Novel composition, precursor composition including the same, and method of manufacturing thin film using the same

Abstract

To provide a precursor composition for vapor deposition capable of thin film deposition through vapor deposition.SOLUTION: The invention provides a novel composition applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD). The novel composition is excellent in reactivity, volatility and thermal stability, and comprises an indium-containing compound and a gallium-containing compound. Also provided are a precursor composition containing the novel composition, and a method of manufacturing a thin film using the precursor composition. The indium-containing compound is represented by the formula in the figure, and the gallium-containing compound has a structure obtained by replacing In by Ga in the formula.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a novel composition capable of being deposited as a thin film by vapor phase deposition, a precursor composition comprising the novel composition, and a method for producing a thin film using the precursor composition. [Background technology]

[0002] As semiconductor devices become more highly integrated and miniaturized, it is becoming increasingly important to form thin metal and metal oxide films of uniform thickness for use in a variety of technologies, such as microelectronics, magnetic information storage, and catalysis.

[0003] Chemical vapor deposition (CVD) or atomic layer deposition (ALD) are used to manufacture metal and metal oxide thin films, and ALD in particular is capable of forming the desired thin film by sequentially injecting and removing reactants into a chamber, making it easy to adjust the composition and forming a thin film of uniform thickness. ALD also has the advantage of excellent step coverage, allowing thin films to be grown uniformly on complex and sophisticated devices.

[0004] In order to manufacture a thin film by atomic layer deposition, a precursor plays an important role, and is required to have high volatility, high thermal stability, high reactivity in the chamber, etc. To date, precursors have been developed using various ligands, and representative ligands known include halogens, alkoxides, cyclopentadiene, betadiketonate, amides, amidinates, etc. However, most of the known precursors are solid compounds, have low volatility or stability, or may cause problems such as impurity contamination during thin film deposition, so there is a need to develop new precursors with excellent properties that overcome the above-mentioned shortcomings.

[0005] In particular, silicon dioxide (SiO2) has been used as the gate dielectric material for transistors up until now, but as the size of semiconductor elements has become smaller and smaller in recent years, problems such as tunneling leakage current and the resulting increased power dissipation and heat generation have become more serious. Therefore, there is an emerging need to develop new materials with high dielectric constants to replace SiO2 dielectrics, and research on oxide semiconductors as promising candidates is actively underway.

[0006] Indium gallium oxide (IGO) is a ternary n-type oxide semiconductor with good channel mobility and excellent light transmittance, making it very useful for transparent TFTs (thin film transistors). Indium gallium oxide also exhibits a quadratic change in resistance between an amorphous structure that exhibits high resistance and a cubic structure that exhibits low resistance. Due to these characteristics, IGO is considered to be a suitable material for Phase Change Memory (PCM) elements that can be driven with low power. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Republic of Korea Patent Publication No. 2023-0074580 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides a novel composition applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and a precursor composition including the same.

[0009] In particular, the present invention aims to provide a precursor composition that is liquid, has excellent thermal stability and volatility, has excellent ALD properties, is almost free of impurities, is capable of thin film deposition with excellent step coverage, and allows for uniform thin film deposition over a wide temperature range.

[0010] The present invention also provides a method for producing a thin film using the precursor composition.

[0011] However, the problems to be solved by the present application are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0012] One aspect of the present application provides a composition comprising a first compound represented by the following chemical formula 1, and a second compound represented by the following chemical formula 2:

[0013] [ka]

[0014] In the above Chemical Formula 1, R1 and R2 each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 10 , or N.R. 11 R 12 and; R3, R8 and R9 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R4 to R7 are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms; R 10 ~R 12 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0015] [ka]

[0016] In the above Chemical Formula 2, R 13 and R 14 each independently represents hydrogen or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; OR 22 , or N.R. 23 R 24 and; R 15 , R 20 and R 21 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 16 ~R 19 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms; R 22 ~R 24 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0017] Another aspect of the present application provides a vapor deposition precursor composition comprising the composition.

[0018] Yet another aspect of the present application provides a method for producing a thin film, comprising the step of introducing the vapor deposition precursor composition into a chamber. Effect of the Invention

[0019] The composition according to the present invention is liquid, has excellent ALD properties, and enables uniform thin film deposition, thereby ensuring thin films that are almost free of impurities and have excellent step coverage properties.

[0020] The above physical properties provide the precursor suitable for atomic layer deposition and chemical vapor deposition.

[0021] In addition, a thin film deposited using the composition of the present invention is expected to be used as an active layer of an oxide thin film transistor (TFT) in a display device in the future, and can be used as a channel in the manufacture of a memory semiconductor. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1(a) is a graph showing the change in deposition rate depending on the change in precursor injection time in the preparation of an indium gallium oxide film according to Preparation Example 1 of the present application, FIG. 1(b) is a graph showing the change in deposition rate depending on the change in reactant gas injection time in the preparation of an indium gallium oxide film according to Preparation Example 2 of the present application, and FIG. 1(c) is a graph showing the change in deposition rate depending on the change in process temperature of a composition of an example of the present application. [Diagram 2] 1 is a graph showing the results of NMR measurement of compositions according to examples of the present application. [Diagram 3] 1 is a graph showing the results of analysis of compositions of examples of the present application by thermogravimetric analysis (TGA). [Figure 4] FIG. 4(a) is a graph and a table showing the results of high-resolution X-ray photoelectron spectroscopy (High-Resolution XPS) analysis of a 20 nm thick indium gallium oxide film deposited at a process temperature of 280° C., and FIG. 4(b) is a graph and a table showing the results of measuring the XPS depth profile of the 20 nm thick indium gallium oxide film deposited at a process temperature of 280° C. [Diagram 5] 1 is a graph and a table showing the results of X-ray diffraction (XRD) analysis of indium gallium oxide films deposited using compositions of the examples of the present application at process temperatures of 100° C. and 280° C. [Figure 6]1 is a graph and a table showing the analysis results of an indium gallium oxide film deposited using a composition of an example of the present application at process temperatures of 100° C. and 280° C. by X-ray reflectometry (XRR). [Figure 7] FIG. 7(a) is a transmission electron microscope (TEM) image of an indium gallium oxide film deposited at a process temperature of 280°C and fabricated in a trench structure with an aspect ratio of 40:1, and FIG. 7(b) is an image showing the mapping results of the indium gallium oxide film by energy dispersive X-ray spectrometry (EDS). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The functions and effects of the present invention will be described in more detail below through specific examples of the present invention, however, these examples are presented as examples of the present invention and do not define the scope of the invention.

[0024] Prior to this, the terms and words used in this specification and claims should not be interpreted limited to their ordinary or dictionary meanings, but should be interpreted with meanings and concepts that correspond to the technical ideas of the present invention, in accordance with the principle that an inventor can appropriately define the concepts of terms in order to explain his / her invention in the best possible way.

[0025] Therefore, it should be understood that the configuration of the embodiment described in this specification is merely one of the most preferred embodiments of the present invention and does not fully represent the technical ideas of the present invention, and that there may be various equivalents and modifications that can replace them at the time of this application.

[0026] In this specification, the singular expression includes the plural expression unless the context clearly indicates otherwise. It should be understood that in this specification, the terms "comprise", "comprise", "have" and the like are intended to specify the presence of embodied features, numbers, steps, components, or combinations thereof, and do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0027] A composition according to one embodiment of the present application may include a first compound represented by Chemical Formula 1 below, and a second compound represented by Chemical Formula 2 below.

[0028] [ka]

[0029] In the above Chemical Formula 1, R1 and R2 each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 10 , or N.R. 11 R 12 and; R3, R8 and R9 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R4 to R7 are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms; R 10 ~R 12 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0030] [ka]

[0031] In the above Chemical Formula 2, R 13 and R 14 each independently represents hydrogen or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; OR22 , or N.R. 23 R 24 and; R 15 , R 20 and R 21 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 16 ~R 19 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms; R 22 ~R 24 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0032] In one embodiment of the present application, preferably, R1, R2, R 13 , and R 14 each independently represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an OH group, an OMe group, an OEt group, or an O n Pr group, O i Pr group, NH2 group, NHMe group, NHEt group, NH n Pr group, NH i Pr group, NMe2 group, NMeEt group, NMe n Pr group, NMe i Pr group, NEt2 group, NEt n Pr group, NEt i Pr group, N n 2 Pr groups, N n Pr i Pr group, and N i The Me is methyl, the Et is ethyl, and the Pr group may be any one selected from the group consisting of n Pr is n-propyl; i Pr is iso-propyl.

[0033] R1, R2, R 13 , and R 14More preferably, each may be independently any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group, but is not limited thereto.

[0034] More preferably, R1, R2, R 13 , and R 14 may be a methyl group.

[0035] In one embodiment of the present application, preferably, R3, R8, R9, R 15 , R 20 and R 21 may each independently be any one selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, sec-pentyl, tert-pentyl, hexyl, iso-hexyl, and isomers thereof.

[0036] R3, R8, R9, R 15 , R 20 and R 21 may more preferably be any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group, but is not limited thereto.

[0037] More preferably, R and R 15 is a tert-butyl group, and R, R, R 20 , and R 21 may be a methyl group.

[0038] In one embodiment of the present application, preferably, R4 to R7 and R 16 ~R 19 may each independently be any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.

[0039] R4 to R7 and R 16 ~R 19 More preferably, each may be independently any one selected from the group consisting of hydrogen, a methyl group, and an ethyl group, but is not limited thereto.

[0040] More preferably, R4 to R7 and R 16 ~R 19 may be hydrogen.

[0041] In one embodiment of the present application, preferably, R 10 ~R 12 and R 22 ~R 24 may each independently be any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.

[0042] In one embodiment of the present application, the molar ratio of the first compound to the second compound contained in the composition may be 1:1 to 5:1.

[0043] For example, the molar ratio of the first compound to the second compound may be 1:1 to 5:1, 1.5:1 to 4.5:1, 1.8:1 to 4.2:1, or 2:1 to 4:1.

[0044] If the molar ratio of the first compound to the second compound exceeds the range of the present application, it may be difficult to form a thin film having a desired atomic ratio when the thin film is vapor-deposited.

[0045] In one embodiment of the present application, the composition including the first compound and the second compound may be liquid at room temperature. In addition, the composition has a low melting point and is excellent in volatility at low temperatures.

[0046] A precursor composition for vapor phase deposition according to one embodiment of the present application may include any one of the above compositions.

[0047] A method for producing a thin film according to an embodiment of the present disclosure may include introducing the vapor deposition precursor composition into a chamber.

[0048] In one embodiment of the present application, the step of introducing the vapor deposition precursor composition into the chamber can include the steps of physisorption, chemisorption, or physisorption and chemisorption.

[0049] In one embodiment of the present application, the method for manufacturing the thin film may include both atomic layer deposition (ALD) and chemical vapor deposition (CVD).

[0050] More specifically, the deposition method may include Metal Organic Chemical Vapor Deposition (MOCVD), Low Pressure Chemical Vapor Deposition (LPCVD), Pulsed Chemical Vapor Deposition (P-CVD), Plasma Enhanced Atomic Layer Deposition (PE-ALD), or a combination thereof.

[0051] The method for producing the thin film is preferably atomic layer deposition, but is not limited thereto.

[0052] In atomic layer deposition (ALD), reactants must be highly volatile, stable, and highly reactive. ALD is a method in which reactants are supplied separately, and during one cycle of deposition, a monolayer or less thin film grows through a surface reaction, and the ligands of the reactants adsorbed on the substrate are removed by chemical reactions with other reactants supplied later. When reactant precursor compositions are heated for atomic layer deposition, liquid reactants can be much more advantageous in terms of reaction speed and process than solid reactants.

[0053] In one embodiment of the present application, the method for producing the thin film may further include the step of injecting a compound (or mixture) containing oxygen (O) atoms as a reactive gas.

[0054] Specifically, the oxide thin film can be deposited using one or more selected from water vapor (H2O), hydrogen peroxide vapor (H2O2), oxygen (O2), a mixture of oxygen and hydrogen (O2+H2), and ozone (O3) as a reactive gas, but is not limited thereto.

[0055] In one embodiment of the present application, when the method for producing the thin film is atomic layer deposition (ALD), the method may include a first purge step of purging the precursor composition from the chamber before the step of injecting the reaction gas, and / or a second purge step of purging by-products that do not react with the precursor composition or are generated by the reaction after the step of injecting the reaction gas.

[0056] The purging step assists the transfer of the precursor onto the substrate, ensures that the inside of the reactor has an appropriate pressure for deposition, and also discharges impurities present in the reactor to the outside. That is, before or after the supply of the reaction gas, a process of purging the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be additionally performed.

[0057] In one embodiment of the present application, the method for producing a thin film may have a process temperature of 50° C. or more and 500° C. or less.

[0058] For example, the process temperature may be 60° C. to 480° C., 70° C. to 460° C., 80° C. to 440° C., or 90° C. to 420° C. The process temperature may be preferably 100° C. to 400° C.

[0059] If the process temperature is below the range of the present application, the reaction rate may be insufficient, resulting in a slow deposition rate, which may result in poor deposition, whereas if the process temperature is above the range of the present application, the reaction rate may be too fast, resulting in the generation of impurities, or the precursor or reaction gas may be decomposed, which may result in poor deposition, making it difficult to form a thin film.

[0060] In one embodiment of the present disclosure, in the method of manufacturing a thin film, in which the vapor deposition precursor composition is introduced into a chamber, a period (ALD window) in which the deposition rate is constant regardless of the process temperature may appear at a temperature between 100° C. and 400° C.

[0061] For example, the ALD window may be 100° C. or more and 370° C. or less, 100° C. or more and 340° C. or less, 100° C. or more and 310° C. or less, or 100° C. or more and 280° C. or less.

[0062] In one embodiment of the present application, when a thin film is deposited by the method of the present application at a process temperature in the range of 100° C. to 400° C., the deposition rate may be 0.80 Å / cycle or more and 1.55 Å / cycle or less.

[0063] For example, the thin film deposition rate according to the thin film manufacturing method of the present application when the process temperature is in the range of 100° C. to 400° C. may be 0.85 Å / cycle to 1.50 Å / cycle, 0.90 Å / cycle to 1.46 Å / cycle, 0.91 Å / cycle to 1.02 Å / cycle, 0.93 Å / cycle to 0.96 Å / cycle, 0.94 Å / cycle to 1.01 Å / cycle, 0.90 Å / cycle to 0.95 Å / cycle, 0.82 Å / cycle to 0.99 Å / cycle, or 1.06 Å / cycle to 1.46 Å / cycle.

[0064] In one embodiment of the present application, in the method for producing a thin film, a temperature of a canister may be 30° C. or higher and 100° C. or lower.

[0065] For example, the canister temperature may be 35° C. to 95° C., 40° C. to 90° C., 45° C. to 85° C., 50° C. to 80° C., 55° C. to 75° C., 60° C. to 70° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C. The canister temperature may preferably be 65° C.

[0066] The canister is used to supply a source gas into a chamber for a reaction in a thin film manufacturing method. Typically, the canister vaporizes a precursor composition to generate a source gas, and then supplies the source gas into the chamber.

[0067] When the canister temperature is less than 30° C. or more than 100° C., the thickness uniformity of the thin film produced by the method for producing a thin film may be significantly reduced. This is because, when the canister temperature is less than 30° C., the amount of the precursor composition supplied to the chamber is insufficient, and when the canister temperature is more than 100° C., it may be difficult to obtain a uniform film quality due to decomposition of the precursor composition by thermal energy or an excessive amount of the precursor composition supplied to the chamber.

[0068] In one embodiment of the present application, the injection time of the precursor composition may be 1 second or more and 30 seconds or less, and the injection rate of the precursor composition carrying gas may be 10 sccm or more and 1000 sccm or less.

[0069] For example, the injection time of the precursor composition may be from 1 to 27 seconds, from 2 to 24 seconds, from 3 to 21 seconds, from 4 to 18 seconds, or from 5 to 15 seconds; The amount of purge gas injected in the first purge step may be 20 sccm or more and 800 sccm or less, 40 sccm or more and 700 sccm or less, 60 sccm or more and 600 sccm or less, 80 sccm or more and 500 sccm or less, 100 sccm or more and 450 sccm or less, 150 sccm or more and 400 sccm or less, or 250 sccm or more and 350 sccm or less.

[0070] If the process is carried out above or below the above range, it may be difficult to form a suitable thin film.

[0071] Specifically, when the injection time of the precursor composition is below the range of the present application, the reactants required for forming the thin film may be insufficient, and the thin film may not have an appropriate thickness. On the other hand, when the injection time of the precursor composition is above the range of the present application, the composition ratio of the thin film may not be constant due to impurities caused by residual compounds after the reaction.

[0072] In addition, if the amount of the precursor composition carrying gas injected is below the range of the present application, the amount of residual precursor composition reactants increases, which may cause inappropriate reactions, and impurities may not be purged, resulting in non-uniform deposition of the thin film layer.

[0073] In one embodiment of the present application, an injection time of the reaction gas may be 1 second or more and 30 seconds or less, and an injection amount of the reaction gas may be 50 sccm or more and 3000 sccm or less.

[0074] For example, the reaction gas injection time may be 2 to 27 seconds, 3 to 24 seconds, 4 to 21 seconds, 5 to 19 seconds, 6 to 17 seconds, or 7 to 15 seconds.

[0075] The amount of the reaction gas injected may be, for example, 100 sccm to 2500 sccm, 300 sccm to 2000 sccm, 500 sccm to 1500 sccm, 700 sccm to 1300 sccm, or 900 sccm to 1100 sccm.

[0076] Furthermore, if the amount of the reactant gas injected is less than 50 sccm, the amount of residual reactant precursor composition increases, which may cause inappropriate reactions and impurities may be generated, resulting in non-uniform deposition of the thin film layer, whereas if the amount of the reactant gas injected is more than 3000 sccm, impurities due to the reactant gas compound may be generated.

[0077] In one embodiment of the present application, an injection time of the purge gas may be 1 second or more and 1 minute or less, and an injection amount of the purge gas may be 100 sccm or more and 4000 sccm or less.

[0078] For example, the injection time of the purge gas in the first purge step may be from 2 to 55 seconds, from 3 to 50 seconds, from 4 to 45 seconds, from 5 to 40 seconds, from 6 to 35 seconds, from 7 to 28 seconds, from 8 to 21 seconds, or from 9 to 15 seconds. The injection amounts of the purge gas are each independently 100 sccm or more and 200 sccm or less, 100 sccm or more and 400 sccm or less, 100 sccm or more and 600 sccm or less, 100 sccm or more and 800 sccm or less, 100 sccm or more and 1000 sccm or less, 100 sccm or more and 1400 sccm or more and 100 sccm or more and 1800 sccm or more and 100 sccm or more and 2200 sccm or less, 100 sccm or more and 3600 sccm or less, 100 sccm or more and 3000 sccm or more and 100 sccm or more and 3300 sccm or less, 100 sccm or more and 3600 sccm or less, 100 sccm or more and ... m or more and 3900 sccm or less, 200 sccm or more and 3500 sccm or less, 300 sccm or more and 3000 sccm or less, 400 sccm or more and 2500 sccm or less, 500 sccm or more and 2400 sccm or less, 600 sccm or more and 1300 sccm or less, 700 sccm or more and 2200 sccm or less, 800 sccm or more and 2100 sccm or less, 900 sccm or more and 2000 sccm or less, 1000 sccm or more and 1900 sccm or less, 1100 sccm or more and 1800 sccm or less, 1200 sccm or more and 1700 sccm or less, or 1300 sccm or more and 1600 sccm or less.

[0079] In one embodiment of the present application, the cycle may be repeated 10 or more times.

[0080] For example, the cycle may be repeated 10 times or more, 100 times or more, 200 times or more, 500 times or more, 1,000 times or more, 5,000 times or more, 10,000 times or more, 50,000 times or more, or 100,000 times or more and 1,000,000 times or less.

[0081] If the above-mentioned process conditions for the reaction gas, process temperature, precursor composition and purge gas are not satisfied, a thin film with excellent properties cannot be obtained.

[0082] The thin film according to one aspect of the present application can be produced by the thin film production method described above.

[0083] In one embodiment of the present application, the refractive index (RI) of the thin film may be 1.75 to 2.20, for example, 1.85 to 2.15, or 1.95 to 2.10.

[0084] In one embodiment of the present application, the thin film (In x Ga y O z ) may have an atomic % ratio (x:y) of indium to gallium of 1:1 to 5:1. For example, the atomic % ratio of indium to gallium may be 1:1 to 5:1, 1.5:1 to 4.5:1, 1.8:1 to 4.2:1, or 2:1 to 4:1. That is, the atomic % ratio of indium to gallium in the indium gallium oxide thin film may be the same as the molar ratio of the first compound to the second compound.

[0085] In one embodiment of the present application, the indium (In) content of the thin film, as analyzed by X-ray photoelectron spectroscopy (XPS), may be 25 atomic % or more and 43 atomic % or less, the gallium (Ga) content may be 7 atomic % or more and 25 atomic % or less, and the oxygen (O) content may be 44 atomic % or more and 56 atomic % or less.

[0086] In one embodiment of the present application, when the thin film is analyzed by X-ray diffractometry (XRD), a broad peak, a (211) peak, a (222) peak, a (431) peak, a (440) peak, or a (622) peak may appear.

[0087] In one embodiment of the present application, the phase of the thin film analyzed by X-Ray Diffractometry (XRD) may be nanocrystalline or polycrystalline.

[0088] In one embodiment of the present application, the density of the thin film analyzed by X-ray reflectometry (XRR) is 6.0 g / cm 3 For example, 6.1 g / cm 3 More than 6.15g / cm 3 or more than 6.18g / cm 3 The thin film may have a roughness of 5 Å to 9.5 Å, for example, 5.6 Å to 9.2 Å, or 6.2 Å to 8.9 Å. The thin film may have excellent interface properties and corrosion resistance due to its surface properties and density.

[0089] The present invention will be described in more detail with reference to the following examples. However, the following examples are provided to further explain the present invention, and the scope of the present invention is not limited to the following examples.

[0090] [Synthesis example] Synthesis Example 1: Dimethylchloroindium (In(CH 3 ) 2 Synthesis of Cl) Trimethyl indium and pentane were placed in a Schrenk flask and cooled to -20℃. Trichloro indium was slowly added to the solution and stirred for 30 minutes. The temperature was then gradually increased and the mixture was stirred at room temperature to obtain dimethylchloroindium (In(CH3)2Cl).

[0091] The synthesis method of dimethylchloroindium (In(CH3)2Cl) is as shown in the following formula 1. Formula 1

[0092] TIFF2025031626000006.tif22160

[0093] Synthesis Example 2: Dimethylchlorogallium (Ga(CH 3 ) 2 Synthesis of Cl) Trimethyl gallium and pentane were placed in a Schrenk flask and cooled to -20℃. Trichloro gallium was slowly added to the solution and stirred for 30 minutes. The temperature was then gradually raised and the mixture was stirred at room temperature to obtain dimethylchlorogallium (Ga(CH3)2Cl). The synthesis method of dimethylchlorogallium (Ga(CH3)2Cl) is as shown in the following formula 2. Formula 2

[0094] TIFF2025031626000007.tif24160

[0095] Synthesis Example 3: Synthesis of N-tert-butyl-N',N'-dimethylethane-1,2-diamine ligand A transparent aqueous solution was prepared by adding 2-chloro-N,N-dimethylethylamine and water (H2O) to a flask and stirring. The flask was placed in a water bath at 20°C, and tert-butylamine was slowly added, followed by reflux stirring at 70°C for about 18 hours. The flask was then transferred to an ice bath to cool, and an aqueous NaOH solution was added and stirred for 10 minutes. After stirring, the compound was extracted using hexane, and the solvent was removed under reduced pressure to obtain N-tertbutyl-N',N'-dimethylethane-1,2-diamine. The synthesized N-tertbutyl-N',N'-dimethylethane-1,2-diamine is a transparent liquid compound at room temperature. The synthesis method of N-tertbutyl-N',N'-dimethylethane-1,2-diamine is as shown in the following formula 3.

[0096] TIFF2025031626000008.tif27159

[0097] Synthesis example 4: In(CH 3 ) 2 [(CH 3 ) 2 NCH 2 CH 2 Synthesis of NtBu] precursor compound After placing n-butyl lithium (2.5M in hexane) in a Schrenk flask, it was cooled to -20℃ and N-tert-butyl-N',N'-dimethylethane-1,2-diamine (Synthesis Example 3) diluted with pentane or hexane was slowly added. After the addition, the temperature of the flask was gradually increased and the solution was stirred at room temperature for 1 hour. The solution was slowly added to dimethylchloroindium (Synthesis Example 1), and the temperature of the flask was gradually increased and the solution was stirred at room temperature for 18 hours. Then, the solids in the solution were filtered and the solvent was removed using a vacuum to obtain a pale yellow liquid, which was then vacuum distilled to obtain the In(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound from which impurities had been removed. The synthesized In(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound is a transparent liquid compound.

[0098] The synthesis method of the precursor compound In(CH3)2[(CH3)2NCH2CH2NtBu] is shown in the following formula 4. Formula 4

[0099] TIFF2025031626000009.tif25160

[0100] The NMR measurement results of the synthesized In(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound are as follows. 1 H-NMR (C6D6): δ -0.06(s, 6H), 1.32(s, 9H), 1.65(s,6H), 2.19(t, 2H), 3.00(t, 2H)

[0101] Synthesis Example 5: Ga(CH 3 ) 2 [(CH 3 ) 2 NCH 2 CH 2 Synthesis of NtBu] precursor compound After placing n-butyl lithium (2.5M in hexane) in a Schrenk flask, it was cooled to -20℃ and N-tert-butyl-N',N'-dimethylethane-1,2-diamine (Synthesis Example 3) was diluted with pentane or hexane and slowly added. After the addition, the temperature of the flask was gradually increased and the solution was stirred at room temperature for 1 hour. The solution was slowly added to dimethylchlorogallium (Synthesis Example 2), and the temperature of the flask was gradually increased and the solution was stirred at room temperature for 18 hours. Then, the solids in the solution were filtered and the solvent was removed using a vacuum to obtain a pale yellow liquid, which was then vacuum distilled to obtain a Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound with impurities removed. The synthesized Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound is a transparent liquid compound.

[0102] The synthesis method of the Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound is shown in the following formula 5. Formula 5

[0103] TIFF2025031626000010.tif19129

[0104] The NMR measurement results of the synthesized Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound are as follows. 1 H-NMR (C6D6): δ -0.16(s, 6H), 1.33(s, 9H), 1.66(s,6H), 2.17(t, 2H), 2.90(t, 2H)

[0105] [Example] Example: Preparation of the composition The composition of the example was produced by mixing the In(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound (Synthesis Example 4) and the Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound (Synthesis Example 5) in a molar ratio of 3:1.

[0106] [Production Example] Manufacturing Examples 1-3: Manufacturing of indium gallium oxide films using atomic layer deposition (ALD) Using the composition of the example (In(CH3)2[(CH3)2NCH2CH2NtBu]:Ga(CH3)2[(CH3)2NCH2CH2NtBu] = 3:1), an indium gallium thin film (In x Ga y O z ) was manufactured.

[0107] The substrate used in this experiment was a boron-doped p-type silicon wafer with a 100 nm thick silicon oxide film deposited on its surface. The silicon oxide film of the substrate was fabricated by a dry oxidation process.

[0108] Reactive gas: 200g / m 3 Ozone (O3) with a concentration of 1000 sccm was used, which was generated from oxygen gas at 1,000 sccm. Inert gas argon (Ar) was used to carry the precursor and to purge the precursor and reaction gases, with the flow rate of carrier argon being 300 sccm and the flow rate of purge argon being 1,500 sccm.

[0109] [Production Example 1] (Injection of precursor for x seconds)-(Injection of purge gas for 10 seconds)-(Injection of reaction gas for 12 seconds)-(Injection of purge gas for 10 seconds) were carried out in this order, which constituted one cycle.

[0110] In the supply of the indium gallium mixed precursor composition of Preparation Example 1, the x seconds was set to 5 to 15 seconds, the process temperature was set to 100° C. or 280° C., and the number of cycles was set to 100 to deposit an indium gallium oxide film.

[0111] Specific process conditions are shown in Table 1 below.

[0112] [Table 1]

[0113] FIG. 1(a) shows the change in deposition rate depending on the change in precursor injection time in the production of the indium gallium oxide film in Production Example 1.

[0114] As shown in Figure 1(a), at a process temperature of 100°C, the deposition rate increased from 0.90 Å / cycle to 0.95 Å / cycle as the precursor injection time increased from 5 seconds to 10 seconds, and the deposition rate remained constant after 10 seconds, confirming the self-limited reaction that is a characteristic of atomic layer deposition (ALD).

[0115] In addition, as shown in Figure 1(a), at a process temperature of 280°C, when the precursor injection time was 5 to 7 seconds, the deposition rate was maintained at 0.91 Å / cycle to 1.02 Å / cycle, confirming the self-limited reaction that is a characteristic of atomic layer deposition (ALD).

[0116] [Production Example 2] The following sequence was carried out: (injection of precursor for 10 seconds)-(injection of purge gas for 10 seconds)-(injection of reaction gas for y seconds)-(injection of purge gas for 10 seconds), which constituted one cycle.

[0117] In the supply of the reaction gas in Production Example 2, the y seconds was set to 7 to 15 seconds, the process temperature was set to 100° C. or 280° C., and the number of cycles was set to 100 to deposit the indium gallium oxide film.

[0118] Specific process conditions are shown in Table 2 below.

[0119] [Table 2]

[0120] FIG. 1(b) shows the change in deposition rate according to the change in reaction gas injection time in the production of the indium gallium oxide film in Production Example 2.

[0121] As shown in Figure 1(b), at a process temperature of 100°C, when the reaction gas injection time was 7 to 15 seconds, the deposition rate was maintained at 0.93 Å / cycle to 0.96 Å / cycle, confirming the self-limited reaction that is a characteristic of atomic layer deposition (ALD).

[0122] In addition, as shown in Figure 1(b), at a process temperature of 280°C, the deposition rate was maintained at 0.94 Å / cycle to 1.01 Å / cycle when the reaction gas injection time was 7 to 15 seconds, confirming the self-limited reaction that is a characteristic of atomic layer deposition (ALD).

[0123] [Production Example 3] The following sequence was performed: (injection of precursor for 10 seconds)-(injection of purge gas for 10 seconds)-(injection of reaction gas for 12 seconds)-(injection of purge gas for 10 seconds), which constituted one cycle.

[0124] In Production Example 3, the process temperature was 100° C. to 400° C., and the number of cycles was 100 to deposit an indium gallium oxide film.

[0125] The specific process conditions are shown in Table 3 below.

[0126] [Table 3]

[0127] The change in deposition rate according to the change in process temperature in the production of the indium gallium oxide film of Production Example 3 is shown in FIG. 1(c).

[0128] As shown in Figure 1(c), the deposition rate was maintained constant at 0.82 Å / cycle to 0.99 Å / cycle at process temperatures of 100°C to 280°C, confirming that the ALD window (a region in which the deposition rate is constant regardless of the process temperature) when using the composition of the example is 100°C to 280°C. As the process temperature increased from 310°C to 400°C, the deposition rate increased significantly from 1.06 Å / cycle to 1.46 Å / cycle.

[0129] It was confirmed that the refractive index remained at 2.05 regardless of the process temperature.

[0130] [Evaluation example] Evaluation example 1: NMR measurement Using a Varian 400MHz, the composition of the example 1 H NMR was measured. As shown in FIG. 2, the NMR measurement results of the composition of the example confirmed that the ratio of In's methyl H peak δ-0.06 (s, 6H) to Ga's methyl H peak δ-0.16 (s, 6H) was 3:1, which was the same as the molar ratio between the compound of Synthesis Example 4 and the compound of Synthesis Example 5.

[0131] Evaluation example 2: Thermogravimetric analysis (TGA) Thermogravimetric analysis of the example compositions was carried out using a Netzsch TG209 F1 Libra instrument.

[0132] An alumina crucible with a capacity of 50 μL was used, and the amount of each sample was 10 mg. The temperature was increased from 30° C. to 500° C. at a rate of 10° C. / min. for measurement.

[0133] The results of TGA measurement of the composition of the example are shown in FIG.

[0134] As a result of the thermogravimetric analysis, as shown in FIG. 3, the half-life (T 1 / 2, °C) was 161.9°C. It was also confirmed that the residual amount of the composition of the example at 200°C was 3.0 wt%, and the residual amount at 300°C was 1.8 wt%.

[0135] Evaluation example 3: Composition analysis of oxide film The composition and impurity content of the indium gallium oxide film deposited using the composition of the example were analyzed by X-ray Photoelectron Spectroscopy (XPS).

[0136] Figure 4 shows the measurement results of high-resolution XPS (Figure 4(a)) and XPS depth profile (Figure 4(b)) of the 20 nm thick indium gallium oxide film deposited at a process temperature of 280°C.

[0137] As shown in Figure 4(a), the high-resolution XPS scan results confirmed that the indium to gallium ratio of the indium gallium oxide film deposited using the composition of the embodiment was 3.2:1. In addition, the oxygen-deficiency bond was 4.3%, the oxygen-hydrogen bond was 8.9%, and the oxygen-metal (indium or gallium) bond was 86.8%, confirming that oxygen is mostly bonded to indium or gallium (O-Metal) rather than oxygen deficiency bond (O-deficiency) or bonded to hydrogen (OH).

[0138] As shown in Figure 4(b), the XPS depth profile measurement results showed that indium (In) was 33.9 atomic %, gallium (Ga) was 10.5 atomic %, and oxygen (O) was 55.6 atomic %, while no impurities such as carbon, nitrogen, or hydrogen were detected, and the oxygen to metal ratio was 1.25.

[0139] That is, it was confirmed that the ratio of indium and gallium atoms contained in the indium gallium oxide film manufactured by the ALD window depends on the mixing ratio of the indium precursor compound (Synthesis Example 4) and the gallium precursor compound (Synthesis Example 5) in the composition. It was also confirmed that the impurities (carbon, nitrogen, hydrogen, etc.) contained in the indium gallium oxide film were at a negligible level.

[0140] Evaluation example 4: Crystallinity and density analysis of oxide film The crystallinity and density of the indium gallium oxide film deposited using the composition of the examples were analyzed by X-ray diffractometry (XRD) and X-ray reflectometry (XRR).

[0141] FIG. 5 shows the XRD analysis results of the indium gallium oxide films deposited using the composition of the example at process temperatures of 100° C. and 280° C.

[0142] At a process temperature of 100°C, a broad peak appeared, proving that the oxide film had a nanocrystalline structure close to amorphous. At a process temperature of 280°C, several sharp peaks appeared, including the (211) peak, (222) peak, (431) peak, (440) peak, and (622) peak, proving that the oxide film had a polycrystalline structure. The polycrystalline oxide film was confirmed to be in the Ia-3 space group of the cubic crystal system by referring to the ICDD card (00-006-0316).

[0143] FIG. 6 shows the XRR analysis results of the indium gallium oxide films deposited using the composition of the example at process temperatures of 100° C. and 280° C.

[0144] As shown in FIG. 6, the density of the oxide film deposited at a process temperature of 100°C is 6.18g / cm 3The density of the oxide film deposited at a process temperature of 280°C is 6.88g / cm 3 In addition, the roughness of the oxide film deposited at a process temperature of 100°C was 6.31 Å, and the roughness of the oxide film deposited at a process temperature of 280°C was 8.85 Å.

[0145] That is, it was confirmed that as the process temperature increases, the crystallinity of the thin film increases, the density also increases, and ultimately the density of the thin film increases.

[0146] Evaluation example 5: Analysis of step coverage of oxide film The step coverage of the indium gallium oxide film deposited using the composition of the examples was analyzed by observation with a transmission electron microscope (TEM) and energy dispersive X-ray spectrometry (EDS).

[0147] FIG. 7(a) shows a TEM image of an indium gallium oxide film deposited at a process temperature of 280° C. and fabricated in a trench structure with an aspect ratio of 40:1.

[0148] As shown in FIG. 7(a), it was confirmed that the indium gallium oxide film deposited using the composition of the example had excellent step coverage.

[0149] Figure 7(b) shows the results of EDS mapping of the indium gallium oxide film.

[0150] As shown in FIG. 7(b), it was confirmed that indium and gallium atoms were uniformly distributed in the indium gallium oxide film deposited using the composition of the example.

[0151] As described above, the composition of the present invention has excellent ALD properties, the ratio of indium and gallium atoms in the indium gallium oxide film in the ALD window is consistent with the mixing ratio of the indium precursor compound and the gallium precursor compound in the composition, and it was confirmed that there are almost no impurities in the thin film. It was also confirmed that the composition has excellent step coverage even in a trench structure having an aspect ratio of 40:1.

[0152] Due to such excellent properties, a thin film deposited using the composition of the present invention is expected to be used as an active layer of oxide thin film transistors (TFTs) in display devices in the future, and can be used as a channel in the manufacture of memory semiconductors.

[0153] The scope of the present invention is indicated by the claims set forth below rather than by the above detailed description, and all modifications and variations that fall within the meaning and scope of the claims and their equivalent concepts should be interpreted as being included within the scope of the present invention.

Claims

1. The present invention includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2: Composition: 【Chemistry 1】 In the above Chemical Formula 1, R 1 and R 2 each independently represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 10 , or N.R. 11 R 12 and R 3 , R 8 and R 9 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 4 ~R 7 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms; R 10 ~R 12 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms. 【Chemistry 2】 In the above Chemical Formula 2, R 13 and R 14 each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; OR 22 , or N.R. 23 R 24 and R 15 , R 20 and R 21 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 16 ~R 19 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms; R 22 ~R 24 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

2. R 1 , R 2 , R 13 , and R 14 each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an OH group, an OMe group, an OEt group, an O n Pr group, O i Pr group, NH 2 group, NHMe group, NHEt group, NH n Pr group, NH i Pr group, NMe 2 group, NMeEt group, NMe n Pr group, NMe i Pr group, NEt 2 Group, NEt n Pr group, NEt i Pr group, N n P 2 Base, N n P i Pr group, and N i P 2 any one selected from the group consisting of groups The composition of claim 1. (Me is methyl, Et is ethyl, n Pr is n-propyl; i Pr is iso-propyl.

3. R 3 , R 8 , R 9 , R 15 , R 20 and R 21 each independently represents any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neo-pentyl group, a sec-pentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, and isomers thereof; The composition of claim 1.

4. R 4 ~R 7 and R 16 ~R 19 are each independently any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group; The composition of claim 1.

5. R 10 ~R 12 and R 22 ~R 24 are each independently any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group; The composition of claim 1.

6. the molar ratio of the first compound to the second compound is 1:1 to 5:1; The composition of claim 1.

7. The composition according to any one of claims 1 to 6, Precursor compositions for vapor phase deposition.

8. 8. The method of claim 7, further comprising the step of: introducing the vapor deposition precursor composition of claim 7 into a chamber; Methods for producing thin films.

9. The method of claim 8, wherein the method comprises atomic layer deposition (ALD) or chemical vapor deposition (CVD).

10. The method further includes the step of injecting a compound containing oxygen (O) atoms as a reactive gas; The reaction gas is water vapor (H 2 O), hydrogen peroxide vapor (H 2 O 2 ), oxygen (O 2 ), a mixture of oxygen and hydrogen (O 2 +H 2 ) and ozone (O 3 ) Any one or more selected from the following: The method for producing a thin film according to claim 8 .

11. Produced by the method for producing a thin film according to claim 8. Thin film.

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