Indium compounds, methods for their manufacture, compositions for indium-containing thin film deposition, and methods for manufacturing indium-containing thin films.

Abstract

This invention relates to indium compounds, methods for manufacturing the same, compositions for depositing indium-containing thin films comprising the same, and methods for manufacturing indium-containing thin films using the same. The indium compounds of this invention have excellent thermal stability, high volatility, and increased vapor pressure, thereby enabling the manufacture of indium-containing thin films of uniform thickness at increased deposition rates.

Description

Technical Field

[0001] This invention relates to indium compounds, methods for manufacturing the same, compositions for thin film deposition containing the same, methods for manufacturing indium-containing thin films, and indium-containing thin films. Background Technology

[0002] The next generation of displays is being developed with the goal of low power consumption, high resolution, and high reliability. To achieve these goals, thin-film transistor (TFT) materials with high charge mobility are required.

[0003] Thin films are used in a variety of important applications, including the fabrication of semiconductor devices and nanotechnology. These applications include, for example, conductive films, high-refractive-index optical coatings, anti-corrosion coatings, photocatalyst self-cleaning glass coatings, biocompatible coatings, gate dielectric insulating films in field-effect transistors (FETs), dielectric capacitor layers, capacitor electrodes, gate electrodes, binder diffusion barriers, and integrated circuits. Furthermore, thin films are also used in microelectronic applications such as high-k dielectric oxides for dynamic random access memory (DRAM) applications, infrared detectors, and ferroelectric perovskites for non-volatile ferroelectric random access memories (NV-FeFAMs). The need for such dielectric thin films is increasing due to the continuous miniaturization of microelectronic components.

[0004] Previously, amorphous silicon was used in thin-film transistors, but in recent years, metal oxides, which have higher charge mobility than silicon and are easier to process at low temperatures than polycrystalline silicon, have been used. These metal oxides are materials with added indium, zinc, and other metal atoms, and are fabricated through processes such as sputtering, ALD (atomic layer deposition), PLD (pulsed laser deposition), and CVD (chemical vapor deposition).

[0005] Indium (In) exhibits excellent transparency and conductivity, making it widely used in transparent electrodes. However, when forming In-containing metal thin films using sputtering targets, the composition of the deposited film is crystallized using the sputtering target, limiting the ability to uniformly control the film composition. Furthermore, maintaining uniform film composition and thickness is difficult during large-area deposition, resulting in challenges in achieving uniform film properties. Additionally, when using chemical vapor deposition (CVD) instead of sputtering, the prevalent Indium precursors, such as trimethylindium (CAS NO. 3385-78-2), are mostly solid, leading to problems in vapor pressure control and reproducibility of uniform films. In particular, most Indium precursors exhibit thermal decomposition characteristics at temperatures above 250°C, making it difficult to obtain high-quality films and limiting the achievement of uniform thickness and consistent multi-component compositions during large-area deposition.

[0006] Therefore, there is a need to develop high-quality indium precursors that exhibit excellent thermal stability at high temperatures and are deposited uniformly.

[0007] Existing technical documents

[0008] Patent documents

[0009] (Patent Document 1) Korean Patent Publication No. 10-2328782 (March 6, 2017)

[0010] (Patent Document 2) Korean Patent Publication No. 10-1953893 (November 8, 2012) Summary of the Invention

[0011] The purpose of this invention is to provide novel indium compounds and a method for manufacturing indium compounds that are easy to mass-produce.

[0012] Another object of the present invention is to provide a composition for indium-containing thin film deposition comprising an indium compound according to an embodiment of the present invention.

[0013] Another object of the present invention is to provide a method for manufacturing an indium-containing thin film exhibiting a uniform thickness by utilizing an indium compound and an indium-containing thin film deposition composition comprising therein.

[0014] In addition, the present invention provides an indium-containing thin film with an indium content of 35% or more.

[0015] The present invention provides indium compounds represented by the following chemical formula 1.

[0016] [Chemical Formula 1]

[0017]

[0018] [In the above chemical formula 1,]

[0019] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0020] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0021] R5 to R6 are independently C1-C10 alkyl groups.

[0022] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0023] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11 and R 12 They can be connected to form a loop.

[0024] In the above chemical formula 1, L is a C1-C6 alkylene group, R1 to R4 are independently hydrogen or C1-C6 alkyl groups, R5 to R6 are independently C1-C6 alkyl groups, and Y is -NR. 11 R 12 -OR 13 or -SR 14 R 11 To R 14 Each of them is independently hydrogen or C1-C6 alkyl, or the above-mentioned R 11 and R 12 They can connect to form alicyclic rings.

[0025] According to an embodiment of the present invention, the above-mentioned indium compound can be represented by the following chemical formula 2.

[0026] [Chemical Formula 2]

[0027]

[0028] In the above chemical formula 2,

[0029] R1 to R4 are independently hydrogen or C1-C6 alkyl groups.

[0030] R5 to R6 are independently C1-C6 alkyl groups.

[0031] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0032] R 11 To R 14 Each of them is independently hydrogen or C1-C6 alkyl, or the above-mentioned R 11 and R 12 They can connect to form alicyclic rings.

[0033] m is an integer from 1 to 3.

[0034] The indium compound described above according to an embodiment of the present invention may be selected from the following compounds.

[0035]

[0036] In addition, the present invention provides a method for manufacturing an indium compound, wherein the indium compound represented by the following chemical formula 1 can be manufactured by reacting a compound of the following chemical formula 5 and the following chemical formula 6 with a compound of the following chemical formula 4.

[0037] [Chemical Formula 1]

[0038]

[0039] [Chemical Formula 4]

[0040]

[0041] [Chemical Formula 5]

[0042] R5MgX 1

[0043] [Chemical Formula 6]

[0044] R6MgX 2

[0045] [In the above chemical formulas 1, 4, 5, and 6,]

[0046] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0047] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0048] R5 and R6 are independently C1-C10 alkyl groups.

[0049] Y is -NR 11 R 12 -OR 13 、or -SR 14 ,

[0050] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11and R 12 They can be connected to form a ring.

[0051] X, X 1 and X 2 They are halogens, independent of each other.

[0052] The compound of chemical formula 4 can be produced by reacting the compound of chemical formula 7 and the compound of chemical formula 8.

[0053] [Chemical Formula 7]

[0054]

[0055] [Chemical Formula 8]

[0056] InX3

[0057] [In the above chemical formulas 7 and 8,]

[0058] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0059] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0060] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0061] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11 and R 12 They can be connected to form a ring.

[0062] X is a halogen.

[0063] The present invention provides a composition for indium-containing thin film deposition comprising an indium compound according to an embodiment of the present invention.

[0064] In addition, the present invention provides a method for manufacturing an indium-containing thin film using an indium compound or an indium-containing thin film deposition composition comprising an indium compound according to an embodiment of the present invention.

[0065] The above manufacturing method may include the following steps: a) heating the substrate mounted in the chamber, and b) injecting the reactive gas and the indium-containing thin film deposition composition into the chamber to manufacture an indium-containing thin film.

[0066] The reacting gases mentioned above can be any one or more selected from oxygen (O2), ozone (O3), water vapor (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amine, diamine, carbon monoxide (CO), carbon dioxide (CO2), C1 to C12 saturated or unsaturated hydrocarbons, hydrogen (H2), argon (Ar), silane, and helium (He).

[0067] The present invention provides an indium-containing thin film containing more than 35% indium.

[0068] According to an embodiment of the invention, the indium compound exhibits improved thermal stability, high volatility, and increased vapor pressure, thereby enabling the formation of highly reliable thin films with stable deposition rates.

[0069] According to an embodiment of the present invention, a method for manufacturing indium compounds can be easily and industrially produced in high yields of high-purity indium compounds using a simple process.

[0070] According to an embodiment of the present invention, a method for manufacturing indium-containing thin films utilizes the indium compound of the present invention or an indium-containing thin film deposition composition containing the indium compound, thereby achieving high film uniformity and good doping control using atomic layer deposition (ALD) or similar methods. Furthermore, the above-described manufacturing method can provide conformal step coverage for three-dimensional semiconductor devices.

[0071] According to an embodiment of the present invention, the indium-containing thin film contains more than 35% indium, thereby exhibiting excellent physical properties. Attached Figure Description

[0072] Figure 1 This is a graph showing the TG analysis results of Embodiment 1 of the present invention.

[0073] Figure 2 This is a graph showing the DSC analysis results of Embodiment 1 of the present invention.

[0074] Figure 3 This is a graph showing the TG analysis results of Embodiment 2 of the present invention.

[0075] Figure 4 This is a graph showing the DSC analysis results of Embodiment 2 of the present invention. Detailed Implementation

[0076] The present invention provides an indium compound, a method for manufacturing the same, an indium-containing thin film deposition composition comprising the same, and a method for manufacturing a thin film using the same.

[0077] The singular forms used in this invention may also be intended to include plural forms unless otherwise indicated in the context.

[0078] The term "comprising / including" as used in this invention is an open-ended description having a meaning equivalent to expressions such as "possessing," "containing," "having," or "characterized in," and does not exclude elements, materials, or processes not further listed.

[0079] The term "alkyl" as used in this invention encompasses both straight-chain and branched forms, and can have 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. Furthermore, in other embodiments, alkyl groups can have 1 to 4 carbon atoms.

[0080] In this invention, "alkylene" refers to a divalent organic radical derived by removing a hydrogen atom from an "alkyl" radical. Here, alkyl is the same as defined above.

[0081] The term "halogenated" or "halogen" as used in this invention refers to fluorine, chlorine, bromine, or iodine.

[0082] In this invention, "halogenated alkyl" refers to an alkyl group in which one or more hydrogen atoms are each replaced by a halogen atom. For example, halogenated alkyl groups include -CF3, -CHF2, -CH2F, -CBr3, -CHBr2, -CH2Br, -CCl3, -CHCl2, -CH2Cl, -CI3, -CHI2, -CH2I, -CH2-CF3, -CH2-CHF2, -CH2-CH2F, -CH2-CBr3, -CH2-CHBr2, -CH2-CH2Br, -CH2-CCl3, -CH2-CHCl2, -CH2-CH2Cl, -CH2-CI3, -CH2-CHI2, -CH2-CH2I, and similar groups. Here, alkyl and halogen are defined as described above.

[0083] The number of carbon atoms described in the alkyl group, etc., as described in this invention does not include the number of carbon atoms of the substituents. As an example, C1-C10 alkyl refers to alkyl with a number of carbon atoms of 1 to 10, excluding the number of carbon atoms of the substituents of the alkyl group.

[0084] In this invention, "substituted" means that the hydrogen atoms of the substituted portion (e.g., alkyl, aryl, or cycloalkyl) are replaced by substituents.

[0085] The present invention will now be described in more detail. In this description, unless otherwise defined, the technical and scientific terms used will have the meanings commonly understood by those skilled in the art to which this invention pertains. In the following description, descriptions of well-known functions and structures that may unnecessarily obscure the essence of the invention are omitted.

[0086] The present invention provides indium compounds represented by the following chemical formula 1.

[0087] [Chemical Formula 1]

[0088]

[0089] [In the above chemical formula 1,]

[0090] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0091] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0092] R5 to R6 are independently C1-C10 alkyl groups.

[0093] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0094] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11 and R 12 They can be connected to form a loop.

[0095] The indium compound represented by the above-described chemical formula 1 according to the present invention exhibits excellent thermal stability, high volatility and increased vapor pressure, and therefore, when used therein, indium-containing thin films with high reliability can be obtained.

[0096] For the indium compound according to an embodiment of the present invention, in the above chemical formula 1, L is a C1-C6 alkylene, R1 to R4 are independently hydrogen or C1-C6 alkyl, R5 to R6 are independently C1-C6 alkyl, and Y is -NR. 11 R 12 -OR 13 or -SR 14 R 11 To R 14 Each of them is independently hydrogen or C1-C6 alkyl, or the above-mentioned R 11 and R 12 They can connect to form alicyclic rings.

[0097] According to a preferred embodiment, the indium compound can be represented by the following chemical formula 2.

[0098] [Chemical Formula 2]

[0099]

[0100] In the above chemical formula 2,

[0101] R1 to R4 are independently hydrogen or C1-C6 alkyl groups.

[0102] R5 to R6 are independently C1-C6 alkyl groups.

[0103] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0104] R 11 To R 14 Each of them is independently hydrogen or C1-C6 alkyl, or the above-mentioned R 11 and R 12 They can connect to form alicyclic rings.

[0105] m is an integer from 1 to 3.

[0106] For the indium compound represented by the above chemical formula 2, more specifically, R1 to R4 can be hydrogen or C1-C4 alkyl, R5 to R6 can be C1-C4 alkyl, and Y is -NR. 11 R 12 -OR 13 or -SR 14 R 11 To R 14 Each of them is independently hydrogen or C1-C4 alkyl, or the above-mentioned R 11 and R 12 They can be connected to form a ring, where m is an integer of 2 or 3.

[0107] According to a more preferred embodiment, the indium compound can be represented by the following chemical formula 2-1.

[0108] [Chemical Formula 2-1]

[0109]

[0110] In the above chemical formula 2-1,

[0111] R is a C1-C4 alkyl group.

[0112] R1 to R4 are independently hydrogen or C1-C4 alkyl groups.

[0113] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0114] R 11 To R14 Each of them is independently hydrogen or C1-C4 alkyl, or the above-mentioned R 11 and R 12 Alicyclic rings can be formed by the linkage of C2-C6 alkylene groups.

[0115] m is an integer of 2 or 3.

[0116] In one embodiment, the indium compound may be selected from the following compounds, but is not limited thereto.

[0117]

[0118] The present invention provides a method for manufacturing an indium compound according to an embodiment of the present invention, wherein the indium compound represented by the following chemical formula 1 can be manufactured by reacting a compound of the following chemical formula 5 and the following chemical formula 6 with a compound of the following chemical formula 4.

[0119] [Chemical Formula 1]

[0120]

[0121] [Chemical Formula 4]

[0122]

[0123] [Chemical Formula 5]

[0124] R5MgX 1

[0125] [Chemical Formula 6]

[0126] R6MgX 2

[0127] [In the above chemical formulas 1, 4, 5, and 6,]

[0128] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0129] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0130] R5 and R6 are independently C1-C10 alkyl groups.

[0131] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0132] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11 and R12 They can be connected to form a ring.

[0133] X, X 1 and X 2 They are halogens, independent of each other.

[0134] Specifically, in a method for manufacturing an indium compound according to an embodiment of the present invention, the indium compound represented by the following chemical formula 1 is manufactured by reacting the compounds of the above chemical formula 5 and the above chemical formula 6 with the compound of the above chemical formula 4, and can be manufactured by slowly adding the compounds of chemical formula 5 and the compounds of chemical formula 6, or by adding the compound of chemical formula 5 and reacting for a certain period of time before adding the compound of chemical formula 6 to carry out the reaction.

[0135] The compound of chemical formula 4 can be produced by reacting the compound of chemical formula 7 and the compound of chemical formula 8.

[0136] [Chemical Formula 7]

[0137]

[0138] [Chemical Formula 8]

[0139] InX3

[0140] [In the above chemical formulas 7 and 8,]

[0141] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0142] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0143] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0144] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11 and R 12 They can be connected to form a ring.

[0145] X is a halogen.

[0146] In addition, the compound represented by the above chemical formula 7 can be produced by reacting alkyllithium with a compound of the following chemical formula 9.

[0147] [Chemical Formula 9]

[0148]

[0149] In the above chemical formula 9,

[0150] L is a C1-C10 alkylene or a halo-C1-C10 alkylene.

[0151] R1 to R4 are independently hydrogen or C1-C10 alkyl groups.

[0152] Y is -NR 11 R 12 -OR 13 or -SR 14 ,

[0153] R 11 To R 14 Each of the above is independently hydrogen, C1-C10 alkyl, or halo-C1-C10 alkyl, or R. 11 and R 12 They can be connected to form a loop.

[0154] Specifically, the aforementioned alkyl lithium can be C1-C10 alkyl lithium, and can be one or more selected from methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium and n-hexyl lithium, but is not limited thereto.

[0155] The above-mentioned method for manufacturing indium compounds can be easily used to mass-produce them using simple procedures.

[0156] The solvent used in the manufacturing method according to one embodiment can be any common organic solvent, but preferably one or more of the following: hexanal, pentane, dichloromethane (DCM), dichloroethane (DCE), benzene, toluene, acetonitrile (MeCN), nitromethane (Nitromethan), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA).

[0157] The reaction temperature can be the temperature commonly used in organic synthesis, or it can be varied depending on the amount of reactants and starting materials. Preferably, it can be carried out at -30°C to 40°C, more specifically at -20°C to 30°C, and even more specifically at -10°C to 20°C.

[0158] The reaction was terminated after confirmation by NMR or other means that the starting material had been completely consumed. The target analyte can then be separated and purified using conventional methods such as extraction, solvent distillation under reduced pressure, and column chromatography.

[0159] The aforementioned cyclopentadiene compounds are stably coordinated with the central metal through a resonance structure, thus significantly improving the thermal stability of the indium compounds. Therefore, according to an embodiment of the present invention, the indium compound enables the formation of thin films composed of indium, indium nitride (InNx), or indium oxide (InOx) with high reliability.

[0160] The aforementioned cyclopentadiene compounds may be combined with aminoalkyl, alkoxyalkyl, or alkyl mercapto groups. Therefore, the thermal stability of these cyclopentadiene compounds can be further improved during the deposition process.

[0161] The present invention provides a composition for indium-containing thin film deposition comprising an indium compound according to an embodiment of the present invention.

[0162] In addition, the present invention provides a method for manufacturing an indium-containing thin film using an indium compound or an indium-containing thin film deposition composition comprising an indium compound according to an embodiment of the present invention.

[0163] The above-mentioned method for manufacturing indium-containing thin films can be a conventional method used in the art. Specifically, it can be atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD).

[0164] More preferably, the method for manufacturing the indium-containing thin film according to one embodiment can be atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), etc.

[0165] The above manufacturing method may include the following steps: a) heating the substrate mounted in the chamber, and b) injecting the reactive gas and the indium-containing thin film deposition composition into the chamber to manufacture an indium-containing thin film.

[0166] In one embodiment of the present invention, in step a) above, the substrate mounted in the chamber can be heated to 200°C to 1000°C, specifically, to 250°C to 500°C, and more specifically, to 300°C to 400°C. Since the deposition of the indium-containing thin film deposition composition can be performed at relatively low temperatures as described above, process efficiency is improved, and thermal decomposition of the compounds used in the deposition process is reduced, thus resulting in a significant improvement in the stability and productivity of the deposition process. Furthermore, the content of impurities such as carbon in the indium-containing thin film is reduced, thereby improving the physical properties of the manufactured thin film.

[0167] The substrate according to one embodiment may include one or more substrates selected from glass, silicon, metal polyester (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyetherimide (PEI), polyethersulfone (PES), polyetheretherketone (PEEK), and polyimide (PI), but is not limited thereto.

[0168] In step b) above, the indium-containing thin film deposition composition can be used alone, or a mixture obtained by mixing one or more gallium precursors and zinc precursors in the above composition can be used.

[0169] Specifically, the gallium precursor mentioned above can be TMG (trimethylgallium), and the zinc precursor mentioned above can be DEZ (diethylzinc), but is not limited to these.

[0170] According to an embodiment of the present invention, the method for manufacturing an indium-containing thin film can produce a multilayer structure containing different metals, and can be a structure in which precursors of metals different from the above-mentioned composition for depositing indium-containing thin films are deposited in sequence.

[0171] In addition, the aforementioned multilayer thin film may be deposited by mixing a precursor of a metal different from the composition for indium thin film deposition. Specifically, it may be a structure in which a compound selected from gallium precursor and zinc precursor is mixed with the composition for indium thin film deposition and deposited on a substrate.

[0172] More specifically, the aforementioned multilayer thin film can be IGZO (indium / gallium / zinc / oxide), and the composition ratio of indium:gallium:zinc can be (1 to 10):(1 to 10):(1 to 10), preferably (1 to 5):(1 to 5):(1 to 5), and more preferably 1:1:1.

[0173] In step b) of the above manufacturing method, the deposition conditions can be adjusted according to the structure or thermal properties of the target thin film. Examples of deposition conditions according to one embodiment include the indium compound feed rate, the reactant gas and the transport gas feed rate, pressure, RF power, etc.

[0174] As a non-limiting example of such deposition conditions, the indium compound feed flow rate could be adjusted in a Bubbler type range of 1 to 1000 sccm, the transport gas flow rate in a range of 1 to 5000 sccm, the reactant gas flow rate in a range of 10 to 5000 sccm, the pressure in a range of 0.1 to 10 torr, and the RF power in a range of 10 to 1000 W, but is not limited thereto.

[0175] In step b) of the above manufacturing method, the injection time when injecting the indium-containing thin film deposition composition can be 1 to 30 seconds, preferably 1 to 20 seconds, and more preferably 2 to 10 seconds. Within such a range, the uniformity of the film thickness is improved, and a uniform film can be manufactured even in substrates with complex shapes.

[0176] In one embodiment, the reactant gas may be any one or more selected from oxygen (O2), ozone (O3), water vapor (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amine, diamine, carbon monoxide (CO), carbon dioxide (CO2), C1 to C12 saturated or unsaturated hydrocarbons, hydrogen (H2), argon (Ar), silane, and helium (He).

[0177] Specifically, the reactant gas can be any one or more selected from water vapor (H2O), oxygen (O2), ozone (O3), hydrogen (H2), silane, ammonia (NH3), and hydrazine (N2H4). When deposition is completed in the presence of oxidizing reactant gases such as water vapor (H2O), oxygen (O2), and ozone (O3), indium oxide (InO) can be formed. x Indium-containing films can be formed when deposition is completed in the presence of reactive gases such as hydrogen (H2) and silane, and indium nitrides (InN2H4) can be formed when deposition is completed in the presence of nitrogen-based reactive gases such as ammonia (NH3) and hydrazine (N2H4). x )film.

[0178] In one embodiment, the transport gas in the deposition step is an inactive gas, which may be any one or more of argon (Ar), helium (He) and nitrogen (N2), specifically nitrogen (N2), but is not limited thereto.

[0179] In the manufacturing method described above according to an embodiment of the present invention, a step c) of injecting a reaction gas into the chamber after step b) may be included. Steps b) and c) can be performed as a cycle and the cycle can be repeated.

[0180] In one embodiment, after the delivery gas and the indium-containing thin film deposition composition are injected into the chamber, a purging step can be performed to remove any indium-containing thin film deposition composition not adsorbed on the substrate using the delivery gas.

[0181] In one embodiment, after the reaction gas is injected into the chamber, a purging step can be performed to remove reaction byproducts and residual reaction gas using the transport gas.

[0182] In one embodiment, the implantation step, purging step, reactant gas implantation step, and purging process of the above-described indium-containing thin film deposition composition can be performed as one cycle and repeated until a thin film of the desired thickness is formed. Specifically, this process can be repeated 50 to 1000 times, and more specifically, 100 to 300 times. In this case, a suitable thin film thickness can be achieved, and process efficiency can be improved.

[0183] The film manufactured by the above-described indium-containing thin film manufacturing method according to an embodiment of the present invention is uniform, exhibits an improved deposition rate, and can provide conformal step coverage for structures with large aspect ratios.

[0184] The resistivity of the aforementioned indium-containing thin film at 25°C can be 1×10⁻⁶. -5 Up to 1×10 -1 Ωcm, preferably 1×10 -4 Up to 1×10 -2 Ωcm, more preferably 1×10 -3 Up to 5×10 -3 Ωcm.

[0185] The resistivity measurement method described herein is not particularly limited as long as it is a well-known measurement method commonly practiced in the technical field to which this invention pertains. As a specific example, it can be measured by the 4-probe method.

[0186] In the indium-containing thin film according to the present invention, the indium content can be 35% or more, preferably 35% to 65%, and more preferably 35% to 50%.

[0187] The following specific embodiments will be used to describe in more detail the method for manufacturing the indium compound according to the present invention and the method for manufacturing thin films using the same.

[0188] However, the following embodiments are merely a reference for describing the invention in detail, and the invention is not limited thereto and can be implemented in various forms. Furthermore, the terminology used in the description of this invention is only for effectively describing specific embodiments and is not intended to limit the invention.

[0189] In addition, unless otherwise indicated, all embodiments were carried out using techniques commonly known in the art for treating air-sensitive substances under an inactive atmosphere such as purified nitrogen (N2) or argon (Ar).

[0190] [Example 1] Manufacturing of (C5H4(CH2CH2N(CH3)2))In(CH3)2

[0191] In a 1L double-necked flask equipped with a magnetic stirrer and a condenser, 59 ml of n-Butyllittium (0.14 mol of 2.3 M n-Hexane solution) was added, followed by the addition of 200 ml of n-Hexane and stirring.

[0192] The internal temperature of the above mixture was maintained at 0°C, and (2-dimethylaminoethyl)cyclopentadiene was slowly added. The mixture was then stirred at room temperature for 2 hours to synthesize lithium (2-dimethylaminoethyl)cyclopentadiene.

[0193] In a 2L double-necked flask equipped with a magnetic stirrer and a condenser, 30g (0.14mol) of InCl3 was added, followed by 200ml of n-hexane. The mixture was kept at 0°C and stirred. Li(2-Dimethylaminoethyl)cyclopentadiene was then slowly added to the flask, and the mixture was stirred at room temperature for 2 hours to synthesize (C5H4(CH2CH2N(CH3)2))2In(Cl)2.

[0194] In the aforementioned flask, MeMgCl (90 ml, 3.0 M THF solution, 0.27 mol) was slowly added while maintaining an internal temperature of 10 °C, resulting in the formation of a light gray precipitate. The synthesized mixture was filtered, and the solvent was removed under reduced pressure, yielding 34 g of a light yellow liquid (85% from InCl3).

[0195] 1 H NMR(400MHz,C6D6)δ6.5,5,6,1.7(m,4H,Cp),2.5(t,2H),1.8(t,2H),1.5(s,6H),-0.1(s,6H)

[0196] Figure 1 The figure shows the TG graph of (C5H4(CH2CH2N(CH3)2))In(CH3)2 produced in Example 1. It can be seen that the indium compound produced in Example 1 has a single evaporation step at about 200°C, and the residual mass at 500°C is confirmed to be 4.2%. Therefore, it can be seen that the indium compound of the present invention has excellent thermal stability.

[0197] in addition, Figure 2 The results of DSC analysis are shown, confirming an endothermic peak at 260°C, indicating effective evaporation.

[0198] [Example 2] Preparation of (C5H4(CH2CH2O(CH3)))In(CH3)2

[0199] In a 1L double-necked flask equipped with a magnetic stirrer and a condenser, 0.14 mol of n-butyllithium (59 ml of 2.3 M n-hexane solution) was added, followed by the addition of 200 ml of n-hexane and stirring.

[0200] The internal temperature of the above mixture was maintained at 0°C, and (2-methoxyethyl)cyclopentadiene was slowly added. The mixture was then stirred at room temperature for 2 hours to synthesize lithium (2-methoxyethyl)cyclopentadiene.

[0201] In a 2L double-necked flask equipped with a magnetic stirrer and a condenser, 30 g (0.14 mol) of InCl3 was added, followed by 200 mL of n-hexane. The mixture was stirred while maintaining the internal temperature at 0°C. Li(2-Methoxyethyl)cyclopentadiene was then slowly added to the same flask, and the mixture was stirred at room temperature for 2 hours to synthesize (C5H4(CH2CH2O(CH3))In(Cl)2. In the same flask, 0.27 mol (90 mL of 3.0 M THF solution) was slowly added while maintaining the internal temperature at 10°C, resulting in the formation of a light gray precipitate. The synthesized mixture was filtered, and the solvent was removed under reduced pressure to obtain 20.5 g of a pale yellow liquid (76% from InCl3).

[0202] 1 H NMR(400MHz,C6D6)δ6.5,5.7,3.0(m,4H,Cp),2.9(t,2H),2.7(s,3H),2.6(t,2H),-0.3(s,6H)

[0203] Figure 3 The figure shows the TG graph of (C5H4(CH2CH2O(CH3)))In(CH3)2 produced in Example 2. It can be seen that the indium compound produced in Example 2 has a single evaporation step at 190°C, and the residual mass at 500°C is confirmed to be 4%. Therefore, it can be seen that the indium compound of the present invention has excellent thermal stability.

[0204] in addition, Figure 4 The results of DSC analysis are shown, confirming an endothermic peak at 230°C, indicating effective evaporation.

[0205] [Example 3] Fabrication of an indium-containing thin film using (C5H4(CH2CH2N(CH3)2))In(CH3)2

[0206] Using the indium compound according to Example 1 above, ozone (O3) was used as the reactant gas, and an indium-containing thin film was fabricated by atomic layer deposition (ALD).

[0207] A silicon substrate is loaded inside the deposition chamber, and the temperature of the substrate is adjusted to 350°C. (C5H4(CH2CH2N(CH3)2))In(CH3)2, manufactured in Example 1, is filled into a stainless steel foam container as an organometallic precursor, and the temperature is adjusted to 100°C.

[0208] Using nitrogen as the transport gas (100 sccm), the aforementioned organometallic precursor was injected into the deposition chamber for 3 seconds. A 5-second purification process was then performed using nitrogen (500 sccm) to remove any remaining organometallic precursor and reaction byproducts from the deposition chamber.

[0209] Ozone was injected for 5 seconds as a reactant gas to deposit an indium oxide film. Then, nitrogen gas (500 sccm) was used for 5 seconds to purge residual reactant gases and reaction byproducts.

[0210] The above process was repeated 1000 times as a single cycle to produce an indium-containing oxide film. XPS analysis of the indium-containing film revealed an indium content of 38.2% and an oxygen (O) content of 58.1%, confirming the substantial formation of an indium oxide film.

[0211] [Example 4] Fabrication of an indium-containing thin film using (C5H4(CH2CH2O(CH3)))In(CH3)2

[0212] Using the indium compound according to Example 1 above, ozone (O3) was used as the reactant gas, and an indium-containing thin film was fabricated by atomic layer deposition (ALD).

[0213] A silicon substrate with grown silicon oxide was loaded inside the deposition chamber, and the temperature of the substrate was adjusted to 350°C. (C5H4(CH2CH2O(CH3)))In(CH3)2, manufactured in Example 1, was filled into a stainless steel foam container as an organometallic precursor, and the temperature was adjusted to 100°C.

[0214] Using nitrogen as the transport gas (100 sccm), the aforementioned organometallic precursor was injected into the deposition chamber for 3 seconds. A 5-second purification process was then performed using nitrogen (500 sccm) to remove any remaining organometallic precursor and reaction byproducts from the deposition chamber.

[0215] Ozone was injected for 3 seconds as a reactant gas to deposit an indium oxide film. Then, nitrogen gas (500 sccm) was used for 5 seconds to purge residual reactant gases and reaction byproducts.

[0216] The above process was repeated 1000 times as a single cycle to produce an indium-containing oxide film. XPS analysis of the indium-containing film revealed an indium content of 38.5% and an oxygen content of 59.1%, confirming the substantial formation of an indium oxide film.

[0217] Therefore, the indium compound according to an embodiment of the present invention exhibits a uniform and stable deposition rate when used to manufacture thin films by having further improved thermal stability, high volatility and increased vapor pressure, thus enabling the formation of thin films with high reliability, providing uniform film thickness for three-dimensional devices, and manufacturing thin films exhibiting excellent composition ratios of indium and oxygen.

[0218] As described above, the present invention has been illustrated by specific details and limited embodiments and comparative examples, but these are provided only to help to understand the invention more completely. The present invention is not limited to the embodiments described above, and various modifications and variations can be made based on such descriptions by those skilled in the art.

[0219] Therefore, the concept of the present invention is not limited to the illustrated embodiments. Not only the scope of protection claimed by the present invention, but also all forms that are equivalent to or have equivalent variations of the scope of protection claimed by the present invention are within the scope of the present invention.

Claims

1. An indium compound represented by the following chemical formula 1: Chemical Formula 1 In the chemical formula 1, L is a C1-C4 alkylene group. R1 to R4 are independently hydrogen or C1-C6 alkyl groups. R5 to R6 are independently C1-C6 alkyl groups. Y is -NR 11 R 12 , or -OR 13 , R 11 To R 13 Each is independently hydrogen or C1-C6 alkyl, or the R 11 and R 12 They connect to form a ring.

2. The indium compound according to claim 1, wherein, The indium compound is represented by the following chemical formula 2: Chemical formula 2 In the chemical formula 2, R1 to R4 are independently hydrogen or C1-C6 alkyl groups. R5 to R6 are independently C1-C6 alkyl groups. Y is -NR 11 R 12 、or -OR 13 , R 11 To R 13 Each is independently hydrogen or C1-C6 alkyl, or the R 11 and R 12 They connect to form alicyclic rings. m is an integer from 1 to 3.

3. The indium compound according to claim 1, wherein, The indium compound is selected from the following compounds: 。 4. A method for manufacturing an indium compound, comprising the step of manufacturing an indium compound of chemical formula 1, wherein the indium compound is manufactured by reacting compounds of chemical formulas 5 and 6 with a compound of chemical formula 4. Chemical Formula 1 Chemical Formula 4 Chemical formula 5 R5MgX 1 Chemical Formula 6 R6MgX 2 In the chemical formulas 1, 4, 5, and 6, L is a C1-C4 alkylene group. R1 to R4 are independently hydrogen or C1-C6 alkyl groups. R5 and R6 are independently C1-C6 alkyl groups. Y is -NR 11 R 12 、or -OR 13 , R 11 To R 13 Each is independently hydrogen or C1-C6 alkyl, or the R 11 and R 12 Connect to form a ring, X, X 1 and X 2 They are halogens, independent of each other.

5. The method for manufacturing the indium compound according to claim 4, wherein, The compound of chemical formula 4 is produced by reacting the compound of chemical formula 7 and the compound of chemical formula 8. Chemical Formula 7 Chemical Formula 8 InX3 In the chemical formulas 7 and 8, L is a C1-C4 alkylene group. R1 to R4 are independently hydrogen or C1-C6 alkyl groups. Y is -NR 11 R 12 、or -OR 13 , R 11 To R 13 Each is independently hydrogen or C1-C6 alkyl, or the R 11 and R 12 Connect to form a ring, X is a halogen.

6. A composition for indium-containing thin film deposition, comprising an indium compound selected from any one of claims 1 to 3.

7. A method for manufacturing an indium-containing thin film, comprising manufacturing a thin film using the indium compound of claim 1 or the indium-containing thin film deposition composition of claim 6.

8. The method for manufacturing an indium-containing thin film according to claim 7, wherein, The manufacturing method includes the following steps: a) The step of heating the substrate mounted in the cavity, and b) The step of manufacturing an indium-containing thin film by injecting a reactive gas and the indium-containing thin film deposition composition into the chamber.

9. The method for manufacturing an indium-containing thin film according to claim 8, wherein, The reacting gases are selected from oxygen (O2), ozone (O3), water vapor (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amines, carbon monoxide (CO), carbon dioxide (CO2), and C1 to C2 gases. 12 One or more of saturated or unsaturated hydrocarbons, hydrogen (H2), argon (Ar), silane, and helium (He).

10. The method for manufacturing an indium-containing thin film according to claim 9, wherein, The amine is a diamine.

11. The method for manufacturing an indium-containing thin film according to claim 7, wherein, The indium content of the film is 35% or more.

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