figure 1 This is a flowchart illustrating a pattern forming method according to some exemplary embodiments, and Figures 2A to 2C This is a side cross-sectional view illustrating a pattern forming method according to some exemplary embodiments. Specific examples of positive resist compositions are given below, but the inventive concept is not limited thereto.

[0308] Reference Figure 1 The pattern forming method may include: forming a resist film S101 by applying a resist composition to a substrate; exposing at least a portion of the resist film with high-energy rays to form an exposed resist film S102; and developing the exposed resist film using a developer S103. These operations may be omitted if necessary, and they may be performed in a different order.

[0309] First, refer to Figure 1 and Figure 2A Prepare substrate 100. Substrate 100 may be, for example, a semiconductor substrate such as a silicon or germanium substrate, glass, quartz, ceramic, or copper. In some exemplary embodiments, substrate 100 may include III-V compounds such as GaP, GaAs, or GaSb.

[0310] The resist composition may be applied to substrate 100 to form a resist film 110 having a target thickness, specifically by a coating method. The applied resist composition may be a resist composition as described herein according to any exemplary embodiment. Therefore, the resist film 110 may include a resist composition according to any exemplary embodiment. If desired, post-application baking (PAB) may be performed to remove any organic solvents remaining on the resist film 110.

[0311] The coating method can include spin coating, dip coating, roll coating, or other common coating methods. In particular, spin coating can be used, and the resist film 110 can have a target thickness by adjusting the viscosity, concentration, and / or rotation speed of the resist composition. In some exemplary embodiments, the thickness of the resist film 110 can be from about 10 nm to about 300 nm. In some exemplary embodiments, the thickness of the resist film 110 can be from about 30 nm to about 200 nm.

[0312] The lower limit of the PAB temperature can be 60°C or higher, for example, 80°C or higher. In some implementations, the upper limit of the PAB temperature can be 150°C or lower, for example, 140°C or lower. The lower limit of the PAB time can be 5 seconds or more, for example, 10 seconds or more. The upper limit of the PAB time can be 600 seconds or less, for example, 300 seconds or less.

[0313] Before applying the resist composition to the substrate 100, a sacrificial layer (not shown) for etching purposes may also be formed on the substrate 100. The sacrificial layer may refer to a layer in which an image is transferred from the resist pattern, thereby transforming it into a desired pattern. In some embodiments, the sacrificial layer may be formed comprising an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the sacrificial layer may be formed comprising a conductive material such as a metal, metal nitride, metal silicide, or metal silicon nitride film. In some embodiments, the sacrificial layer may be formed comprising a semiconductor material such as polysilicon.

[0314] In some implementations, an anti-reflective film may be further formed on the substrate 100 to increase or maximize the efficiency of the resist. The anti-reflective film may be organic or inorganic.

[0315] In some embodiments, a protective film may be further provided on the resist film 110 to reduce the impact of alkaline impurities included in the operation. In some embodiments, in the case of immersion exposure, for example, a protective film for immersion may be provided on the resist film 110 to avoid direct contact between the immersion medium and the resist film 110.

[0316] Next, refer to Figure 1 and Figure 2B At least a portion of the resist film 110 can be exposed to high-energy rays, thereby establishing an exposed resist film. In some exemplary embodiments, high-energy rays passing through the mask 120 can irradiate at least a portion of the resist film 110. For this purpose, based on the exposure, the resist film 110 (e.g., an exposed resist film) can have an exposed portion 111 and an unexposed portion 112.

[0317] Although not limited to a specific theory, free radicals can be generated in the exposed portion 111 through exposure. These free radicals can generate polar functional groups, potentially altering the physical properties of the resist composition.

[0318] Therefore, the exposed portion 111 and the unexposed portion 112 may have different water contact angles, and the difference between the water contact angle of the unexposed portion and the water contact angle of the exposed portion 111 may be 25° or greater, for example 40° or greater, for example 50° or greater, and for example 60° or greater, and may be 180° or less, for example 120° or less, for example 90° or less.

[0319] In some implementation examples, the exposure dose can be 100 mJ / cm². 2 Or even smaller, for example, 80 mJ / cm 2 Or even smaller, for example, 60 mJ / cm 2 Or even smaller, for example, 50 mJ / cm2 Or smaller, and may be greater than 0 mJ / cm 2 For example, 0.01 mJ / cm 2 Or larger, for example, 0.1 mJ / cm 2 Or even higher, for example, 1 mJ / cm 2 The difference between the water contact angle of the unexposed portion 112 and the water contact angle of the exposed portion 111 may be 25° or greater, for example 40° or greater, for example 50° or greater, for example 60° or greater, and may be 180° or less, for example 120° or less, for example 90° or less.

[0320] When the exposure dose is 100mJ / cm 2 or smaller and greater than 0 mJ / cm 2 For example, 0.01 mJ / cm 2 Up to 100mJ / cm 2 For example, 0.1 mJ / cm 2 Up to 100mJ / cm 2 For example, 1mJ / cm 2 Up to 100mJ / cm 2 At that time, the difference between the water contact angle of the unexposed portion 112 and the water contact angle of the exposed portion 111 can be 25° or greater, for example 30° or greater, and can be 180° or less, for example 120° or less, for example 90° or less, and in particular, when the exposure dose is 80 mJ / cm 2 or smaller and greater than 0 mJ / cm 2 For example, 0.01 mJ / cm 2 Up to 80mJ / cm 2 For example, 0.1 mJ / cm 2 Up to 80mJ / cm 2 For example, 1mJ / cm 2 Up to 80mJ / cm 2 At that time, the difference between the water contact angle of the unexposed portion 112 and the water contact angle of the exposed portion 111 can be 25° or greater, for example 30° or greater and can be 180° or less, for example 120° or less, for example 90° or less.

[0321] In some cases, exposure can be performed by (for example, based on) using a liquid such as water as a medium to irradiate high-energy rays through a patterned mask 120. Examples of high-energy rays are: electromagnetic waves such as ultraviolet rays, far-ultraviolet rays (DUV), extreme ultraviolet rays (EUV rays, wavelength 13.5 nm), X-rays, gamma rays, etc.; charged particle beams such as electron beams (Eb), alpha rays, etc.; and so on. Irradiation by these high-energy rays can be collectively referred to as "exposure".

[0322] Various options can be used as the exposure light source: lasers that radiate light in the ultraviolet region, such as KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm); lasers that radiate harmonic lasers in the far ultraviolet or vacuum ultraviolet regions by wavelength conversion of laser light from a solid-state laser source (e.g., YAG or semiconductor lasers); and lasers that irradiate Eb or extreme ultraviolet (EUV) radiation. During exposure, exposure is typically performed using a mask corresponding to the desired pattern, but when the light being exposed is EB, exposure can be performed by direct writing without a mask.

[0323] The integrated dose of high-energy radiation, for example, when using extreme ultraviolet radiation as the high-energy radiation, can be 2000 mJ / cm². 2 Or even smaller, for example, 500 mJ / cm 2 Or even smaller. Additionally, when using Eb as the high-energy ray, the integrated dose can be 5,000 μC / cm². 2 Or smaller, or 1,000 μC / cm 2 Or smaller.

[0324] Additionally, post-exposure baking (PEB) can be performed. The lower limit of the PEB temperature can be 50°C or higher, for example, 80°C or higher. The upper limit of the PEB temperature can be 250°C or lower, for example, 200°C or lower. The lower limit of the PEB time can be 5 seconds or more, for example, 10 seconds or more. The upper limit of the PEB time can be 600 seconds or less, for example, 300 seconds or less.

[0325] Next, refer to Figure 1 and Figure 2C The exposed resist film 110 can be developed using a developer. The unexposed portions 112 or the exposed portions 111 can be washed away by the developer, and the remaining portions of the exposed resist film 110 (which can be the unexposed portions 112 or the exposed portions 111) can be retained without being washed away by the developer. Figure 2C The resulting structure shown may be and / or may define a resist pattern 115.

[0326] Examples of developers include distilled water, alkaline developers, and developers containing organic solvents (hereinafter also referred to as "organic developers"). Examples of development methods include immersion, puddle, spray, and dynamic injection. Development temperatures may be, for example, about 5°C or higher and about 60°C or lower, and development times may be, for example, about 5 seconds or more and about 300 seconds or less.

[0327] Alkaline developers may include, for example, an aqueous solution of 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, methyl diethylamine, ethyl dimethylamine, 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). Alkaline developers may further include surfactants.

[0328] The lower limit of the amount of alkaline compound included in an alkaline developer may be 0.1% by weight or more, 0.5% by weight or more, or 1% by weight or more. Furthermore, the upper limit of the amount of alkaline compound included in an alkaline developer may be 20% by weight or less, 10% by weight or less, or 5% by weight or less.

[0329] Examples of organic solvents included in organic developers are the same organic solvents exemplified in the <Solvents> section of [Resist Composition]. Alternatively, alcohol-based solvents or lactate-based solvents may be used as organic solvents.

[0330] Examples of alcohol-based solvents include: monohydric alcohol 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-Undecanool, Trimethylnonanol, sec-Tetradecanool, sec-Heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-Trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyol solvents such as ethylene glycol, 1,2-propanediol, 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 containing polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and ethylene glycol monophenyl ether. Ethers, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether.

[0331] Examples of lactate-based solvents include methyl lactate, ethyl lactate, n-butyl lactate, and n-pentyl lactate.

[0332] In some exemplary embodiments, nBA (n-butyl acetate), PGME, PGMEA, ethyl lactate, GBL (gamma-butyrolactone), and IPA (isopropanol) can be used as organic developers. Organic developers may further include organic acids such as acetic acid, formic acid, and citric acid.

[0333] The lower limit of the organic solvent content in organic developers may be 80% by weight or more, for example 90% by weight or more, for example 95% by weight or more, for example 99% by weight or more.

[0334] In some implementations, the developer may include distilled water, alkaline developer, or any combination thereof, and the exposed portion 111 may be removed by the developer.

[0335] Organic developers may include surfactants. In some embodiments, organic developers may include trace amounts of water. In some embodiments, the developing process can be stopped during development by replacing the organic developer with a different type of solvent.

[0336] The resist pattern can be further cleaned after development. Cleaning liquids such as ultrapure water and rinsing solutions can be used. There are no particular limitations on the rinsing solution, as long as it does not dissolve the resist pattern and contains a common organic solvent. In some embodiments, the rinsing liquid may be an alcohol-based solvent or an ester-based solvent. After cleaning, any residual rinsing solution on the substrate and pattern can be removed. When ultrapure water is used, any residual water on the substrate and pattern can be removed.

[0337] In addition, developers can be used alone or in combination of two or more types.

[0338] As described above, after forming the resist pattern, a patterned wiring substrate can be obtained by etching. The etching method is carried out by known methods such as dry etching using plasma gas and wet etching using alkaline solutions, copper(II) chloride solutions or ferric(II) chloride solutions.

[0339] After the resist pattern is formed, plating can be performed. There are no particular limitations on the plating method, but examples include copper plating, solder plating, nickel plating, and gold plating.

[0340] Organic solvents can be used to remove residual resist patterns after etching. The organic solvent is not particularly limited, and examples include PGMEA, PGME, ethyl lactate (EL), etc. The removal method is not particularly limited, and examples include immersion and spraying methods. Furthermore, the wiring substrate with the formed resist pattern can be a multilayer wiring substrate and can have small-diameter vias.

[0341] In some implementation examples, the wiring substrate is formed by depositing metal in a vacuum after forming a resist pattern, and then dissolving the resist pattern in a solution, a method known as a stripping method.

[0342] Although not shown, the resist composition may be a negative composition. When the resist composition is a negative composition, the developer contains an organic solvent, and the unexposed portion 112 is removed by the developer.

[0343] Figure 3A , 3B 3C, 3D, and 3E are side cross-sectional views illustrating a method for forming a patterned structure according to some exemplary embodiments.

[0344] like Figure 3AAs shown, a material layer 130 may be formed on the substrate 100 before the resist film 110 is formed on the substrate 100. The resist film 110 may be formed on top of the material layer 130. The material layer 130 may include an insulating material (e.g., silicon oxide, silicon nitride), a semiconductor material (e.g., silicon), or a metal (e.g., copper). In some exemplary embodiments, the material layer 130 may have a multilayer structure. The material of the material layer 130 may be different from the material of the substrate 100.

[0345] like Figure 3B As shown, the resist film 110 may undergo a pre-baking process before exposure, and then be exposed to high-energy rays through a mask 120. Subsequently, the resist film 110 may include an exposed portion 111 and an unexposed portion 112.

[0346] like Figure 3C As shown, the exposed resist film 110 can be developed using a developer. The exposed portion 111 can be washed away by the developer, while the unexposed portion 112 remains intact to define the resist pattern 115.

[0347] like Figure 3D As shown, the pattern of the resist film (e.g., resist pattern 115) can serve as a mask for etching exposed portions of the material layer 130 to form the material pattern 135 on the substrate 100.

[0348] like Figure 3E As shown, a pattern of the resist film can be removed (e.g., resist pattern 115).

[0349] Figure 4A , 4B 4C, 4D, and 4E are side cross-sectional views illustrating a method for forming a semiconductor device according to some exemplary embodiments.

[0350] like Figure 4A As shown, 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.

[0351] like Figure 4B As shown, a resist pattern 540b can be formed on the hard mask layer 520. The resist pattern 540b can be formed using a resist composition according to some exemplary embodiments. The resist composition may include an organic solvent.

[0352] like Figure 4C As shown, the hard mask layer 520, the gate layer 515, and the gate dielectric 505 can be etched to form the hard mask pattern 520a, the gate pattern 515a, and the gate dielectric pattern 505a.

[0353] like Figure 4D As shown, a spacer layer can be formed on the gate pattern 515a and the gate dielectric pattern 505a. A deposition process (e.g., CVD) can be used to form the spacer layer. The spacer layer can be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate pattern 515a and the gate dielectric pattern 505a. After forming the spacers 535a, ions can be implanted into the substrate 500 to form source / drain impurity regions (S / D).

[0354] like Figure 4E As shown, an interlayer insulating film 560 (e.g., oxide) may be formed on a substrate 500, covering the gate pattern 515a, the gate dielectric pattern 505a, and the spacers 535a. Subsequently, electrical contacts 570a, 570b, and 570c may be formed on the interlayer insulating film 560 to connect with the gate pattern 515a and the S / D region. The electrical contacts 570a, 570b, and 570c may comprise a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating film 560 and the electrical contacts 570a, 570b, and 570c.

[0355] Figures 4A to 4E Examples of transistor formation are shown, but the inventive concept is not limited thereto.

[0356] The resist compositions according to some examples can be used in patterning processes to form other types of semiconductor devices.

[0357] Although the inventive concept will be described in more detail using the following embodiments and comparative examples, the technical scope of the inventive concept is not limited to these embodiments.

[0358] [Example]

[0359] Synthesis Example 1: Synthesis of M1

[0360]

[0361] (1) Synthesis of M1-1

[0362] 8.2 g (69.2 mmol) of Sn powder and 120 mL of dry toluene were placed in a 250 mL three-necked flask, and the temperature was raised to 90 °C. After adding about 1.0 mL of deionized water, 10.0 g (69.2 mmol) of 4-fluorobenzyl chloride was added dropwise over 10 minutes. The mixture was heated under reflux at 130 °C with stirring for 4 hours, and then the unreacted Sn powder was filtered off using a Buchner funnel. Simultaneously, as the filtered solution cooled, the product was obtained in 6.5 g of white crystals, M1-1 (yield 36%).

[0363] (2) Synthesis of M1

[0364] 1.5 g (3.7 mmol) of M1-1 and 21.0 ml of dry acetone were placed in a 50 ml single-necked flask, and the mixture was cooled to 0 °C. After adding 0.6 g (7.4 mmol) of sodium acetate, the mixture was stirred for approximately 12 hours. The solution was filtered using a 0.45 μm filter to remove the NaCl salt formed in the solution. The filtered solution was then concentrated by rotary evaporation and dried under vacuum to give 1.6 g of M1, in 74% yield.

[0365] 1H-NMR (500 MHz, DMSO-d6): δ ~6.9 (8H), ~2.6 (4H), ~1.6 (6H)

[0366] Synthesis Example 2: Synthesis of M2

[0367]

[0368] (1) Synthesis of M2-2

[0369] In a two-necked round-bottom flask purged with N2, diphenylmethane (4.89 g, 29.1 mmol) was added and diluted with THF (tetrahydrofuran) (30 mL). n-BuLi (n-butyllithium) (2.5 M in hexane, 29.1 mmol) was added dropwise to the round-bottom flask at -78 °C and stirred at 0 °C for 0.5 h. Dichlorodiphenyltinane (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 from the vial was added dropwise to the round-bottom flask at -78 °C and stirred for 0.5 h. The reaction temperature was then raised to room temperature, and the mixture was stirred further for 0.5 h. After confirming the completion of the reaction, the solvent was removed, the mixture was filtered through silica / diatomite, and purified by column chromatography (ethyl acetate (EA): n-hexane (EA 5 v / v)) to give M2-2 (6.8 g, 77%).

[0370] (2) Synthesis of M2-1

[0371] M2-2 (6.2 g, 10.2 mmol) was placed in a round-bottom flask and purged with N2. After dilution with dichloromethane (DCM) (102 mL, 0.1 M), a 2 M HCl solution (15.3 mL, 30.67 mmol) in Et2O was added dropwise at -78 °C. The mixture was stirred at -78 °C for 1 hour, then warmed to room temperature and reacted for another 12 hours. After removing the solvent, the precipitate was washed with methyl tert-butyl ether: n-hexane (5 mL: 100 mL) and dried under vacuum to give M2-1 (4.3 g, 80%).

[0372] (3) Synthesis of M2

[0373] M2-1 (1.0 g, 1.91 mmol) was placed in a round-bottom flask and purged with N2. After dilution with acetone (19 mL, 0.1 M), sodium acetate (0.31 g, 3.82 mmol) was added at 0 °C. The reaction was carried out at 0 °C for 16 hours, and the reaction product was then filtered through diatomaceous earth. After removing the solvent, recrystallization was performed (methyl tert-butyl ether: n-hexane = 3 mL: 30 mL). After filtration, the precipitate was dried under vacuum to give M2 (0.54 g, 50%).

[0374] 1 H NMR (500MHz, CD2Cl2) δ 7.42-6.98 (m, 20H), 4.71 (s, 2H), 1.64 (s, 6H).

[0375] 13 C NMR (126MHz, CD2Cl2) δ 182.13, 138.99, 129.41, 128.78, 126.68, 57.91, 19.88.

[0376] 119 Sn NMR (186MHz, CD2Cl2) δ -345.10.

[0377] Preparation Example: Preparation of Casting Solution

[0378] The organometallic compounds and additives synthesized in Examples 1 and 2 were dissolved in cyclopentanone at 2% by weight to prepare casting solutions A-1 and A-2. In this respect, the weight ratio of organometallic compound to additive was 1:1.5.

[0379] Additive A1 was prepared in the same manner as compound A-2 in CN 2025106419144. Specifically, N-hydroxy-N-methylbenzamide (0.5 g, 3.31 mmol) was placed in a two-necked round-bottom flask (RBF) purged with nitrogen (N2) and diluted with THF (5 ml). Pyridine (0.54 ml, 6.62 mmol) was added to this flask at 0 °C, followed dropwise by a THF solution of 3-(chlorosulfonyl)benzoic acid (0.73 g, 3.31 mmol) (6 ml THF, total volume 11 ml, 0.3 M). The reaction mixture was then allowed to warm to room temperature and stirred for 18 hours. After confirming the completion of the reaction, the mixture was diluted with ethyl acetate (EA), 1N HCl (3 ml) was added, and the organic layer was washed three times with distilled water. The collected organic layer was dried over Na2SO4 to remove the solvent. After purification using short column chromatography (elution buffer: dichloromethane (MC): methanol (MeOH) (MeOH 5 v / v%)), the residue was recrystallized using EA / n-hexane to obtain compound A-2 (i.e., additive A1) (0.24 g, yield: 21%).

[0380] In addition, a casting solution B-1 with the same composition as casting solution A-1 is prepared, except that it does not contain any additives.

[0381] [Table 1]

[0382]

[0383]

[0384] Evaluation Example 1: FT-IR Analysis

[0385] A solution of compounds M1, A1, a mixture of compounds M1 and A1, and compound X1, each dissolved in cyclopentanone, was applied to an Au-coated Si wafer to a thickness of 50 nm. The wafer was then dried to prepare the sample, followed by FT-IR analysis. The results are shown in... Figure 5 middle.

[0386] Compound X1 was prepared in the same manner as compound OM-A in CN 2025106419144. Specifically, sodium hydride (0.18 g, 4.5 mmol) was placed in an RBF and diluted with THF (22 ml, 0.2 M) after purging with N2. Compound A-2 (1.5 g, 4.5 mmol) was added to this mixture at 0 °C. The reaction mixture was then stirred at 0 °C for 5 hours. After solvent removal, the residue was recrystallized from a mixture of THF:diethyl ether (Et2O) = 1:5 (10 ml:50 ml) and then filtered to obtain compound A-1 (1.4 g, yield: 89%). Dichlorobis(4-fluorobenzyl)stanane (0.5 g, 1.23 mmol) was placed in an RBF and then purged with N2. Dry acetone (12.3 ml, 0.1 M) was added for dilution, followed by the addition of compound A-1 (0.88 g, 2.45 mmol) at 0 °C. The reaction mixture was stirred at 0 °C for 18 hours and then filtered through diatomaceous earth. The solvent was removed from the filtrate, and the residue was recrystallized from a mixture of dichloromethane:n-hexane (1:10, 5 ml:50 ml). After filtration, the resulting solid was dried under vacuum to obtain compound OM-A (i.e., compound X1) (0.85 g, yield: 69%).

[0387] refer to Figure 5 Characteristic peaks of M1 and A1 were also observed in the mixture of M1 and A1, as well as in X1. This confirms that the ligands of M1 in the mixture of M1 and A1 exchange with A1 to form X1.

[0388]

[0389] Evaluation Example 2: Thin Film Stability Evaluation

[0390] An 8-inch diameter silicon wafer was cut into four equal parts and then treated with O2 plasma for 30 minutes. Casting solutions A-1, A-2, and B-1 were each used for spin-coating at 1200 rpm for 1 minute, followed by PAB treatment at 100°C for 1 minute to produce films with the following preset initial thicknesses. The thicknesses of these films were then measured again after 5, 10, 20, and 30 days, and the thicknesses are expressed as relative values ​​to the initial thicknesses in Table 2 below.

[0391] [Table 2]

[0392]

[0393] Referring to Table 2 above, in the case of B-1 without additives, the film thickness decreased significantly over time after coating, confirming low film stability. However, in the cases of A-1 and A-2 with additives, the film thickness remained the same or substantially the same over time after coating, confirming relatively high film stability.

[0394] Evaluation Example 3: Thin Film Development Evaluation

[0395] (1) Terminology

[0396] For Examples 1-1 and 1-2, E0 refers to the exposure dose when the film is fully developed (the film thickness no longer decreases), and E1 refers to the exposure dose when the film begins to develop.

[0397] For Comparative Examples 1-1, 1-2 and Example 2-1, E0 refers to the exposure dose when the film begins to cure, and E1 refers to the exposure dose at the saturation point when the film no longer thickens.

[0398] γ is the contrast curve, calculated using the following Equation 1.

[0399] <Equation 1>

[0400]

[0401] An 8-inch diameter silicon wafer was cut into four equal parts and then treated with O2 plasma for 30 minutes. Casting solutions A-1, A-2, and B-1 were each spin-coated for 1 minute at the coating speeds shown in Table 3, followed by PAB treatment at 100°C for 1 minute to produce a film with a predetermined initial thickness. Subsequently, a 1 cm thick mask (4 cm × 4 cm) with rectangular holes (1 cm × 1 cm) was placed on top, and each hole was coated with a solution in the range of 0 mJ / cm². 2 Up to 100mJ / cm 2 The film was exposed to DUV rays at a wavelength of 254 nm, followed by PEB treatment for 1 minute at the temperatures shown in Table 3. The dried film was then immersed at 25°C in deionized water (DI), PGMEA:acetic acid (AA) (98:2 wt%), or PGMEA as a developer for 60 seconds. The remaining film thickness was measured and shown. Figures 6A to 6D and 7. Figure 6A This refers to Example 1-1. Figure 6B Examples 1-2 are shown. Figure 6C This refers to comparison example 1-1. Figure 6D This indicates comparison examples 1-2, and Figure 7 Example 2-1 illustrates the change in film thickness after development based on dosage.

[0402] [Table 3]

[0403]

[0404] PTD: Positive Tone Development

[0405] NTD: Negative Tone Development

[0406] refer to Figures 6A to 6D Depending on the polarity of the developer, casting solutions A-1 and A-2 containing additives exhibit the characteristics of either positive or negative resist compositions. In contrast, casting solution B-1 without additives does not allow for the removal of exposed areas, even when the polarity of the developer is changed.

[0407] Evaluation Example 4: Water Contact Angle (WCA) Evaluation

[0408] An 8-inch diameter silicon wafer was cut into four equal parts, treated with O2 plasma, and then spin-coated with casting solutions A-1 and A-2 at 1200 rpm for 1 minute each, followed by drying at 100°C (PAB) for 1 minute to produce a film with an initial thickness of 40 nm. Subsequently, a 1 cm thick mask (4 cm × 4 cm) with rectangular holes (1 cm × 1 cm) was placed on top, and each hole was sprayed with a flux of 0 mJ / cm. 2 Up to 100mJ / cm 2 The film was exposed to 254 nm wavelength DUV rays and then dried at 170 °C (PEB) for 90 seconds. Then, 3 μL of water was dropped onto each well, and the water contact angle (in °) was measured. The results (e.g., the corresponding water contact angles (in °) for films formed from casting solutions A-1 and A-2) are shown in Table 4 below.

[0409] [Table 4] - Water contact angle of films formed from cast solutions based on DUV ray dose

[0410]

[0411] Referring to Table 4, resist composition A-1 containing M1 and A1 and resist composition A-2 containing M2 and A1 each showed significant changes in water contact angle values ​​before and after DUV irradiation, confirming that a change in polarity had occurred in the organometallic compounds.

[0412] Some exemplary embodiments of the present invention can provide resist compositions with improved storage stability and enhanced sensitivity, and provide patterns with improved resolution, thereby enabling the formation of semiconductor devices with improved pattern resolution, thereby enabling miniaturization of semiconductor devices with improved device reliability based on the reduced likelihood of device defects due to the reduced likelihood of defects caused by low pattern resolution.

[0413] It should be understood that the exemplary embodiments described herein are to be considered only in a descriptive sense and are not intended for limiting purposes. The descriptions of features or aspects within each exemplary embodiment should typically be considered applicable to other similar features or aspects in other exemplary embodiments. While some exemplary embodiments have been described with reference to the accompanying drawings, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A resist composition, comprising: an organometallic compound represented by Formula 1; and an additive represented by Formula 2: Formula 1 M 11 (R x ) n (R y ) (m-n) Formula 2 (X2) c2 -(L2) a2 -[Y2-Z2] b2 wherein, in Formulas 1 and 2, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi) or polonium (Po), R x is -X1-Y1, R y is -(L1) a1 -(R1) b1 , n is an integer of 1 to 6, m is an integer of 1 to 6, m-n is 0 or more, Formula 1 optionally includes a plurality of R based on n greater than 1 x , the plurality of R x are the same as or different from each other, Formula 1 optionally includes a plurality of R based on m-n being greater than 1 y , the plurality of R y are the same or different from one another, X1 is O, OC(=O), C(=O)O, OS(=O), S(=O)O, OS(=O)2, S(=O)2O, S, SC(=O), or C(=O)S, Y1is hydrogen, deuterium, or a linear, branched, or cyclic C1-C 30 monovalent hydrocarbon group, L1is a single bond, or a straight chain, branched, or cyclic C1-C6alkyl optionally including heteroatoms 30 a divalent hydrocarbon group, a1 is an integer of 0 to 4, R1is a linear, branched, or cyclic C1-C 30 monovalent hydrocarbon group, b1 is an integer of 1 to 4, wherein Formula 1 optionally includes a plurality of R1 based on b1 being greater than 1, two adjacent groups of the plurality of R1 optionally bind to each other to form a ring, X2 is OH, SH, C(=O)OH, S(=O)OH, S(=O)2OH, or P(=O)(OH)2, c2 is an integer of 1 to 4, each L2is independently a linear, branched, or cyclic C1-C6alkyl group optionally including a heteroatom 30 a divalent hydrocarbon group, a2 is an integer of 0 to 4, Y2-Z2 is a photo-reactive unit, b2 is an integer of 1 to 4, and * is a binding site to an adjacent atom of Formula 1.

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

3. The resist composition according to claim 1, wherein, In Formula 1, X1 is O, OC(=O), C(=O)O, S, SC(=O), or C(=O)S, and Y1is selected from the group consisting of: hydrogen, deuterium, Ci-C 30 alkyl, Ci-C 30 haloalkyl, Ci-C 30 alkoxy, Ci-C 30 alkylthio, Ci-C 30 haloalkoxy, Ci-C 30 haloalkylthio, 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, Ci-C 30 heteroaryl, Ci-C 30 heteroaryloxy, Ci-C 30 heteroarylthio and C2-C 30 heteroarylalkyl, wherein the Ci-C 30 alkyl, the Ci-C 30 haloalkyl, the Ci-C 30 alkoxy, the Ci-C 30 alkylthio, the Ci-C 30 haloalkoxy, the Ci-C 30 haloalkylthio, the C3-C 30 cycloalkyl, the C3-C 30 cycloalkoxy, the C3-C 30 cycloalkylthio, the C3-C 30 heterocycloalkyl, the C2-C 30 alkenyl, the C3-C 30 cycloalkenyl, the C3-C 30 heterocycloalkenyl, the C2-C 30 alkynyl, the C6-C 30 aryl, the C6-C 30 aryloxy, the C6-C 30 arylthio, the C7-C 30 arylalkyl, the Ci-C 30 heteroaryl, the Ci-C 30 heteroaryloxy, the Ci-C 30 heteroarylthio and the C2-C 30 The heteroaryl alkyl group is either unsubstituted or substituted with: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cyclothioyl, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 Heteroaryl thiols or any combination thereof.

4. The resist composition according to claim 1, wherein, In Formula 1, L1is a single bond, 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, a1 is 0, 1, or 2, and R1is selected from the group consisting of C1-C 30 alkyl, C1-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, wherein each of the C1-C 30 alkyl, the C3-C 30 cycloalkyl, the C3-C 30 heterocycloalkyl, the C2-C 30 alkenyl, the C3-C 30 cycloalkenyl, the C3-C 30 heterocycloalkenyl, the C2-C 30 alkynyl, the C6-C 30 aryl, the C7-C 30 arylalkyl, the C1-C 30 heteroaryl, and the C2-C 30 heteroarylalkyl is unsubstituted or substituted by deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, 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, C1-C 20 alkyl, C1-C 20 haloalkyl, C1-C 20 alkoxy, C1-C 20 alkylthio, C1-C 20 haloalkoxy, C1-C 20 haloalkylthio, 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 any combination thereof.

5. The resist composition according to claim 1, wherein the organometallic compound represented by Formula 1 is selected from Group I: <Group I> wherein n in Group I is an integer of 0 to 3.

6. The resist composition according to claim 1, wherein, In Formula 2, X2 is OH or C(=O)OH.

7. The resist composition according to claim 1, wherein, In Formula 2, (L2) a2 represented by any one of formulae 5-1 to 5-7: wherein, in Formulas 5-1 to 5-7, R 51 to R 53 each independently hydrogen, deuterium, halogen, hydroxyl, cyano, C1-C4alkyl, or C1-C4haloalkyl, b51 is an integer of 1 to 4, n51 is an integer of 1 to 3, and * and *' each represent a binding site to an adjacent atom of Formula 2.

8. The resist composition according to claim 1, wherein, In Formula 2, Y2 is OC(=O), C(=O)O, OS(=O)2, or S(=O)2O, Z2 is *-C(R2)(R3)(R4), *-C(R2)=N(R3), *-N=C(R2)(R3), or *-N(R2)(R3), R2and R3are optionally taken together to form a ring, 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C2-C 30 substituted or unsubstituted C2-C 30 substituted or unsubstituted C2-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C3-C 30 substituted or unsubstituted C2-C 30 substituted or unsubstituted C2-C 30 substituted or unsubstituted C2-C 30 substituted or unsubstituted C6-C 30 substituted or unsubstituted C6-C 30 substituted or unsubstituted C6-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C 30 substituted or unsubstituted C1-C R2and R3are optionally taken together to form a ring, R5and R6are each independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C1-C 30 haloalkyl, substituted or unsubstituted C1-C 30 alkoxy, substituted or unsubstituted C1-C 30 alkylthio, substituted or unsubstituted C1-C 30 haloalkoxy, substituted or unsubstituted C1-C 30 haloalkylthio, substituted or unsubstituted C3-C 30 cycloalkyl, substituted or unsubstituted C3-C 30 cycloalkoxy, substituted or unsubstituted C3-C 30 cycloalkylthio, substituted or unsubstituted C3-C 30 heterocycloalkyl, substituted or unsubstituted C3-C 30 heterocycloalkoxy, substituted or unsubstituted C3-C 30 heterocycloalkylthio, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 alkenyloxy, substituted or unsubstituted C2-C 30 alkenylthio, substituted or unsubstituted C3-C 30 cycloalkenyl, substituted or unsubstituted C3-C 30 cycloalkenyloxy, substituted or unsubstituted C3-C 30 cycloalkenylthio, substituted or unsubstituted C3-C 30 heterocycloalkenyl, substituted or unsubstituted C3-C 30 heterocycloalkenyloxy, substituted or unsubstituted C3-C 30 heterocycloalkenylthio, substituted or unsubstituted C2-C 30 alkynyl, substituted or unsubstituted C2-C 30 alkynyloxy, substituted or unsubstituted C2-C 30 alkynylthio, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 aryloxy, substituted or unsubstituted C6-C 30 arylthio, substituted or unsubstituted C1-C 30 heteroaryl, substituted or unsubstituted C1-C 30 heteroaryloxy or substituted or unsubstituted C1-C 30 heteroarylthio, and * is a binding site to an adjacent atom of Formula 2.

9. The resist composition according to claim 1, wherein the additive represented by Formula 2 is selected from Group II: <Group II> wherein Ph in Group II is a phenyl group.

10. The resist composition according to claim 1, wherein the additive is included in the resist composition 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 organometallic compound.

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

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

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

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

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

16. A pattern forming method comprising: forming a resist film by applying the resist composition according to any one of claims 1 to 15 onto a substrate; exposing at least a portion of the resist film to high-energy rays to form an exposed resist film; and developing the exposed resist film based on use of a developer.

17. The pattern forming method according to claim 16, wherein the exposing is based on irradiation of at least one of ultraviolet rays, deep ultraviolet rays (DUV), extreme ultraviolet rays (EUV), X-rays, γ-rays, electron beams (EB), or α-rays.

18. The pattern forming method according to claim 16, wherein based on the exposing of at least a portion of the resist film, the exposed resist film includes an exposed portion and an unexposed portion, and a difference between a water contact angle of the unexposed portion and a water contact angle of the exposed portion is 25° or greater.

19. The pattern forming method according to claim 16, wherein based on the exposing of at least a portion of the resist film, the exposed resist film includes an exposed portion and an unexposed portion, the developer includes distilled water, an alkali developer, or any combination thereof, and the developing of the exposed resist film includes removing the exposed portion.

20. The pattern forming method according to claim 16, wherein based on the exposing of at least a portion of the resist film, the exposed resist film includes an exposed portion and an unexposed portion, the developer includes an organic solvent, and the developing of the exposed resist film includes removing the unexposed portion.

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