Photoresist composition and method for forming pattern using same

Abstract

The invention relates to a photoresist composition and a method for forming a pattern using the same. Disclosed is a photoresist composition including an organometallic compound including a ring including a metal, a first heteroatom coordinated to the metal, and a second heteroatom covalently bonded to the metal, and an aromatic ring substituted or fused to the ring, and a solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the priority of Korean Patent Application No. 10-2023-0124247 filed on September 18, 2023 in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a photoresist composition and a method of forming a pattern using the same. More specifically, the present disclosure relates to a photoresist composition for extreme ultraviolet lithography including a multi-core metal-based supramolecule and a method of forming a pattern using the same. Background Art

[0004] EUV (extreme ultraviolet) lithography is a technology used to manufacture next-generation semiconductor devices. EUV lithography is a pattern forming technology that uses EUV rays having a wavelength of about 13.5 nm as an exposure light source. According to EUV lithography, extremely small patterns (e.g., less than or equal to about 20 nm) can be formed during the exposure process during the manufacture of semiconductor devices.

[0005] EUV lithography is achieved through the development of compatible photoresists that can be performed at a spatial resolution of less than or equal to about 16 nm. Currently, efforts are being made to meet the insufficient specifications (technical parameters) of traditional chemically amplified (CA) photoresists for next-generation devices, such as resolution, photospeed, and feature roughness (or line edge roughness (LER)).

[0006] Intrinsic image blurring due to acid-catalyzed reactions in these polymeric photoresists limits resolution in small feature sizes, which is well known in electron beam (e-beam) lithography. CA photoresists are designed for high sensitivity, but can have more difficulty with EUV exposure because their typical elemental composition reduces the photoresist's light absorption at about 13.5 nm wavelength and thus reduces its sensitivity.

[0007] Additionally, CA photoresists can have difficulty with small feature sizes due to roughness issues, and the line edge roughness (LER) of CA photoresists increases experimentally as photospeed decreases, due in part to the nature of the acid-catalyzed process.

[0008] Due to the disadvantages and problems of CA photoresists, new high performance photoresists are needed in the semiconductor industry. Summary of the invention

[0009] One aspect of the present disclosure provides a photoresist composition that is capable of forming (e.g., configured to form and / or formable) a pattern having a size of 20 nm or less using extreme ultraviolet (EUV), achieving high resolution and low line edge roughness (LER) with only a single exposure process, reducing wafer-to-wafer critical dimension (CD) deviation due to the photoresist composition having excellent moisture stability and environmental stability, and / or reducing the occurrence of defects by reducing photoresist residue in unexposed areas.

[0010] Another aspect of the present disclosure provides a method of forming a pattern using a photoresist composition.

[0011] A photoresist composition according to one aspect includes an organic metal compound including a ring including a metal, a first heteroatom coordinated to the metal and a second heteroatom covalently bonded to the metal, and an aromatic ring substituted or fused to the ring, and a solvent.

[0012] A photoresist composition according to another aspect includes an organic metal compound represented by Chemical Formula 1; and a solvent.

[0013] [Chemical formula 1]

[0014]

[0015] In Chemical Formula 1, M 11 is a metal including Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 and X 12 Each independently is O, S or NR', A 11 and B 11 Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 To replace A 11 The aromatic ring of Z 11 To be fused to A 11 and B 11 The aromatic rings include single bonds, double bonds, alkylene, O, S, NR', NHC (= O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof, R 11 and R21 Each is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, R 11 For M 11 The coordinated solvent, or R 11 and R 21 Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof, R' is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, n 11 M 11 The number of substitutable (combinable, bonding) positions, and n 21 is the number of substitutable positions of the aromatic ring.

[0016] According to another aspect, a method for forming a pattern includes: forming a film to be etched on a substrate; forming a photoresist film by applying the aforementioned photoresist composition on the film to be etched; patterning the photoresist film to form a photoresist pattern; and etching the film to be etched using the photoresist pattern as an etching mask.

[0017] According to example embodiments, the photoresist composition is capable of forming (e.g., configured to form and / or formable) a pattern having a size of 20 nm or less using extreme ultraviolet light, can achieve high resolution and low line edge roughness (e.g., about 1.2 nm or less) with only a single exposure process, can reduce wafer-to-wafer critical dimension deviation due to excellent moisture stability and environmental stability, and can reduce the occurrence of defects by reducing photoresist residue in unexposed areas. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The embodiments will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings:

[0019] Figures 1 to 5 A cross-sectional view illustrating aspects of an intermediate step of a method of forming a pattern.

[0020] Figures 6 to 8 The NMR spectroscopy results of the exemplary organometallic compound prepared in Synthesis Example 1 are shown, showing proton NMR, 13 C NMR and 119 Sn NMR results.

[0021] Fig. 9 is a graph showing the results of thermogravimetric analysis of the organometallic compound prepared in Synthesis Example 1.

[0022] Figures 10A-10B 10A and 10B are scanning electron microscope (SEM) images before ( 10A ) and after ( 10B ) exposure in a photoreactivity test to an electron beam.

[0023] Figures 11A-11I The following is a scanning electron microscope (SEM) image of the after-development inspection (ADI) result for EUV photoreactivity testing. DETAILED DESCRIPTION

[0024] Hereinafter, various embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily implement the present disclosure. The present disclosure can be implemented in many different forms and is not limited to the embodiments described herein.

[0025] The drawings and description should be regarded as illustrative in nature and not restrictive.Throughout the specification, the same reference numerals designate the same elements.

[0026] In addition, in the drawings, for better understanding and ease of description, the size and thickness of each element are arbitrarily presented, but the present disclosure is not limited thereto. In the drawings, for clarity, the thickness of layers, films, panels, regions, etc. are exaggerated. In addition, in the drawings, for better understanding and ease of description, the thickness of some layers and regions are exaggerated.

[0027] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element, or there can be intervening elements. Conversely, when an element is referred to as being "directly on" another element, there are no intervening elements. The term "on" or "above" means disposed on or below an object portion, and does not necessarily mean disposed on the upper side of an object portion based on the direction of gravity.

[0028] In addition, unless explicitly described to the contrary, the word “comprise” and variations such as “comprising”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

[0029] As used herein, when no specific definition is otherwise provided, "substituted" means that a hydrogen atom is replaced by deuterium, halogen, hydroxyl, cyano, nitro, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), C1 to C30 alkyl, C1 to C10 haloalkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, or any combination thereof. "Unsubstituted" means that the hydrogen atom remains unreplaced by another substituent.

[0030] As used herein, when no specific definition is otherwise provided, "alkyl" refers to a substituted or unsubstituted straight-chain or branched saturated aliphatic hydrocarbon group. The alkyl group does not contain double bonds or triple bonds.

[0031] As an example, the alkyl group may be a C1 to C8 alkyl group, such as a C1 to C7 alkyl group, a C1 to C6 alkyl group, a C1 to C5 alkyl group, or a C1 to C4 alkyl group. For example, the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0032] As used herein, when no specific definition is otherwise provided, "alkylene" refers to a substituted or unsubstituted straight chain or branched divalent hydrocarbon group having a specific number of carbon atoms that can link two different groups together. Alkylene may refer to -(CH 2 ) n - (wherein n is an integer from 1 to 8, for example, n is an integer from 1 to 4).

[0033] As an example, the alkylene group may be a C1 to C8 alkylene group, such as a C1 to C7 alkylene group, a C1 to C6 alkylene group, a C1 to C5 alkylene group, or a C1 to C4 alkylene group. For example, the alkylene group may include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, or a 2,2-dimethylpropylene group.

[0034] As used herein, when a specific definition is not otherwise provided, "alkoxy" refers to a monovalent -O-alkyl group in which the alkyl portion has a specific number of carbon atoms. The alkyl portion of the alkoxy group may be a substituted or unsubstituted linear or branched alkyl group.

[0035] For example, the alkoxy group may be a C1 to C8 alkoxy group, such as a C1 to C7 alkoxy group, a C1 to C6 alkoxy group, a C1 to C5 alkoxy group, or a C1 to C4 alkoxy group. For example, the C1-C4 alkoxy group may be a methoxy group (—OCH 3 ), ethoxy (-OCH 2 CH 3 ), isopropoxy (-OCH(CH 3 ) 2 ), or tert-butyloxy (-OC(CH 3 ) 3 ).

[0036] As used herein, when a specific definition is not otherwise provided, "cycloalkyl" refers to a substituted or unsubstituted monovalent cyclic aliphatic saturated hydrocarbon group.

[0037] As an example, the cycloalkyl group may be a C3 to C20 cycloalkyl group, such as a C3 to C10 cycloalkyl group, a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0038] As used herein, when no specific definition is provided, "heterocycloalkyl" refers to a cyclic aliphatic saturated group including at least one heteroatom containing N, O, S, P, Si or any combination thereof in a cycloalkyl group. Two or more heterocycloalkyl groups may be directly connected by a sigma bond, or if the heterocycloalkyl group contains two or more rings, the two or more rings may be fused to each other. When the heterocycloalkyl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0039] For example, the heterocycloalkyl group may be a C3 to C20 heterocycloalkyl group, such as a C3 to C10 heterocycloalkyl group, a C3 to C8 heterocycloalkyl group, a C3 to C7 heterocycloalkyl group, a C3 to C6 heterocycloalkyl group, a C3 to C5 heterocycloalkyl group, or a C3 to C4 heterocycloalkyl group. For example, the heterocycloalkyl group may be a pyrrolidine, tetrahydrofuran, tetrahydrothiophene, or piperidine group.

[0040] As used herein, when no specific definition is otherwise provided, "aryl" refers to a substituted or unsubstituted aromatic ring group, which includes all elements of the ring having p-orbitals forming conjugation, and may be a monocyclic, polycyclic or fused-ring polycyclic (e.g., rings sharing adjacent pairs of carbon atoms) functional group.

[0041] For example, the aryl group may be a C6 to C20 aryl group, such as a C6 to C10 aryl group, a C6 to C8 aryl group, a C6 to C7 aryl group, or a C6 aryl group. For example, the aryl group may be a benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, or perylene group.

[0042] As used herein, when no specific definition is provided, "heteroaryl" refers to an aromatic ring group including at least one heteroatom (including N, O, S, P, Si, or any combination thereof) in the aryl group. Two or more heteroaryls can be directly connected by a sigma bond, or if the heteroaryl contains two or more rings, the two or more rings can be fused to each other. When the heteroaryl is a fused ring, each ring can contain 1 to 3 heteroatoms.

[0043] For example, the heteroaryl group can be a C3 to C20 heteroaryl group, such as a C3 to C10 heteroaryl group, a C3 to C8 heteroaryl group, a C3 to C7 heteroaryl group, a C3 to C6 heteroaryl group, a C3 to C5 heteroaryl group, or a C3 to C4 heteroaryl group. For example, the heteroaryl group can be a pyrazole, imidazole, thiazole, triazole, carbazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indazole, indolizine, benzimidazole, benzothiazole, benzothiophene, benzopurine, isoquinoline, or purine group.

[0044] As used herein, when no specific definition is otherwise provided, "alkenyl" refers to a substituted or unsubstituted straight or branched aliphatic hydrocarbon group containing one or more double bonds. For example, the alkenyl group can be a C2 to C8 alkenyl group, such as vinyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-butenyl, 2-butenyl, or 3-butenyl.

[0045] As used herein, when no specific definition is otherwise provided, "cycloalkenyl" refers to a cyclic aliphatic hydrocarbon group containing one or more double bonds. As an example, the cycloalkenyl group may be a C3 to C20 cycloalkenyl group.

[0046] As used herein, when no specific definition is otherwise provided, "alkynyl" refers to a substituted or unsubstituted straight or branched aliphatic unsaturated hydrocarbon group containing one or more triple bonds. For example, the alkynyl group can be a C2 to C8 alkynyl group, such as ethynyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0047] As used herein, when no specific definition is otherwise provided, "cycloalkynyl" refers to a cyclic aliphatic unsaturated hydrocarbon group containing one or more triple bonds. As an example, the cycloalkynyl group may be a C3 to C20 cycloalkynyl group.

[0048] As used herein, when no specific definition is otherwise provided, "hydroxyl" refers to an -OH group.

[0049] As used herein, when specific definition is not otherwise provided, "halo" or "halogen group" means fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0050] As used herein, when a specific definition is not otherwise provided, "*" indicates a connection point of a structural unit of a compound or a part of a compound.

[0051] A photoresist composition according to some embodiments includes an organometallic compound and a solvent.

[0052] The organometallic compound includes a ring and an aromatic ring substituted or fused to the ring.

[0053] The ring includes a metal and a first heteroatom and a second heteroatom bonded to the metal. The first heteroatom and the second heteroatom are each independently covalently bonded or coordinated to the metal, and at least one of the first heteroatom and the second heteroatom is coordinated to the metal. In some embodiments, the first heteroatom is coordinated to the metal.

[0054] A photoresist composition containing such an organic metal compound can form a pattern having a size of about 20 nm or less using extreme ultraviolet rays, can achieve high resolution and low line edge roughness with only a single exposure process, and has moisture stability and environmental stability, which can reduce critical dimension deviation between wafers and can reduce the occurrence of defects by reducing photoresist residues in unexposed areas.

[0055] In the case of a chemically amplified photoresist, inherent image blurring occurs due to the migration of H generated by an acid catalyst and line edge roughness (LER) deterioration, and thus high resolution and low line edge roughness cannot be achieved in the case of only a single exposure process using extreme ultraviolet rays.

[0056] On the other hand, in the case of an organometallic compound, when an organic ligand dissociates by light absorption or secondary electrons generated thereby, negative tone patterning that is not removed by an organic developer can be achieved by crosslinking with surrounding chains via oxo bonds (oxygen bonds). The organometallic compound can have significantly improved sensitivity while maintaining resolution and line edge roughness, so that high resolution and low line edge roughness can be achieved in the case of only a single exposure process using extreme ultraviolet rays.

[0057] However, conventional organometallic compounds are susceptible to environmental sensitivity such as moisture and heat due to their characteristics of being easily oxidized by moisture and heat. This leads to a reduction in yield due to large critical dimension deviations between wafers, and has poor storage stability, making it difficult to apply to large-scale manufacturing. In particular, when the organometallic compound contains a hydroxyl group (-OH) bonded to a metal, this moiety is highly reactive with moisture.

[0058] The organometallic compound according to some embodiments does not replace the hydroxyl group (-OH) on the metal, but includes two heteroatoms bonded to the metal in a ring (in a ring). In some embodiments, even when moisture attacks, the two heteroatoms remain because the bonds are difficult to break simultaneously, and due to the stability and non-hydrophilic nature of the aromatic ring substituted or fused to the ring, moisture stability and environmental stability can be improved, thereby reducing critical dimension deviation between wafers and enabling large-scale manufacturing.

[0059] The organometallic compound according to some embodiments is represented by Chemical Formula 1.

[0060] [Chemical formula 1]

[0061]

[0062] In Chemical Formula 1, M 11 represents metal, and X 11 and X 12 M represents the first and second heteroatoms bonded to the metal. 11 , X 11 , X 12 , A 11 and B 11 In some embodiments, Z 11 Can be with A 11 Aromatic ring bonded (e.g., substituted to A 11 ), or Z 11 Z 11 , A 11 and B 11 A linker group forms an aromatic ring that can be fused to the ring. 11 Not with Z 11 to form an aromatic ring, but to bond thereto.

[0063] For example, in Chemical Formula 1, M as a metal 11 and X as the first heteroatom 11 Coordinated, and as a metal M 11 and X as the second heteroatom 12 In chemical formula 1, X 11 and A 11 The dotted line between indicates that when M 11 and X 11 When coordinated, in X 11 and A 11 The bond between may be a double bond.

[0064] Although not intending to be bound by a particular theory, as described later, when M 11 is tin (Sn) and A 11 =X11 When it is a carbonyl group (C=O), considering the oxidation number of tin (Sn), O of the carbonyl group (C=O) does not have a separate charge and is coordinated to tin (Sn), which can be represented by A 11 =X 11 -M 11 (C=O-Sn) is represented. However, when considering energy stabilization, it is quite possible that the electrons are actually delocalized, not localized. 11 -X 11 -M 11 (CO-Sn), oxygen (O) may also mean that it has a separate charge, which may lead to confusion about the oxidation number of tin (Sn), and therefore, here, it is represented by A 11 =X 11 -M 11 (C=O-Sn) represents.

[0065] M 11 It is a metal including Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, and may be, for example, Sn.

[0066] X 11 and X 12 Each independently is O, S or NR', wherein R' is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. In this article, its combination may include, for example, hydroxy-alkyl in which alkyl and hydroxyl are combined, alkyl-aryl in which alkyl and aryl are combined, haloalkyl in which alkyl is substituted with halogen, or hydroxy-aryl in which aryl is substituted with hydroxyl, etc.

[0067] A 11 and B 11 Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. Herein, the combination thereof may be, for example, alkylene-CO in which alkylene and CO are combined, alkylene-NR' in which alkylene and NR' are combined, or NR'CO in which NR' and CO are combined.

[0068] As mentioned above, Z 11 is an aromatic ring, and A of the ring may be 11 Substitution at the site, or Z 11 Can be a linking group, wherein Z11 , A 11 and B 11 An aromatic ring fused to the ring is formed.

[0069] In Chemical Formula 1, Z 11 and A 11 The solid line between the two indicates that Z 11 Replace A 11 The situation, and Z 11 and B 11 The dashed line between represents Z 11 , A 11 and B 11 An aromatic ring is formed and fused to the ring.

[0070] When Z 11 When it is an aromatic ring, the aromatic ring may be an aryl group, a heteroaryl group, or any combination thereof. Herein, the combination thereof may be, for example, biphenyl in which benzene and benzene are connected by a single bond, naphthalene in which benzene and benzene are fused, or phenylfuran in which furan is substituted by benzene.

[0071] When Z 11 Fused to A 11 and B 11 To form an aromatic ring, Z 11 includes single bonds, double bonds, alkylene, O, S, NR', NHC (= O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. Herein, the combination thereof may be, for example, alkylene-CO in which alkylene and CO are combined, alkylene-NR' in which alkylene and NR' are combined, or NR'CO in which NR' and CO are combined.

[0072] R' is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. In this article, the combination may include, for example, hydroxy-alkyl in which alkyl and hydroxyl are combined, alkyl-aryl in which alkyl and aryl are combined, haloalkyl in which alkyl is substituted with halogen, or hydroxy-aryl in which aryl is substituted with hydroxyl, etc.

[0073] R 11 and R 21 Each independently is a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. In this article, the combination may include, for example, hydroxy-alkyl wherein alkyl and hydroxyl are combined, alkyl-aryl wherein alkyl and aryl are combined, haloalkyl wherein alkyl is substituted with halogen, or hydroxy-aryl wherein aryl is substituted with hydroxyl, etc.

[0074] At the same time, the solvent or the remaining reactants may be optionally coordinated to M 11 In this case, R 11 A solvent (sol.) may be included. The solvent may be an organic solvent capable of coordination, such as pyridine, tetrahydrofuran (THF), ether, alcohol, amine, acetone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetic acid, or any combination thereof.

[0075] n 11 M 11 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, or an integer of 5 or more, such as an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. As an example, when M 11 When tin (Sn), the oxidation number of tin (Sn) may be trivalent or tetravalent, and the oxidation number of tin (Sn) may be obtained by subtracting only the second heteroatom (X 12 ) without subtracting the bond to the first heteroatom (X) coordinated to tin (Sn) 11 ) bond, which can replace the substituent (R 11 ) 11 ) can be up to 3. Therefore, in Formula 1, n 11 Can be obtained by 11 The integer obtained by subtracting 1 from the oxidation number of

[0076] n 21 is the number of substitutable positions of the aromatic ring, and may be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, an integer of 5 or more, an integer of 6 or more, an integer of 10 or more, an integer of 20 or more, or an integer of 30 or more, such as an integer of 30 or less, an integer of 20 or less, an integer of 10 or less, an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. For example, when Z 11 To replace A 11 When the aromatic ring is benzene, the residue is obtained by subtracting the residue with A 11 The bond of the benzene substituent (R 21 ) total number (n 21 ) can be up to 5, including hydrogen groups.

[0077] Meanwhile, the organometallic compound represented by Chemical Formula 1 may be connected to another organometallic compound represented by Chemical Formula 1, and in this case, the organometallic compound may be a supramolecular structure having a ring structure or a ladder structure. 11 and / or B 11 When NR', the organometallic compound can be substituted by 11 R 11 Any one of 11 R 21 Any one of, or R 'is connected to the other organometallic compound. In this case, R 11 , R 21 or R' are each independently a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof.

[0078] As an example, the organometallic compound may be represented by Chemical Formula 2. That is, the organometallic compound represented by Chemical Formula 2 is one in which Z 11 As the case of an aromatic ring substituted ring.

[0079] [Chemical formula 2]

[0080]

[0081] In Chemical Formula 2, M 11 , X 11 , X 12 , A 11 , B 11 , R 11 , R 21 、n 11 and n 21 is the same as described in Chemical Formula 1, and thus repeated description will be omitted. However, in Chemical Formula 2, Z 11 is an aromatic ring, and the aromatic ring may be an aryl group, a heteroaryl group, or a combination thereof.

[0082] As an example, the organometallic compound represented by Chemical Formula 2 may be represented by Chemical Formula 2-1 or 2-2.

[0083] [Chemical formula 2-1]

[0084]

[0085] [Chemical formula 2-2]

[0086]

[0087] In chemical formulas 2-1 and 2-2, M 11 , R 11 , R 21 and n 11 is the same as described in Chemical Formula 1, and thus repeated description will be omitted. However, in some embodiments of Chemical Formula 2-1, n 21 is an integer of 5, and in Chemical Formula 2-2, n 21 is the integer 3.

[0088] In addition, in Chemical Formula 2-2, R 22 The substituent may include hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or include a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. 22 is the integer 4.

[0089] In chemical formula 2-1, when M 11 Sn, R 11 All CH 3 、n 11 is the integer 3 and R 21 When all of it is hydrogen, it can be represented by chemical formula 2-1-1.

[0090] [Chemical formula 2-1-1]

[0091]

[0092] In chemical formula 2-2, when M 11 Sn, R 11 All CH 3 、n 11 is an integer 3, R 21 and R 22 All are hydrogen groups and n 22 When it is an integer of 4, it can be represented by Chemical Formula 2-2-1.

[0093] [Chemical formula 2-2-1]

[0094]

[0095] The organic metal compound may be represented by Chemical Formula 3. That is, the organic metal compound represented by Chemical Formula 3 is wherein Z 11 For the case of a linking group, where Z 11 , A 11 and B 11An aromatic ring fused to the ring is formed.

[0096] [Chemical formula 3]

[0097]

[0098] In Chemical Formula 3, M 11 , X 11 , X 12 , A 11 , B 11 , R 11 , R 21 、n 11 and n 21 is the same as described in Chemical Formula 1, and thus repeated description will be omitted. However, in Chemical Formula 3, Z 11 is a linking group, such as a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof.

[0099] As an example, the organometallic compound represented by Chemical Formula 3 may be represented by Chemical Formula 3-1.

[0100] [Chemical formula 3-1]

[0101]

[0102] In Chemical Formula 3-1, M 11 , R 11 , R 21 and n 11 is the same as described in Chemical Formula 1, and thus repeated description will be omitted. In some embodiments, in Chemical Formula 3-1, n 21 is the integer 4.

[0103] In chemical formula 3-1, when M 11 Sn, R 11 All CH 3 、n 11 is an integer 2, R 21 All hydrogen and n 21 When it is an integer of 4, it can be represented by Chemical Formula 3-1-1.

[0104] [Chemical formula 3-1-1]

[0105]

[0106] The organic metal compound may be represented by Chemical Formula 4. That is, the organic metal compound represented by Chemical Formula 4 is a supramolecule having a cyclic structure, and is a supermolecule in which three organic metal compounds represented by Chemical Formula 2 are connected by R21 The compound is a compound in which the connecting groups of the first organometallic compound are connected (e.g., bonded) to each other. 21 M that can be connected to the second organometallic compound 11 , R of the second organometallic compound 21 M that can be connected to the third organometallic compound 11 , and R of the third organometallic compound 21 M that can be connected to the first organometallic compound 11 In Formula 4, R connected to another organometallic compound 21 X 21 , X 22 and X 23 express.

[0107] As shown in Chemical Formula 4, in some embodiments, when the organic metal compound has a ring structure, sensitivity can be improved and high resolution can be achieved in the case of only a single exposure process using extreme ultraviolet rays. In some embodiments, moisture stability and environmental stability can be improved, and since the molecular size (size) is small by including only 2 to 4 metals, line edge roughness can be further improved.

[0108] [Chemical formula 4]

[0109]

[0110] In Chemical Formula 4, M 11 To M 13 Each is independently a metal including Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe. A more detailed description thereof is the same as for M in Chemical Formula 1. 11 The descriptions are the same, and thus duplicate descriptions are omitted.

[0111] X 11 To X 16 Each independently is O, S or NR'. A more detailed description thereof is the same as for X in Chemical Formula 1 11 and X 12 The description is the same as that of , and therefore repeated description is omitted.

[0112] A 11 To A 13 , B 11 To B 13 , and X 21 To X 23Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for A in Chemical Formula 1. 11 and B 11 The descriptions are the same, and thus duplicate descriptions are omitted.

[0113] In chemical formula 4, Z 11 To Z 13 Each independently replaces A 11 To A 13 A more detailed description is the same as for Z in Chemical Formula 1. 11 The descriptions are the same, and thus duplicate descriptions are omitted.

[0114] R 11 To R 13 and R 21 To R 23 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 To R 13 Coordinated to M 11 To M 13 A more detailed description is the same as for R in Chemical Formula 1. 11 and R 21 The descriptions are the same, and thus duplicate descriptions are omitted.

[0115] R' is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description thereof is the same as that for R' in Chemical Formula 1, and thus repeated description is omitted.

[0116] n 11 to n 13 Each independently is M 11 To M 13 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, or an integer of 5 or more, such as an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. For example, when M 11 When Sn is used, the oxidation number of Sn may be trivalent or tetravalent, and the oxidation number of Sn may be obtained by subtracting the second heteroatom (X 12) and through the linking group (X 21 ) with another aromatic ring (Z 13 ) without subtracting the bond to the first heteroatom (X 11 ) bond, which can replace the substituent (R 11 ) 11 ) can be up to 2. Therefore, in Formula 4, n 11 to n 13 Can be obtained by 11 To M 13 The integer obtained by subtracting 2 from the oxidation number of

[0117] n 21 to n 23 Each independently is Z 11 To Z 13 The more detailed description is the same as for n in chemical formula 1. 21 The descriptions are the same, and thus duplicate descriptions are omitted.

[0118] n 21 to n 23 Z 11 To Z 13 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, an integer of 5 or more, an integer of 6 or more, an integer of 10 or more, an integer of 20 or more, or an integer of 30 or more, such as an integer of 30 or less, an integer of 20 or less, an integer of 10 or less, an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. For example, when Z 11 For benzene, by subtracting 11 The key and X 22 The bond of the benzene substituent (R 21 ) total number (n 21 ) can be up to 4, including hydrogen groups.

[0119] As an example, the organometallic compound represented by Chemical Formula 4 may be represented by Chemical Formula 4-1.

[0120] [Chemical formula 4-1]

[0121]

[0122] In Chemical Formula 4-1, M 11 To M 13 , R 11 To R 13 , R 21To R 23 , and n 11 to n 13 is the same as described in Chemical Formula 4, and thus repeated description will be omitted. However, in Chemical Formula 4-1, n 21 to n 23 is the integer 4.

[0123] In chemical formula 4-1, when M 11 To M 13 is tin (Sn), R 11 To R 13 All CH 3 , n 11 to n 13 is an integer of 2, and R in each aromatic ring 21 To R 23 One of them is fluorine (F), and the remaining R 21 To R 23 All are hydrogen groups, and n 21 to n 23 When it is an integer of 4, it can be represented by Chemical Formula 4-1-1.

[0124] [Chemical formula 4-1-1]

[0125]

[0126] The organic metal compound may be represented by Chemical Formula 5. That is, the organic metal compound represented by Chemical Formula 5 is wherein M 11 The substituent (R 11 ) are fused to form a cyclic compound.

[0127] [Chemical formula 5]

[0128]

[0129] In Chemical Formula 5, M 11 , X 11 , X 12 , A 11 , B 11 , Z 11 , R 11 , R 21 and n 21 It is the same as described in Chemical Formula 1, and thus a repeated description will be omitted.

[0130] In chemical formula 5, X 21 and X 22 Each independently is O, S or NR'. A more detailed description is the same as for X in Chemical Formula 1 11 and X 12 The descriptions are the same, and therefore repeated descriptions are omitted.

[0131] B 21 includes single bonds, double bonds, alkylene, O, S, NR', NHC (= O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for B in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0132] Ar 21 To replace X 21 and B 21 The aromatic ring of the present invention can be aryl, heteroaryl, or a combination thereof. In this article, the combination thereof can be, for example, biphenyl in which benzene and benzene are connected by a single bond, naphthalene in which benzene and benzene are fused, or phenylfuran in which furan is substituted by benzene.

[0133] R 13 is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 13 includes single bonds, double bonds, alkylene, O, S, NR', NHC (= O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for R in Formula 1. 11 and R 21 The descriptions are the same, and therefore repeated descriptions are omitted.

[0134] R' is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description thereof is the same as that of R' in Chemical Formula 1, and thus repeated description is omitted.

[0135] n 11 M 11 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, or an integer of 5 or more, such as an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. As an example, when M 11 When Sn is used, the oxidation number of Sn may be trivalent or tetravalent, and the oxidation number of Sn may be obtained by subtracting the second heteroatom (X 12 ) key, and X 21 The key, and X 22without subtracting the bond with the first heteroatom (X) coordinated to tin (Sn) 11 ) bond, which can replace the substituent (R 11 ) 11 ) can be up to 1. Therefore, in Formula 5, n 11 Can be obtained by 11 The integer obtained by subtracting 3 from the oxidation number of

[0136] At the same time, the solvent or the remaining reactants may be optionally coordinated to M 11 In this case, R 11 A solvent (sol.) may be included. The solvent may be an organic solvent capable of coordination, such as pyridine, tetrahydrofuran (THF), ether, alcohol, amine, acetone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetic acid, or any combination thereof.

[0137] n 13 Ar 21 The number of substitutable positions can be, for example, 0 or more integers, 1 or more integers, 2 or more integers, 3 or more integers, 4 or more integers, 5 or more integers, 6 or more integers, 10 or more integers, 20 or more integers, or 30 or more integers, such as 30 or less integers, 20 or less integers, 10 or less integers, 6 or less integers, 5 or less integers, 4 or less integers, 3 or less integers, 2 or less integers, or 1 or less integers. For example, when Ar 21 In the case of benzene, by subtracting 21 and B 21 The bond of the benzene substituent (R 13 ) total number (n 13 ) can be up to 4, including hydrogen groups.

[0138] The organometallic compound may be represented by Chemical Formula 6. That is, the organometallic compound represented by Chemical Formula 6 is a supramolecule having a cyclic structure, and is a supermolecule in which four organometallic compounds represented by Chemical Formula 2 are connected by R 21 and B 11 For example, R of the first organometallic compound is 21 and B 11 M connected to the second organometallic compound 11 To form a ring, the second organometallic compound R 21 and B 11 M connected to the third organometallic compound 11 To form a ring, the third organometallic compound R 21 and B 11M connected to the fourth organometallic compound 11 To form a ring, and R of the fourth organometallic compound 21 and B 11 M connected to the first organometallic compound 11 In Formula 6, R connected to another organometallic compound 21 X 21 , X 22 , X 23 and X 24 express.

[0139] As shown in Chemical Formula 6, when the organic metal compound has a cyclic structure, sensitivity is improved and high resolution can be achieved in only a single exposure process using extreme ultraviolet rays, moisture stability and environmental stability are improved, and since the molecular size is small by containing only 2 to 4 metals, line edge roughness can be further improved.

[0140] [Chemical formula 6]

[0141]

[0142] In Chemical Formula 6, M 11 To M 14 Each is independently a metal including Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe. A more detailed description is the same as for M in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0143] X 11 To X 18 Each independently is O, S or NR'. A more detailed description is the same as for X in Chemical Formula 1 11 and X 12 The descriptions are the same, and therefore repeated descriptions are omitted.

[0144] A 11 To A 14 and X 21 To X 24 Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for A in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0145] At the same time, B 11 To B 14 It may be a linking group having a substituent bonded to the metal of another organometallic compound, for example, N, or N and a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, or a combination of OCO.

[0146] Z 11 To Z 14 Each independently replaces A 11 To A 14 and X 11 To X 14 A more detailed description is the same as for Z in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0147] R 11 To R 14 and R 21 To R 24 Each is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description is the same as for R in Chemical Formula 1. 11 and R 21 The descriptions are the same, and therefore repeated descriptions are omitted.

[0148] R' is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description thereof is the same as that of R' in Chemical Formula 1, and thus repeated description is omitted.

[0149] n 11 to n 14 Each independently is M 11 To M 14 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, or an integer of 5 or more, such as an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. As an example, when M 11 When Sn is used, the oxidation number of Sn may be trivalent or tetravalent, and the oxidation number of Sn may be obtained by subtracting the bond (X 12 ), and the aromatic ring (Z 14 ) through the linking group (X 21) and the bond with another organometallic compound B 14 without subtracting the bond with the first heteroatom (X) coordinated to tin (Sn) 11 ) bond, which can replace the substituent (R 11 ) 11 ) can be up to 1. Therefore, in Formula 6, n 11 to n 14 Each independently is passed from M 11 To M 14 The integer obtained by subtracting 3 from the oxidation number of

[0150] At the same time, the solvent or the remaining reactants may be optionally coordinated to M 11 To M 14 In this case, R 11 To R 14 A solvent (sol.) may be included. The solvent may be an organic solvent capable of coordination, such as pyridine, tetrahydrofuran (THF), ether, alcohol, amine, acetone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetic acid, or any combination thereof.

[0151] n 21 to n 24 Each independently is Z 11 To Z 14 The more detailed description is the same as for n in chemical formula 1. 21 The descriptions are the same, and therefore repeated descriptions are omitted.

[0152] n 21 to n 24 Z 11 To Z 14 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, an integer of 5 or more, an integer of 6 or more, an integer of 10 or more, an integer of 20 or more, or an integer of 30 or more, such as an integer of 30 or less, an integer of 20 or less, an integer of 10 or less, an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. For example, when Z 11 For benzene, by subtracting 11 The key and X 22 The bond of the benzene substituent (R 21 ) total number (n 21 ) can be up to 4, including hydrogen groups.

[0153] As an example, the organometallic compound represented by Chemical Formula 6 may be represented by Chemical Formula 6-1.

[0154] [Chemical formula 6-1]

[0155]

[0156] In Chemical Formula 6-1, M 11 To M 14 , R 11 To R 14 , R 21 To R 24 , and n 11 to n 14 is the same as described in Chemical Formula 6, and thus repeated description will be omitted. However, in Chemical Formula 6-1, n 21 to n 24 is the integer 4.

[0157] In chemical formula 6-1, when M 11 To M 14 is tin (Sn), n 11 to n 14 is 2, R 11 To R 14 One of each is CH 3 , R 11 To R 14 The other of each is sol, R 21 To R 24 All are hydrogen groups, and n 21 to n 24 When it is an integer of 4, it can be represented by Chemical Formula 6-1-1. In Chemical Formula 6-1-1, each Sol replacing tin (Sn) represents a solvent coordinated with tin (Sn).

[0158] [Chemical formula 6-1-1]

[0159]

[0160] The organometallic compound may be represented by Chemical Formula 7. That is, the organometallic compound represented by Chemical Formula 7 is a supramolecule having a ladder structure, and the two metals (M 11 ) and the first coordinating heteroatom (X 11 ) are connected to each other to form a ring. For example, X of the first organometallic compound 11 and the second organometallic compound M 11 connected, and the second organometallic compound X 11 The first organometallic compound M 11 Connect to form a ring.

[0161] [Chemical formula 7]

[0162]

[0163] In Chemical Formula 7, M 11 and M 12 Each is independently a metal including Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe. A more detailed description is the same as for M in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0164] X 11 To X 14 Each independently is O, S or NR'. A more detailed description is the same as for X in Chemical Formula 1 11 and X 12 The same as described above, and thus repeated description is omitted. At this time, since X of the first organometallic compound 11 With M 11 Coordinate, so X 11 Can be used with A 11 and the second organometallic compound M 12 bonding, and X 12 Can be used with A 12 and M of the first organometallic compound 11 Bonding.

[0165] A 11 , A 12 , B 11 and B 12 Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for A in Chemical Formula 1. 11 and B 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0166] Z 11 and Z 12 Each independently replaces A 11 The aromatic ring of Z 11 and Z 12 Each independently is fused to A 11 and B 11 or A 12 and B 12 The aromatic rings include single bonds, double bonds, alkylene, O, S, NR', NHC (= O), SO, SO 2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for Z in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0167] R 11 and R 12 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 and R 12 and M 11 and M 12 A more detailed description is the same as for R in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0168] R 21 and R 22 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 21 and R 22 Each independently includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. A more detailed description is the same as for R in Formula 1. 21 The descriptions are the same, and therefore repeated descriptions are omitted.

[0169] R' is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description thereof is the same as that of R' in Chemical Formula 1, and thus repeated description is omitted.

[0170] n 11 and n 12 Each independently is M 11 and M 12 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, or an integer of 5 or more, such as an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. As an example, when M 11When Sn is used, the oxidation number of Sn may be trivalent or tetravalent, and the oxidation number of Sn may be obtained by subtracting the second heteroatom (X 12 ) and the first heteroatom (X 13 ) without subtracting the bond to the first heteroatom (X) coordinated to tin (Sn) 11 ) bond, which can replace the substituent (R 11 ) 11 ) can be up to 2.

[0171] Therefore, in Chemical Formula 7, n 11 and n 12 Can be obtained by 11 To M 12 The integer obtained by subtracting 2 from the oxidation number of

[0172] n 21 and n 22 Each independently is Z 11 and Z 12 The more detailed description is the same as for n in chemical formula 1. 21 The descriptions are the same, and therefore repeated descriptions are omitted.

[0173] As an example, the organometallic compound represented by Chemical Formula 7 may be represented by Chemical Formulas 7-1 to 7-3.

[0174] [Chemical formula 7-1]

[0175]

[0176] [Chemical formula 7-2]

[0177]

[0178] [Chemical formula 7-3]

[0179]

[0180] In Chemical Formulas 7-1 to 7-3, M 11 、M 12 , R 11 , R 12 , R 21 , R 22 、n 11 and n 12 is the same as described in Chemical Formula 7, and thus repeated description will be omitted. However, in Chemical Formula 7-1, n 21 and n 22 is the integer 4.

[0181] R 23 and R24 The substituents may include hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol, amine, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or may include a single bond, a double bond, an alkylene, O, S, NR', NHC(=O), SO, SO 2 , CO, O-CO-O, C(=O)O, OCO, or any combination thereof. 23 and n 24 is the integer 2.

[0182] In chemical formulas 7-1 to 7-3, when M 11 and M 12 is tin (Sn), n 11 and n 12 is the integer 3, R 11 and R 12 Each of the two is CH 3 , R 11 and R 12 The other of each is sol, R 21 and R 22 All hydrogen, n 21 and n 22 is 4, R 23 and R 24 All hydrogen, and n 23 and n 24 When it is an integer of 2, it can be represented by Chemical Formulae 7-1-1 to 7-3-1. In Chemical Formulae 7-1-1 to 7-3-1, each Sol replacing tin (Sn) represents a solvent coordinated with tin (Sn).

[0183] [Chemical formula 7-1-1]

[0184]

[0185] [Chemical formula 7-2-1]

[0186]

[0187] [Chemical formula 7-3-1]

[0188]

[0189] The organic metal compound may be represented by Chemical Formula 8. That is, the organic metal compound represented by Chemical Formula 8 has a structure in which the organic metal compound of the ladder structure represented by Chemical Formula 7 is repeated. For example, Z 11 A with a second organometallic compound 12 and B 12 An aromatic ring is formed.

[0190] [Chemical formula 8]

[0191]

[0192] In Chemical Formula 8, M 11 、M 12 , X 11 To X 14 , A 11 , A 12 , B 11 , B 12 , R 11 , R 12 , R 21 , Z 11 、n 11 、n 12 and n 21 It is the same as described in Chemical Formula 7, and thus repeated description will be omitted.

[0193] In chemical formula 8, n 31 is the repeating number of the organometallic compound, and may be, for example, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, an integer of 5 or more, an integer of 10 or more, an integer of 20 or more, an integer of 60 or more, an integer of 40 or more, an integer of 50 or more, an integer of 40 or more, an integer of 70 or more, an integer of 80 or more, an integer of 90 or more, or an integer of 100 or more, and for example, an integer of 100 or less, an integer of 90 or less, an integer of 80 or less, an integer of 70 or less, an integer of 60 or less, an integer of 50 or less, an integer of 40 or less, an integer of 30 or less, an integer of 20 or less, an integer of 10 or less, an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less.

[0194] As an example, the organometallic compound represented by Chemical Formula 8 may be represented by Chemical Formula 8-1.

[0195] [Chemical formula 8-1]

[0196]

[0197] In chemical formula 8-1, M 11 、M 12 , R 11 , R 12 、n 11 and n 12 is the same as described in Chemical Formula 7, and thus repeated description will be omitted. However, in Chemical Formula 8-1, n 13 and n 22is the integer 2.

[0198] R 22 and R 23 is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description is the same as for R in Chemical Formula 1. 21 The descriptions are the same, and therefore repeated descriptions are omitted.

[0199] In chemical formula 8-1, when M 11 and M 12 is tin (Sn), n 11 and n 12 is the integer 3, R 11 and R 12 Each of the two is CH 3 , R 11 and R 12 The other of each is sol, R 21 and R 22 All hydrogen, and n 13 and n 22 When is 2, it can be represented by Chemical Formula 8-1-1. In Chemical Formula 8-1-1, each Sol replacing tin (Sn) represents a solvent coordinated with tin (Sn).

[0200] [Chemical formula 8-1-1]

[0201]

[0202] The organometallic compound according to some embodiments may be formed by coordinating a metal precursor including a metal with an organic ligand including an aromatic ring in which first and second heteroatoms bonded to the metal are substituted.

[0203] The metal precursor may be represented by Chemical Formula 9.

[0204] [Chemical formula 9]

[0205]

[0206] In Chemical Formula 9, M 11 is a metal including Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe. A more detailed description thereof is the same as for M in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0207] R 91is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description is the same as for R in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0208] n 91 M 11 The number of substitutable positions can be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, or an integer of 5 or more, such as an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. For example, when M 11 When Sn is used, the oxidation number of Sn can be trivalent or tetravalent, and the substituent (R 91 ) 91 ) can be an integer of 3 or 4. Therefore, n 91 Can be with M 11 The same value of the oxidation number.

[0209] For example, when M 11 When it is tin (Sn), the metal precursor may be represented by Chemical Formulas 9-1 to 9-4.

[0210] [Chemical formula 9-1]

[0211]

[0212] [Chemical formula 9-2]

[0213]

[0214] [Chemical formula 9-3]

[0215]

[0216] [Chemical formula 9-4]

[0217]

[0218] In Chemical Formulas 9-1 to 9-4, R 91 To R 93 Each is independently a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof. A more detailed description is the same as for R in Chemical Formula 1. 11 The descriptions are the same, and therefore repeated descriptions are omitted.

[0219] X91 To X 93 Each is independently a halogen, and may be, for example, fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0220] The organic ligand may be represented by Chemical Formulas 11 to 25.

[0221]

[0222]

[0223] In chemical formula 12, Ar 91 It may be an aryl group, a heteroaryl group, or a combination thereof. Herein, the combination thereof may be, for example, biphenyl in which benzene and benzene are linked by a single bond, naphthalene in which benzene and benzene are fused, or phenylfuran in which furan is substituted with benzene.

[0224] In Chemical Formulas 11 to 25, X 96 To X 99 Each is independently a substituent comprising OH, OR′, SH, SR′ or NRR′, wherein R and R′ are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof.

[0225] X 95 The substituents include hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, wherein the combination may include, for example, hydroxy-alkyl in which alkyl and hydroxyl are combined, alkyl-aryl in which alkyl and aryl are combined, haloalkyl in which alkyl is substituted with halogen, or hydroxy-aryl in which aryl is substituted with hydroxyl, etc.

[0226] n 95 For which X 95 The number of substitutable positions of the substituted aromatic ring may be, for example, an integer of 0 or more, an integer of 1 or more, an integer of 2 or more, an integer of 3 or more, an integer of 4 or more, an integer of 5 or more, an integer of 6 or more, an integer of 10 or more, an integer of 20 or more, or an integer of 30 or more, such as an integer of 30 or less, an integer of 20 or less, an integer of 10 or less, an integer of 6 or less, an integer of 5 or less, an integer of 4 or less, an integer of 3 or less, an integer of 2 or less, or an integer of 1 or less. For example, in Chemical Formula 11, the aromatic ring is benzene, and thus, the substitutable substituent (X) in benzene is substituted by subtracting the bonds to -C(=O)-NH-OH and -OH in benzene. 95 ) total number (n 95 ) may be 4, including hydrogen groups.96 to n 99 Each independently represents an integer from 1 to 8, for example, n 96 to n 99 Each independently represents an integer from 1 to 4.

[0227] As an example, the organic ligand represented by Chemical Formula 11 may be represented by Chemical Formulas 11-1 to 11-15.

[0228]

[0229]

[0230] As an example, the organic ligand represented by Chemical Formula 12 may be represented by Chemical Formulas 12-1 to 12-28.

[0231]

[0232]

[0233] As an example, the organic ligand represented by Chemical Formula 13 may be represented by Chemical Formulas 13-1 to 13-6.

[0234]

[0235]

[0236] As an example, the organic ligands represented by Chemical Formulas 14 to 17 may be represented by Chemical Formulas 14-1 to 14-5.

[0237]

[0238] As an example, the organic ligands represented by Chemical Formulas 18 and 19 may be represented by Chemical Formulas 18-1 to 18-31.

[0239]

[0240]

[0241] In Chemical Formulas 18-1 to 18-31, X may each independently be a halogen, and may be, for example, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0242] As an example, the organic ligands represented by Chemical Formulas 20 to 23 may be represented by Chemical Formulas 20-1 to 20-15.

[0243] [Chemical formula 20-1] to [Chemical formula 20-15]

[0244]

[0245] As an example, the organic ligands represented by Chemical Formulas 24 and 25 may be represented by Chemical Formulas 24-1 to 25-1.

[0246] [Chemical formula 24-1]

[0247]

[0248] [Chemical formula 25-1]

[0249]

[0250] Meanwhile, the organic ligands may be classified into an organic ligand forming a 5-membered ring, an organic ligand forming a 6-membered ring, or an organic ligand forming a 7-membered ring, depending on the type of ring they form by combining with a metal.

[0251] The organic ligand forming a 5-membered ring may be a compound represented by Group 1 as an example.

[0252] [Group 1]

[0253]

[0254]

[0255]

[0256]

[0257] As an example, the organic ligand forming a 6-membered ring may be a compound represented by Group 2.

[0258] [Group 2]

[0259]

[0260] As an example, the organic ligand forming a 7-membered ring may be a compound represented by Group 3.

[0261] [Group 3]

[0262]

[0263]

[0264] As described above, the organometallic compound may be formed by coordinating a metal precursor and an organic ligand, and the final product of the synthesis may be obtained by concentrating the solvent under reduced pressure.

[0265] The obtained organometallic compound may be recrystallized, and the recrystallization may be performed by heating the solvent and then cooling it. The recrystallization solvent may be methanol, ethanol, acetone, acetonitrile, ethyl acetate, toluene, hexane or heptane.

[0266] As an alternative to recrystallization methods, the product can be obtained by precipitation, wherein the precipitate can generally be obtained based on differences in solubility in solvents. Suitable solvents for precipitation may include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane or octane; alicyclic hydrocarbons such as cyclohexane or methylcyclohexane; or aromatic hydrocarbons such as benzene, toluene or xylene); halogenated hydrocarbons (aliphatic halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride; or aromatic halogenated hydrocarbons such as chlorobenzene or dichlorobenzene); nitro compounds (nitromethane or nitroethane, etc.); nitriles (such as acetonitrile or benzonitrile); ethers (chain ethers such as diethyl ether, diisopropyl ether or dimethoxyethane; or cyclic ethers such as tetrahydrofuran or dioxane); ketones (such as acetone, methyl ethyl ketone or diisobutyl ketone); esters (such as ethyl acetate or butyl acetate, etc.); carbonates (such as dimethyl carbonate, diethyl carbonate, ethylene carbonate or propylene carbonate); alcohols (such as methanol, ethanol, propanol, isopropanol or butanol); carboxylic acids (such as acetic acid, etc.); water; or any combination thereof, but are not limited thereto. The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency and yield.

[0267] The photoresist composition may include the organometallic compound in an amount of about 1 wt % to about 30 wt %, such as about 1 wt % to about 25 wt %, about 1 wt % to about 20 wt %, about 1 wt % to about 15 wt %, about 1 wt % to about 10 wt %, or about 1 wt % to about 5 wt %, based on the total weight. When the organometallic compound is included within this range, the storage stability and solubility characteristics of the photoresist composition may be improved, thin film formation may be promoted, and sensitivity and resolution characteristics may be improved.

[0268] At the same time, as mentioned above, the metal (M 11 ) in the solvent provide additional coordination bonding sites for the lone pair of electrons of the solvent and thus provide clusters in which bonding between the organometallic compound and the solvent can be induced.

[0269] Compared with the usual single molecule form, the cluster form satisfies the coordination number of the metal due to the additional coordination bond and hides the metal atoms in the structure, thereby improving moisture stability and preventing aggregation due to condensation reaction after hydrolysis, which can lead to increased long-term storage stability. Therefore, defects are effectively reduced during the coating process, which can also affect the coating (coating) stability.

[0270] Furthermore, in some embodiments, since an aggregation phenomenon is prevented, it may be coated in an amorphous form without using an additive during spin coating, and thus sensitivity and coating properties may be improved.

[0271] The solvent included in the photoresist composition according to some embodiments may include an aromatic compound, an alcohol, an ether, an ester, a ketone, naphtha, or a combination thereof.

[0272] The aromatic compound may be, for example, benzene, xylene or toluene.

[0273] The alcohol may be, for example, 4-methyl-2-pentanol, 2-methyl-2-propanol, 1-butanol, methanol, ethanol, isopropanol, 1-propanol or butanol.

[0274] The ether may be, for example, dimethoxymethane, diethyl ether, methyl tert-butyl ether, anisole, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether or dioxane.

[0275] The ester may be, for example, n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate or ethyl acetate.

[0276] The ketone may be, for example, acetone, methyl ethyl ketone or 2-heptanone.

[0277] Optionally, the photoresist composition may further include a photoinitiator.

[0278] The photoinitiator may be a PAG (photo acid generator) configured to generate an acid by light, a PRG (photo radical generator) configured to generate free radicals by light, or a combination of a PAG and a PRG.

[0279] PAG can generate acid when exposed to light from a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or an EUV laser (13.5 nm).

[0280] As an example, the PAG may include a triarylsulfonium salt, a diaryliodonium salt, a sulfonate, or a mixture thereof. For example, the PAG may include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium antimonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium antimonate, methoxydiphenyliodonium trifluoromethanesulfonate, di-tert-butyldiphenyliodonium trifluoromethanesulfonate, 2,6-dinitrobenzyl sulfonate, pyrogallol tris(alkylsulfonate), trifluoromethanesulfonic acid N-hydroxysuccinimide, trifluoromethanesulfonic acid N-hydroxynorbornene-dicarboximide, triphenyl nonafluorobutanesulfonate, or a mixture thereof. sulfonium, diphenyl iodonium nonafluorobutanesulfonate, methoxydiphenyl iodonium nonafluorobutanesulfonate, di-tert-butyldiphenyl iodonium nonafluorobutanesulfonate, N-hydroxysuccinimide nonafluorobutanesulfonate, N-hydroxynorbornene-dicarboximide nonafluorobutanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate (PFOS), diphenyl iodonium PFOS, methoxydiphenyl iodonium PFOS, di-tert-butyldiphenyl iodonium PFOS, N-hydroxysuccinimide PFOS, N-hydroxynorbornene-dicarboximide PFOS, or a mixture thereof.

[0281] For example, when PRG is exposed to light from a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or an EUV laser (13.5 nm), it absorbs light and generates free radicals, thereby generating photochemical properties to initiate polymerization of the organometallic compound contained in the photoresist composition.

[0282] For example, the PRG may include an acylphosphine oxide-based compound, an oxime ester-based compound, etc. The acylphosphine oxide compound may include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, etc. The oxime ester compound may include, for example, 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio] 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, and the like.

[0283] As an example, the PRG may include commercially available products such as IRGACURE 651, IRGACURE 184, IRGACURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE TPO, IRGACURE 819, IRGACURE OXE01, IRGACURE OXE02, IRGACURE MBF, or IRGACURE 754 (BASF product, brand name).

[0284] For example, the photoresist composition may include the photoinitiator in an amount of about 2 wt % to about 60 wt % based on the total weight, but is not limited thereto.

[0285] Optionally, the composition for a semiconductor resist may further include additives.

[0286] For example, the additive may be a surfactant, a cross-linking agent, a leveling agent, a dispersant, an organic acid, a hygroscopic agent, a coupling agent, a quencher, or any combination thereof.

[0287] The surfactant can work in improving the coating uniformity and wettability of the photoresist composition. As an example, the surfactant can include sulfate, sulfonate, phosphoric acid ester, soap, amine salt, quaternary ammonium salt, polyethylene glycol, alkylphenol ethylene oxide adduct, polyol, nitrogenous vinyl polymer or any combination thereof, but is not limited thereto. In addition, the surfactant can include alkylbenzene sulfonate, alkyl pyridinium salt, polyethylene glycol or quaternary ammonium salt. When the photoresist composition includes a surfactant, the surfactant can be included in an amount of about 0.001 % by weight to about 3 % by weight of the gross weight of the photoresist composition.

[0288] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent. In addition, a crosslinking agent having at least two crosslinking substituents may include, for example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoylguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicarboxyl compound, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0289] The leveling agent is intended to improve coating smoothness during printing, and commercially available known leveling agents may be used.

[0290] The dispersant can be used to ensure that the components constituting the photoresist composition are uniformly dispersed in the photoresist composition. As an example, the dispersant may include epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, glucose, sodium lauryl sulfate, sodium citrate, oleic acid, linoleic acid, or any combination thereof, but is not limited to these. When the photoresist composition includes a dispersant, the dispersant may be included in an amount of about 0.001 wt % to about 5 wt % based on the gross weight of the photoresist composition.

[0291] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or any combination thereof, but is not limited thereto.

[0292] The hygroscopic agent can play a role in preventing adverse effects caused by moisture in the photoresist composition. For example, the hygroscopic agent can include polyoxyethylene nonylphenol ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or any combination thereof, but is not limited thereto. When the photoresist composition includes a hygroscopic agent, the hygroscopic agent can be included in an amount of about 0.001 wt % to about 10 wt % based on the total weight of the photoresist composition.

[0293] The coupling agent can be used for improving the adhesion of the resist lower film when the photoresist composition is coated on the resist lower film. As an example, the coupling agent may include a silane coupling agent. For example, the silane coupling agent may include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, 3-methacryloxy propyl trimethoxy silane, 3-acryloxy propyl trimethoxy silane, p-phenylyl trimethoxy silane, 3-methacryloxy propyl methyl dimethoxy silane, 3-methacryloxy propyl methyl diethoxy silane or trimethoxy [3- (phenyl amino) propyl] silane, but is not limited thereto. When the photoresist composition includes a coupling agent, the coupling agent may be included in an amount of about 0.001 wt % to about 5 wt % based on the gross weight of the photoresist composition.

[0294] The quencher may be methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or any combination thereof.

[0295] In the photoresist composition, when the solvent consists of only an organic solvent, the photoresist composition may further include water, and in this case, the water content may be about 0.001 wt % to about 0.1 wt % based on the total weight of the photoresist composition.

[0296] Even when a pattern having a high aspect ratio is formed, the photoresist composition does not cause the pattern to collapse. Therefore, in order to form a micropattern having a width of about 5 nm to about 100 nm, for example, a micropattern having a width of about 5 nm to about 80 nm, a micropattern having a width of about 5 nm to about 70 nm, a micropattern having a width of about 5 nm to about 50 nm, a micropattern having a width of about 5 nm to about 40 nm, a micropattern having a width of about 5 nm to about 30 nm, or a micropattern having a width of about 5 nm to about 20 nm, a photolithography process using light having a wavelength of about 5 nm to about 150 nm, for example, a photolithography process using light having a wavelength of about 5 nm to about 100 nm, a photolithography process using light having a wavelength of about 5 nm to about 80 nm, a photolithography process using light having a wavelength of about 5 nm to about 50 nm, a photolithography process using light having a wavelength of about 5 nm to about 30 nm, or a photolithography process using light having a wavelength of about 5 nm to about 20 nm may be used.

[0297] According to another embodiment, a method of forming a pattern using the photoresist composition may be provided.

[0298] A method of forming a pattern according to some embodiments includes forming a film to be etched on a substrate, forming a photoresist film by applying the aforementioned photoresist composition on the film to be etched, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.

[0299] In the following, reference is made to Figures 1 to 5 , describing a method for forming a pattern using the above-mentioned photoresist composition. Figures 1 to 5 is a cross-sectional view showing an intermediate step of the method of forming a pattern.

[0300] Reference Figure 1 ,First, prepare the object to be etched.

[0301] As an example, the object to be etched may be a thin film 102 formed on a semiconductor substrate 100 .

[0302] As an example, the substrate 100 may include a semiconductor substrate, and the thin film 102 may be an insulating film, a conductive (electrically conductive) film, or a semiconductor film. For example, the thin film 102 may include a metal, an alloy, a metal carbide, a metal nitride, a metal oxynitride, a metal oxycarbide, a semiconductor, polysilicon, an oxide, a nitride, an oxynitride, or a combination thereof, but is not limited thereto.

[0303] Optionally, the surface of the film 102 may be cleaned to remove contaminants remaining on the film 102 .

[0304] In addition, optionally, a resist underlayer film 104 may be formed on the surface of the thin film 102 .

[0305] The resist lower layer film 104 is formed on Figure 2 Between the substrate 100 and the photoresist film 106 shown in the figure, which will be described later, and when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask is scattered into unwanted photoresist areas, non-uniformity of the photoresist line width and interference with pattern formation can be prevented.

[0306] As an example, a composition for forming the resist underlayer film 104 is applied on the surface of the cleaned thin film 102 by spin coating, spray coating, dip coating, knife edge coating, or inkjet printing. After coating by applying a printing method such as screen printing, a drying and baking process may be performed to form the resist underlayer film 104 on the thin film 102. The baking process may be performed at between about 100° C. and about 500° C., for example, between about 100° C. and about 300° C.

[0307] As an example, the resist underlayer film 104 may include an organic or inorganic anti-reflective coating (ARC) material for a KrF excimer laser, an ArF excimer laser, an EUV laser, or any other light source. For example, the resist underlayer film 104 may include a bottom anti-reflective coating (BARC) layer or a developable bottom anti-reflective coating (DBARC) layer. In addition, the resist underlayer film 104 may include an organic component having a light absorbing structure. The light absorbing structure may be, for example, a hydrocarbon compound having one or more benzene rings or a structure in which benzene rings are condensed. The resist underlayer film 104 may be formed to have a thickness of about 1 nm to about 100 nm, but is not limited thereto.

[0308] Reference Figure 2 , the above-mentioned photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106 .

[0309] As an example, the photoresist film 106 is formed by applying the above-mentioned photoresist composition to the substrate 100 on which the thin film 102 is formed using spin coating, spray coating, dip coating or knife edge coating, or by applying the above-mentioned photoresist composition using a printing method such as inkjet printing, screen printing, and then drying the applied photoresist composition. That is, the photoresist film 106 can be formed by coating the above-mentioned photoresist composition on the thin film 102 formed on the substrate 100, and then curing it through a heat treatment process.

[0310] Next, a first baking process of heating the substrate 100 on which the photoresist film 106 is formed may be performed. The first baking process may be performed at a temperature of about 80° C. to about 180° C. for about 30 seconds to about 3 minutes.

[0311] Reference Figure 3 , so that the photoresist film 106 is selectively exposed.

[0312] For example, examples of light that can be used during exposure may include light with a high energy wavelength such as EUV (extreme ultraviolet; wavelength 13.5 nm) or E-Beam (electron beam), and light with a short wavelength such as activation radiation i-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm). For example, the light for exposure may be short wavelength light having a wavelength range of about 5 nm to about 150 nm, and may be light with a high energy wavelength such as EUV or E-Beam.

[0313] When a polymer is formed by a cross-linking reaction such as condensation between the organic metal compounds, the exposed region 106 b of the photoresist film 106 has different solubility from the unexposed region 106 a of the photoresist film 106 .

[0314] Subsequently, a second baking process may be performed on the substrate 100. The second baking process may be performed at a temperature of about 120°C to about 200°C for about 30 seconds to about 3 minutes. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes difficult to dissolve in a developer.

[0315] Reference Figure 4 , the photoresist film 106 corresponding to the unexposed area 106a is dissolved and removed using a developer to form a photoresist pattern 108. As an example, the photoresist film 106 corresponding to the unexposed area 106a is dissolved using an organic solvent such as 2-heptanone and then removed to produce a photoresist pattern 108 corresponding to a negative tone image.

[0316] As an example, the developer may be an organic solvent, for example, a ketone such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, an alcohol such as methanol, 2-methyl-2-propanol, 1-butanol, isopropanol, and 1-propanol, or an ester such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, or an aromatic compound such as benzene, xylene, and toluene, or any combination thereof. In addition, the developer may be an organic solvent containing about 9% by weight or less of an acidic or alkaline substance based on the total weight.

[0317] However, the pattern forming method according to some embodiments is not limited to forming a negative tone image, and can be formed to have a positive tone image. In this case, the developer that can be used to form the positive tone image can be, for example, a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or any combination thereof.

[0318] The photoresist pattern 108 formed by the pattern forming method may have a width of about 5 nm to about 100 nm, for example, about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0319] In addition, the photoresist pattern 108 may have a pitch of about 50 nm or less, for example, about 40 nm or less, about 30 nm or less, about 20 nm or less, about 15 nm or less, about 10 nm or less, or about 5 nm or less, and a line width roughness of about 3 nm or less, or about 2 nm or less.

[0320] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask, thereby forming an organic film pattern 112. The organic film pattern 112 may also have a width corresponding to that of the photoresist pattern 108 described above.

[0321] Reference Figure 5 , a photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102 to form a thin film pattern 114 .

[0322] As an example, the etching of the thin film 102 can be performed by wet etching or dry etching. In the case of dry etching, an etching gas containing, for example, CHF 3 CF 4 , Cl 2 , BCl 3 , or a mixture thereof.

[0323] The thin film pattern 114 may have a width corresponding to the photoresist pattern 108. As an example, the thin film pattern 114 may have a width of about 5 nm to about 100 nm, e.g., about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0324] In addition, the thin film pattern 114 may have a pitch of about 50 nm or less, for example, about 40 nm or less, 30 nm or less, about 20 nm or less, about 15 nm or less, and a half pitch of about 10 nm or less, about 5 nm or less, and a line width roughness of about 3 nm or less, or about 2 nm or less.

[0325] Hereinafter, the present embodiment will be described in more detail through examples related to the manufacture of the above-mentioned photoresist composition. However, the technical features of the present embodiment are not limited to the following examples.

[0326] [Preparation Example 1: Synthesis of organometallic compound]

[0327] (Synthesis Example 1)

[0328] In a 250 mL round-bottom flask, 0.3 g (1.82 mmol) of dimethyltin oxide (metal precursor) was dispersed in 100 mL of toluene, 0.285 g (1.86 mmol) of salicylic hydroxamic acid (organic ligand) was added thereto, and then a reflux device was installed thereto to replace the internal gas with nitrogen. After the mixture was stirred at 180° C. for 3 hours, the compound was obtained therefrom by removing the solvent under reduced pressure and washing it with methanol to obtain compound C represented by chemical formula 4-1-2 with a yield of 65%. 27 H 33 N 3 O 9 Sn 3 .

[0329] [Chemical formula 4-1-2]

[0330]

[0331] (Synthesis Example 2)

[0332] In a 250 mL round-bottom flask, 0.3 g (1.21 mmol) of diamyltin oxide (metal precursor) was dispersed in 100 mL of methanol, 0.185 g (1.21 mmol) of salicylic hydroxamic acid (organic ligand) was added thereto, and then a reflux device was installed thereto to replace the internal gas with nitrogen. After the mixture was stirred at 120° C. for 3 hours, the following viscous fluid was obtained therefrom by removing the solvent under reduced pressure and dissolved in toluene, and then by After filtration and concentration, a red viscous fluid represented by Chemical Formula 6-1-2 was obtained with a yield of 70%.

[0333] [Chemical formula 6-1-2]

[0334]

[0335] (Synthesis Examples 3 to 19)

[0336] Each organometallic compound was synthesized in the same manner as in Synthesis Example 1 or Synthesis Example 2 by changing the types of the metal precursor and the organic ligand as shown in Table 1.

[0337] (Table 1)

[0338]

[0339]

[0340]

[0341] [Experimental Example 1: Evaluation of organometallic compounds]

[0342] The molecular structure of each of the organometallic compounds according to Synthesis Examples 1 to 19 was examined by using NMR, IR spectroscopy, and X-ray diffraction, and then thermal properties were analyzed by using a thermogravimetric analyzer.

[0343] Figures 6 to 8 The NMR spectroscopy results of the organometallic compound prepared in Synthesis Example 1 are shown, which are proton NMR, 13 C NMR, and 119 Sn NMR results.

[0344] Reference Figures 6 to 8 , proton NMR showed that the -NH peak appeared at a very deshielded 13.59 ppm, indicating a binding interaction with tin. In addition, the -99.24 ppm 119 The Sn NMR peaks correspond to the range of peaks typically occurring for alkoxide tin, which are indicative of Sn—O bonds.

[0345] In addition, through XRD structural analysis, the organometallic compound of Synthesis Example 1 has C 27 H 33 N 3 O 9 Sn 3 The chemical formula is three C 9 H 11 NO 3 Sn forms a ring-like supramolecular structure.

[0346] also, Fig. 9 is a graph showing the results of thermogravimetric analysis of the organometallic compound according to Synthesis Example 1, which shows that the organometallic compound has a decomposition temperature of 233° C. reaching 90% of its mass and is thus very stable to heat.

[0347] [Preparation Example 2: Synthesis of Photoresist Composition]

[0348] (Examples 1 to 19)

[0349] The organometallic compounds of Synthesis Examples 1 to 19 were each dissolved in toluene at a weight ratio of 2 wt%, and then filtered with a 0.2 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0350] [Experimental Example 2: Evaluation of Photoresist Composition]

[0351] (Evaluation 1: UV test)

[0352] The photoresist compositions of Examples 1 to 19 were each tested for their photoreactivity to UV. For example, the toluene solutions were each spin-coated on a bare Si wafer, but a portion thereof was exposed to 254 nm UV for 2 hours.

[0353] As a result, it can be seen that the photoresist compositions of Examples 1 to 19 exhibited selective solubility with respect to ethyl acetate (EA), toluene, and propylene glycol methyl ether acetate (PGMEA) depending on exposure.

[0354] (Evaluation 2: Electron beam experiment)

[0355] The photoresist compositions of Examples 1 to 19 were each tested for their photoreactivity to electron beams. For example, the test was performed in 16 steps, from 50 μC / cm 2 Start with 50 μC / cm 2 Increase, and Figures 10A-10B Scanning electron microscope (SEM) images before and after exposure are shown.

[0356] exist Figures 10A-10B middle, Fig. 10A is a scanning electron microscope photograph before exposure, and Fig. 10B is a scanning electron microscope photo after exposure. Figures 10A-10B As shown in , the changes before and after exposure confirm the reactivity to the electron beam.

[0357] (Evaluation 3: EUV experiment)

[0358] The photoresist compositions of Examples 1 to 19 were each tested for their photoreactivity to EUV. For example, by using a circular silicon wafer having a native oxide surface and a diameter of 4 inches as a thin film coating substrate, the photoresist composition was spin-coated at 3000 rpm for 30 seconds. The coated composition was baked at 100° C. (or, additionally, a post-baking (PAB) was applied) for 90 seconds to form a photoresist film.

[0359] After coating and baking, the thickness of the film was 44 nm when measured by ellipsometry.

[0360] On a circular silicon wafer, the photoresist film formed by coating is exposed to extreme ultraviolet light to form a line / space pattern of 8nm to 50nm by changing the energy and focus. After exposure, the film is baked at 180°C for 90 seconds, and then immersed in propylene glycol methyl ether acetate for 30 seconds and taken out therefrom. Finally, the film is baked at 150°C for 5 minutes.

[0361] Refer to the UV exposure results. 2 The highest result was obtained with an energy of 1000 mJ / cm and a focal spot of -20 nm, thus at 132.3 mJ / cm 2 The size of each line / space (L / S) pattern area in the horizontal direction was measured at an energy of -20 nm and a focus of -20 nm, and the results are shown in 11A-11I and Table 2.

[0362] Figures 11A-11I CD-SEM images including after-development inspection (ADI) results showing the pattern in each area, wherein Figures 11A-11I 50P100, 35P70, 22P44, 20P40, 18P36, 16P32, 15P30, 13P26 and 11P22 results are shown respectively. Here, 50P100, for example, shows a line width of 50 nm and a pitch of 100 nm (ie, a space width of 50 nm).

[0363] Table 2 summarizes the actual pattern width measurement results in each area and the line edge roughness (LER) at each left and right side in the ADI results in each area of ​​the pattern.

[0364] (Table 2)

[0365]

[0366]

[0367] Reference Figures 11A-11I As shown in Table 2, the pattern of the 20P40 area can achieve LER≤1.2nm, and 16P32 can be the lowest resolution area where the pattern is transferable (definable). The pattern of the 20P40 area can achieve LWR≤5nm or less, or LWR≤2nm or less.

[0368] While the present disclosure has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the disclosure is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0369] <symbol description>

[0370] 100: Substrate 102: Film

[0371] 104: resist underlayer film 106: photoresist film

[0372] 106b: exposed area 106a: unexposed area

[0373] 108: Photoresist pattern 112: Organic film pattern

[0374] 114: Thin film pattern

Claims

1. A photoresist composition comprising: An organometallic compound comprising a ring comprising a metal, a first heteroatom coordinated to the metal, and a second heteroatom covalently bonded to the metal, and an aromatic ring substituted or fused to the ring; and Solvent.

2. The photoresist composition according to claim 1, wherein The organometallic compound is represented by Chemical Formula 1: [Chemical formula 1] in, In Chemical Formula 1, M 11 is a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 and X 12 are each independently selected from O, S or NR', A 11 and B 11 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 To replace A 11 The aromatic ring of Z 11 For A 11 and B 11 A linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof fused to form an aromatic ring, R 11 and R 21 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 For M 11 The coordinated solvent, or R 11 and R 21 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, R' is independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, n 11 M 11 The number of positions that can be replaced, and n 21 is the number of substitutable positions on the aromatic ring.

3. The photoresist composition according to claim 2, wherein The organometallic compound is represented by Chemical Formula 2: [Chemical formula 2] in, Z 11 To replace A 11 Aromatic ring.

4. The photoresist composition according to claim 3, wherein The organometallic compound is represented by Chemical Formula 2-1 or 2-2: [Chemical formula 2-1] [Chemical formula 2-2] in, In chemical formula 2-2, R 22 is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or a linking group including a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, and n 22 is the integer 4.

5. The photoresist composition according to claim 2, wherein The organometallic compound is represented by Chemical Formula 3: [Chemical formula 3] 6. The photoresist composition according to claim 5, wherein The organometallic compound is represented by Chemical Formula 3-1: [Chemical formula 3-1] 7. The photoresist composition according to claim 1, wherein The organometallic compound is represented by Chemical Formula 4: [Chemical formula 4] in, In chemical formula 4, M 11 To M 13 are each independently a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 To X 16 are each independently selected from O, S or NR', A 11 To A 13 , B 11 To B 13 , and X 21 To X 23 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 To Z 13 Each independently replaces A 11 To A 13 The aromatic rings, R 11 To R 13 and R 21 To R 23 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 To R 13 For M 11 To M 13 Coordinating solvent, R' is independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, n 11 to n 13 Each independently is M 11 To M 13 the number of positions each can replace; and n 21 to n 23 Each independently is Z 11 To Z 13 The number of positions each can replace.

8. The photoresist composition according to claim 7, wherein The organometallic compound is represented by Chemical Formula 4-1: [Chemical formula 4-1] 9. The photoresist composition according to claim 2, wherein The organometallic compound is represented by Chemical Formula 5: [Chemical formula 5] in, In Chemical Formula 5, X 21 and X 22 are each independently selected from O, S or NR', B 21 is a linking group selected from a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Ar 21 To replace X 21 and B 21 The aromatic rings, R 13 is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 13 and R 21 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, n 13 Ar 21 The number of positions that can be replaced.

10. The photoresist composition according to claim 2, wherein The organometallic compound is represented by Chemical Formula 6: [Chemical formula 6] in, In Chemical Formula 6, M 11 To M 14 are each independently a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 To X 18 are each independently selected from O, S or NR', A 11 To A 14 , B 11 To B 14 , and X 21 To X 24 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 To Z 14 Each independently replaces A 11 To A 14 and X 11 To X 14 The aromatic rings, R 11 To R 14 and R 21 To R 24 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 To R 14 For M 11 To M 14 one or more coordinating solvents, R' is independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, n 11 to n 14 Each independently is M 11 To M 14 The number of positions each can replace, and n 21 to n 24 Z 11 To Z 14 The number of positions each can replace.

11. The photoresist composition according to claim 10, wherein The organometallic compound is represented by Chemical Formula 6-1: [Chemical formula 6-1] 12. The photoresist composition according to claim 2, wherein The organometallic compound is represented by Chemical Formula 7: [Chemical formula 7] in, In Chemical Formula 7, M 11 and M 12 are each independently a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 To X 14 are each independently selected from O, S or NR', A 11 , A 12 , B 11 and B 12 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 and Z 12 Each independently replaces A 11 and A 12 The aromatic ring of Z 11 and Z 12 Each independently is fused to A 11 and B 11 or A 12 and B 12 A connecting group including a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof to form an aromatic ring, R 11 and R 12 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 and R 12 For M 11 and M 12 The respective coordinated solvents, R 21 and R 22 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 21 and R 22 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, n 11 and n 12 Each independently is M 11 and M 12 The number of positions each can replace, and n 21 and n 22 Z 11 and Z 12 The number of positions each can replace.

13. The photoresist composition according to claim 12, wherein The organometallic compound is represented by Chemical Formulas 7-1 to 7-3: [Chemical formula 7-1] [Chemical formula 7-2] [Chemical formula 7-3] 14. The photoresist composition according to claim 2, wherein The organometallic compound is represented by Chemical Formula 8: [Chemical formula 8] in, In Chemical Formula 8, M 11 and M 12 are each independently a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 To X 14 are each independently selected from O, S or NR', A 11 , A 12 , B 11 and B 12 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 To be fused to A 11 , B 11 , A 12 and B 12 A connecting group including a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof to form an aromatic ring, R 11 , R 12 and R 21 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 and R 12 For M 11 and M 12 Coordinating solvent, n 11 and n 12 Each independently is M 11 and M 12 The number of positions each can replace, n 21 Z 11 The number of positions that can be replaced, and n 31 An integer from 1 to 100.

15. The photoresist composition according to claim 14, wherein The organometallic compound is represented by Chemical Formula 8-1: [Chemical formula 8-1] where n 13 and n 22 is the integer 2, R 22 and R 23 is a substituent including hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof.

16. The photoresist composition according to claim 1, wherein The organometallic compound is formed by coordinating a metal precursor including the metal and an organic ligand including an aromatic ring in which the first and second heteroatoms are substituted and bonded to the metal, The metal precursor is represented by Chemical Formula 9, and The organic ligand is represented by one of Chemical Formulas 11 to 25: [Chemical formula 9] in, In Chemical Formula 9, M 11 is a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, R 91 is a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, and n 91 M 11 The number of positions that can be replaced, Wherein, in Chemical Formulas 11 to 25, Ar 91 is aryl, heteroaryl, or any combination thereof, X 96 and X 99 are each independently a substituent comprising OH, OR', SH, SR', or NR', R' is independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, X 95 is a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, and n 95 For X 95 the number of substitutable positions of the aromatic ring in which the substitution is made, n 96 to n 99 Each independently represents an integer from 1 to 8.

17. The photoresist composition according to claim 1, wherein The photoresist composition includes the organometallic compound in an amount of 1 wt % to 30 wt % based on the total weight of the photoresist composition.

18. The photoresist composition according to claim 1, wherein The solvent is selected from aromatic compounds, alcohols, ethers, esters, ketones, naphtha, or mixtures thereof.

19. A photoresist composition comprising an organometallic compound represented by Chemical Formula 1; and Solvents [Chemical formula 1] in, In Chemical Formula 1, M 11 is a metal selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe, X 11 and X 12 are each independently selected from O, S or NR', A 11 and B 11 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, Z 11 To replace A 11 The aromatic ring of Z 11 For A 11 and B 11 A linking group that together forms an aromatic ring includes a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, R 11 and R 21 are each independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, or R 11 For M 11 The coordinated solvent, or R 11 and R 21 Each independently is a linking group comprising a single bond, a double bond, an alkylene group, O, S, NR', NHC(=O), SO, SO2, CO, O-CO-O, C(=O)O, OCO, or any combination thereof, R' is independently a substituent comprising hydrogen, hydroxyl, halogen, alkyl, alkoxy, thiol group, amine group, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, or any combination thereof, n 11 M 11 The number of positions that can be replaced, and n 21 is the number of substitutable positions on the aromatic ring.

20. A method for forming a pattern, the method comprising: forming a film to be etched on a substrate; Forming a photoresist film by applying the photoresist composition according to any one of claims 1 to 19 on the film to be etched; patterning the photoresist film to form a photoresist pattern; as well as The film to be etched is etched using the photoresist pattern as an etching mask.

Images