Novel composition, precursor composition containing the same, and method for manufacturing a 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 thin film deposition by vapor deposition, a precursor composition containing the novel composition, and a method for manufacturing a thin film using the precursor composition.

Background Art

[0002] With the progress of high integration and high miniaturization of semiconductor devices, it has become important to form metal and metal oxide thin films with a uniform thickness for application to various technologies such as microelectronics, magnetic information storage, and catalysts.

[0003] Chemical vapor deposition (CVD) or atomic layer deposition (ALD) is used to manufacture metal and metal oxide thin films. In particular, the atomic layer deposition method can form a desired thin film by sequentially injecting and removing reactants into the chamber, allows for easy adjustment of the composition, and can form a thin film with a uniform thickness. In addition, the atomic layer deposition method has the advantage of excellent step coverage and can grow a thin film uniformly on complex and delicate devices.

[0004] Precursors play an important role in manufacturing thin films by the atomic layer deposition method, and high volatility, high thermal stability, and high reactivity in the chamber are required. To date, the development of precursors has been promoted by applying various ligands. Representative ligands that are known include halogens, alkoxides, cyclopentadienes, beta-diketonates, amides, amidinates, and the like. 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. Therefore, the development of novel precursors with excellent properties that improve the above-mentioned disadvantages is required.

[0005] In particular, silicon dioxide (SiO2) has been used as the gate dielectric material for transistors until now. However, as semiconductor devices have become smaller in size recently, problems such as tunneling leakage current, resulting power dissipation, and heat generation have become serious. Therefore, the need to develop new materials with high dielectric constants to replace SiO2 dielectrics has emerged, and research on oxide semiconductors is actively progressing as a promising candidate.

[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 use in transparent TFTs (thin-film transistors). Furthermore, indium gallium oxide exhibits a resistance change of magnitude between an amorphous structure, which has high resistance, and a cubic structure, which has low resistance. Due to these characteristics, it is considered 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 Published Patent No. 2023-0074580 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The present invention aims to provide novel compositions applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD), and precursor compositions containing the same.

[0009] In particular, the objective is to provide a precursor composition that is liquid, has excellent thermal stability and volatility, possesses excellent ALD properties, contains almost no impurities, enables thin film deposition with excellent step coverage, and allows for uniform thin film deposition over a wide temperature range.

[0010] Furthermore, the present invention aims to provide a method for producing a thin film using the precursor composition described above.

[0011] However, the problems that this application seeks to solve are not limited to those mentioned above, and other problems not mentioned will be clearly understood by an ordinary engineer 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 aforementioned chemical formula 1, R1 and R2 are, independently, hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 10 , or NR 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 hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms. R 10 ~R 12 Each of these is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0015] [ka]

[0016] In the chemical formula 2, R 13 and R 14 are each independently hydrogen, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 22 , or NR 23 R 24 ; 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 precursor composition for vapor deposition containing the above composition.

[0018] Still another aspect of the present application provides a method for manufacturing a thin film including a step of introducing the above precursor composition for vapor deposition into a chamber. [Effect of the Invention]

[0019] The composition according to the present invention is a liquid, has excellent ALD characteristics, enables uniform thin film deposition, thereby having almost no impurities, and enables securing of a thin film having excellent step coverage characteristics.

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

[0021] Furthermore, thin films deposited using the composition of the present invention are expected to be used in the future as the active layer of oxide thin-film transistors (TFTs) in display devices, and can be used as channels or the like during the manufacturing of memory semiconductors. [Brief explanation of the drawing]

[0022] [Figure 1] Figure 1(a) is a graph showing the change in deposition rate due to a change in the injection time of the precursor in the production of the indium gallium oxide film of Production Example 1 of the present invention; Figure 1(b) is a graph showing the change in deposition rate due to a change in the injection time of the reaction gas in the production of the indium gallium oxide film of Production Example 2 of the present invention; and Figure 1(c) is a graph showing the change in deposition rate due to a change in the process temperature of the composition of the example of the present invention. [Figure 2] This graph shows the NMR measurement results of the compositions of the embodiments of this application. [Figure 3] This graph shows the results of thermogravimetric analysis (TGA) of the compositions of the embodiments of this application. [Figure 4] Figure 4(a) shows a graph and table of the analysis results obtained by high-resolution X-ray photoelectron spectroscopy (High-Resolution XPS) of a 20 nm thick indium gallium oxide film deposited at a process temperature of 280°C, and Figure 4(b) shows a graph and table of the results of measuring the XPS depth profile of a 20 nm thick indium gallium oxide film deposited at a process temperature of 280°C. [Figure 5] These graphs and tables show the results of X-ray diffraction (XRD) analysis of indium gallium oxide films deposited using the compositions of the examples of this application at process temperatures of 100°C and 280°C. [Figure 6]These graphs and tables show the results of X-ray reflectometry (XRR) analysis of indium gallium oxide films deposited using the compositions of the examples of this application at process temperatures of 100°C and 280°C. [Figure 7] Figure 7(a) is a transmission electron microscope (TEM) image of an indium gallium oxide film fabricated in a trench structure with an aspect ratio of 40:1, deposited at a process temperature of 280°C, and Figure 7(b) is an image showing the results of mapping the indium gallium oxide film by energy dispersive X-ray spectroscopy (EDS). [Modes for carrying out the invention]

[0023] The operation and effects of the invention will be described in more detail below through specific embodiments of the invention. However, these embodiments are presented merely as examples of the invention and do not define the scope of the invention's rights.

[0024] Prior to this, terms and words used in this specification and in the claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather in a manner consistent with the technical idea of ​​the present invention, in accordance with the principle that inventors may appropriately define the concepts of terms in order to best describe their invention.

[0025] Therefore, the configurations of the embodiments described herein represent only one of the most preferred embodiments of the present invention and do not represent the entire technical concept of the invention. It should be understood that, at the time of filing, there are various equivalents and modifications that can be substituted for these embodiments.

[0026] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “includes,” “equip,” or “have” are intended to specify the existence of an implemented feature, number, stage, component, or combination thereof, and should be understood not to preemptively exclude the possibility of the existence or addition of one or more other features, numbers, stages, components, or combinations thereof.

[0027] A composition according to one aspect of the present application may contain a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2.

[0028] [ka]

[0029] In the above chemical formula 1, R1 and R2 are, independently, hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 10 , or NR 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 hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms. R 10 ~R 12 Each of these is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0030] [ka]

[0031] In the aforementioned chemical formula 2, R 13 and R 14 Each is independently a hydrogen atom, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR22 , or NR 23 R 24 and; R 15 , R 20 and R 21 Each of these is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 16 ~R 19 Each of these is independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms. R 22 ~R 24 Each of these is independently a hydrogen atom 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 These are, independently, hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, OH group, OMe group, OEt group, 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 It may be any one selected from the group consisting of two Pr groups. The Me is methyl, the Et is ethyl, and the n Pr is n-propyl, and the above i Pr stands for iso-propyl.

[0033] R1, R2, R 13 , and R 14More preferably, each of these may be independently 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 It may be a methyl group.

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

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

[0037] More preferably, R3 and R 15 This is a tert-butyl group, and R8, R9, R 20 , and R 21 It may be a methyl group.

[0038] In one embodiment of the present application, preferably R4 to R7 and R 16 ~R 19 Each of these may independently be 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~R7 and R 16 ~R 19 More preferably, each of these may be independently 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 It may be hydrogen.

[0041] In one embodiment of the present application, preferably, R 10 ~R 12 and R 22 ~R 24 Each of these may independently be 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 this application, it may be difficult to form a thin film with the desired atomic ratio when the thin film is deposited.

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

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

[0047] A method for manufacturing a thin film according to one aspect of the present invention may include the step of introducing the vapor deposition precursor composition into a chamber.

[0048] In one embodiment of the present invention, the step of introducing the vapor deposition precursor composition into a chamber may include steps of physical adsorption, chemiadsorption, or both physical and chemiadsorption.

[0049] In one embodiment of the present invention, 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 manufacturing the thin film may preferably be 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. During one deposition cycle, a thin film of monolayer thickness or less grows through surface reactions, and ligands of the reactants adsorbed onto the substrate are removed by chemical reactions with other reactants supplied later. When heating the reactant precursor compositions for atomic layer deposition, a liquid state can be far more advantageous in terms of reaction rate and process than a solid state.

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

[0054] Specifically, oxide thin films can be deposited using one or more of the following as reaction gases: water vapor (H2O), hydrogen peroxide vapor (H2O2), oxygen (O2), a mixture of oxygen and hydrogen (O2+H2), and ozone (O3), but are not limited to these.

[0055] In one embodiment of the present application, if the method for manufacturing the thin film is atomic layer deposition (ALD), the method may include a first purging step of purging the precursor composition from the chamber before the step of injecting the reaction gas, and / or a second purging step of purging by-products that did not react with the precursor composition or were produced by reacting with it after the step of injecting the reaction gas.

[0056] The purging step assists in the movement of the precursor onto the substrate, ensures that the inside of the reactor has a pressure suitable for deposition, and releases impurities present in the reactor to the outside. In other words, an additional step may be performed to purge the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) before and after the supply of the reaction gas.

[0057] In one embodiment of the present invention, the method for manufacturing the thin film may have a process temperature of 50°C or higher and 500°C or lower.

[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. Preferably, the process temperature may be 100°C to 400°C.

[0059] If the process temperature falls below the range specified in this application, the reaction rate may be insufficient, resulting in a slow deposition rate and potentially improper deposition. If the process temperature exceeds the range specified in this application, the reaction rate may be excessively fast, leading to the generation of impurities or decomposition of precursors or reaction gases, resulting in improper deposition and difficulty in forming a thin film.

[0060] In one embodiment of the present invention, when the thin film manufacturing method of the present invention is used, which involves introducing the vapor deposition precursor composition into a chamber, a constant deposition rate (ALD window) can be observed between 100°C and 400°C, regardless of the process temperature.

[0061] For example, the ALD window may have a temperature range of 100°C to 370°C, 100°C to 340°C, 100°C to 310°C, or 100°C to 280°C.

[0062] In one embodiment of the present application, when a thin film is deposited by the thin film manufacturing 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, in a process temperature range of 100°C to 400°C, the thin film deposition rate by the thin film manufacturing method of the present invention 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 invention, the method for manufacturing the thin film may involve a canister temperature of 30°C or higher and 100°C or lower.

[0065] For example, the temperature of the canister 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, or 100°C. Preferably, the temperature of the canister may be 65°C.

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

[0067] When the canister temperature is below 30°C or above 100°C, the uniformity of the thickness of the thin film produced by the thin film manufacturing method described above may decrease significantly. This is because, below 30°C, the amount of precursor composition supplied to the chamber is insufficient, and above 100°C, it may be difficult to obtain a uniform film quality due to the decomposition of the precursor composition by thermal energy or an excessive supply of the precursor composition 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 amount of the precursor composition transport gas may be 10 sccm or more and 1000 sccm or less.

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

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

[0071] Specifically, if the injection time of the precursor composition is less than the range specified in this application, there may be insufficient reactants necessary for the formation of a thin film, resulting in the failure to form a thin film of appropriate thickness. Conversely, if the injection time of the precursor composition exceeds the range specified in this application, the composition ratio of the thin film produced may become inconsistent due to impurities from residual compounds after the reaction.

[0072] Furthermore, if the injection amount of the precursor composition transport gas falls below the range of this application, the residual amount of the precursor composition, which is a reactant, may increase, leading to an inappropriate reaction, and impurities may not be purged, resulting in the non-uniform deposition of the thin film layer.

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

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

[0075] Furthermore, the amount of 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 injection volume of the reaction gas is less than 50 sccm, the residual amount of the precursor composition, which is the reactant, may increase, leading to an improper reaction and the generation of impurities, resulting in the uneven deposition of the thin film layer. Conversely, if the injection volume of the reaction gas exceeds 3000 sccm, impurities due to the reaction gas compounds may be generated.

[0077] In one embodiment of the present application, the injection time of the purge gas may be 1 second or more and 1 minute or less, and the injection volume 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 2 seconds or more and 55 seconds or less, 3 seconds or more and 50 seconds or less, 4 seconds or more and 45 seconds or less, 5 seconds or more and 40 seconds or less, 6 seconds or more and 35 seconds or less, 7 seconds or more and 28 seconds or less, 8 seconds or more and 21 seconds or less, or 9 seconds or more and 15 seconds or less. The injection amounts of the purge gas are, independently, 100 sccm to 200 sccm, 100 sccm to 400 sccm, 100 sccm to 600 sccm, 100 sccm to 800 sccm, 100 sccm to 1000 sccm, 100 sccm to 1400 sccm, 100 sccm to 1800 sccm, 100 sccm to 2200 sccm, 100 sccm to 3600 sccm, 100 sccm to 3000 sccm, 100 sccm to 3300 sccm, 100 sccm to 3600 sccm, and 100 sccc. The dimensions may also be m to 3900 sccm or less, 200 sccm to 3500 sccm, 300 sccm to 3000 sccm, 400 sccm to 2500 sccm, 500 sccm to 2400 sccm, 600 sccm to 1300 sccm, 700 sccm to 2200 sccm, 800 sccm to 2100 sccm, 900 sccm to 2000 sccm, 1000 sccm to 1900 sccm, 1100 sccm to 1800 sccm, 1200 sccm to 1700 sccm, or 1300 sccm to 1600 sccm.

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

[0080] For example, the number of repetitions of the cycle may be 10 or more, 100 or more, 200 or more, 500 or more, 1,000 or more, 5,000 or more, 10,000 or more, 50,000 or more, or 100,000 or more but not exceeding 1,000,000.

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

[0082] A thin film according to one aspect of the present invention can be manufactured by the method for manufacturing the thin film 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, it may be 1.85 to 2.15 or 1.95 to 2.10.

[0084] In one embodiment of the present application, a thin film (In) was analyzed by X-ray photoelectron spectroscopy (XPS). x Ga y O z The atomic percentage ratio (x:y) of indium to gallium in the indium gallium oxide thin film may be 1:1 to 5:1. For example, the atomic percentage 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. In other words, the atomic percentage 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 invention, the indium (In) content of the thin film, as analyzed by X-ray photoelectron spectroscopy (XPS), may be 25 atomic% to 43 atomic%, the gallium (Ga) content may be 7 atomic% to 25 atomic%, and the oxygen (O) content may be 44 atomic% to 56 atomic%.

[0086] In one embodiment of the present invention, analysis of the thin film by X-ray diffraction (XRD) may reveal the appearance of a broad peak, (211) peak, (222) peak, (431) peak, (440) peak, or (622) peak.

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

[0088] In one embodiment of the present application, the density of the thin film, as analyzed by X-ray reflectometry (XRR), is 6.0 g / cm³. 3 This is also acceptable. For example, 6.1 g / cm³. 3 More than 6.15g / cm 3 Above, or 6.18 g / cm³ 3 The roughness of the thin film may be greater than or equal to 5 Å or less than or equal to 9.5 Å. For example, it may be greater than or equal to 5.6 Å or less than or equal to 9.2 Å, or greater than or equal to 6.2 Å or less than or equal to 8.9 Å. Depending on the surface properties and density of the thin film, it can have excellent interfacial properties and corrosion resistance.

[0089] The present invention will be described in more detail below through the examples. However, the following examples are for the purpose of further illustrating the present invention, and the scope of the present invention is not limited by the following examples.

[0090] [Example of combination] 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°C. Trichloroindium was slowly added to the solution and stirred for 30 minutes. Then, the temperature was gradually increased and the mixture was stirred at room temperature to obtain dimethylchloroindium (In(CH3)2Cl).

[0091] The synthesis method for dimethylchloroindium (In(CH3)2Cl) is as shown in Formula 1 below. Formula 1

[0092] TIFF0007897289000005.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°C. Trichlorogallium was slowly added to the solution and stirred for 30 minutes. Then, the temperature was gradually increased and the mixture was stirred at room temperature to obtain dimethylchlorogallium (Ga(CH3)2Cl). The synthesis method for dimethylchlorogallium (Ga(CH3)2Cl) is as shown in Equation 2 below. Equation 2

[0094] TIFF0007897289000006.tif24160

[0095] Synthesis Example 3: Synthesis of N-tartbutyl-N',N'-dimethylethane-1,2-diamine ligand A clear 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 20°C water bath, and tert-butylamine was slowly added. The mixture was then refluxed at 70°C for approximately 18 hours. After that, the flask was transferred to an ice bath to cool, and an aqueous NaOH solution was added, followed by stirring 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 clear liquid compound at room temperature. The synthesis method for N-tertbutyl-N',N'-dimethylethane-1,2-diamine is as shown in Formula 3 below. Formula 3

[0096] TIFF0007897289000007.tif27159

[0097] Synthesis example 4: In(CH 3 ) 2 [(CH 3 ) 2 NCH 2 CH 2 NtBu] Precursor Compound Synthesis After adding n-butyllithium (2.5 M in hexane) to a Schrenk flask, N-tartbutyl-N',N'-dimethylethane-1,2-diamine (Synthesis Example 3), diluted with pentane or hexane, was slowly added while the flask was cooled to -20°C. After the addition was complete, the flask temperature was gradually raised and the mixture was stirred at room temperature for 1 hour to prepare the solution. This solution was then slowly added to dimethylchloroindium (Synthesis Example 1), and the flask temperature was gradually raised and the mixture was stirred at room temperature for 18 hours. Subsequently, the solid in the solution was filtered, and the solvent was removed using vacuum to obtain a pale yellow liquid. The obtained liquid 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 clear liquid compound.

[0098] The synthesis method for the In(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound is as shown in Formula 4 below. Formula 4

[0099] TIFF0007897289000008.tif25160

[0100] The NMR measurement results for 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 NtBu] Precursor Compound Synthesis After adding n-butyllithium (2.5 M in hexane) to a Schrenk flask, N-tartbutyl-N',N'-dimethylethane-1,2-diamine (Synthesis Example 3), diluted with pentane or hexane, was slowly added while the flask was cooled to -20°C. After the addition was complete, the flask temperature was gradually raised and the mixture was stirred at room temperature for 1 hour to prepare the solution. This solution was then slowly added to dimethylchlorogallium (Synthesis Example 2), and the flask temperature was gradually raised and the mixture was stirred at room temperature for 18 hours. Subsequently, the solid in the solution was filtered, and the solvent was removed using vacuum to obtain a pale yellow liquid. The obtained liquid was then vacuum distilled to obtain the Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound from which impurities had been removed. The synthesized Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound is a clear liquid compound.

[0102] The synthesis method for the Ga(CH3)2[(CH3)2NCH2CH2NtBu] precursor compound is as shown in Formula 5 below. Formula 5

[0103] TIFF0007897289000009.tif19129

[0104] The NMR measurement results for 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] [Examples] Examples: Preparation of the composition The compositions of the examples were prepared 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] [Manufacturing example] Manufacturing Examples 1-3: Production 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 They 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 on the substrate was manufactured by a dry oxidation process.

[0108] The reaction gas is 200 g / m³ 3 Ozone (O3) at a concentration of 5 was used, which was generated from 1,000 sccm of oxygen gas. Argon (Ar), an inert gas, was used as a carrier for the precursor and for purging the precursor and reaction gases. The flow rate of carrier argon was 300 sccm, and the flow rate of purge argon was 1,500 sccm.

[0109] [Manufacturing Example 1] The following sequence was performed sequentially: (inject precursor for x seconds) - (inject purge gas for 10 seconds) - (inject reaction gas for 12 seconds) - (inject purge gas for 10 seconds). This constituted one cycle.

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

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

[0112] [Table 1]

[0113] Figure 1(a) shows the change in deposition rate due to changes in the precursor injection time during 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 remained constant after 10 seconds. This confirmed the self-limited reaction, a characteristic of atomic layer deposition (ALD).

[0115] Furthermore, 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 characteristic of atomic layer deposition (ALD).

[0116] [Manufacturing Example 2] The following steps were performed sequentially: (inject precursor for 10 seconds) - (inject purge gas for 10 seconds) - (inject reaction gas for y seconds) - (inject purge gas for 10 seconds), and this constituted one cycle.

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

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

[0119] [Table 2]

[0120] Figure 1(b) shows the change in deposition rate due to changes in the reaction gas injection time during 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, the deposition rate was maintained at 0.93 Å / cycle to 0.96 Å / cycle when the reaction gas injection time was 7 to 15 seconds, confirming the self-limited reaction, a characteristic of atomic layer deposition (ALD).

[0122] Furthermore, 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, a characteristic of atomic layer deposition (ALD).

[0123] [Manufacturing Example 3] The following steps were performed sequentially: (inject precursor for 10 seconds) - (inject purge gas for 10 seconds) - (inject reaction gas for 12 seconds) - (inject purge gas for 10 seconds), and this constituted one cycle.

[0124] In manufacturing example 3, the process temperature was set to 100°C to 400°C, and the number of cycles was set to 100, during which an indium gallium oxide film was deposited.

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

[0126] [Table 3]

[0127] Figure 1(c) shows the change in deposition rate due to changes in process temperature during the production of the indium gallium oxide film in Production Example 3.

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

[0129] We confirmed that the refractive index is maintained at 2.05 regardless of the process temperature.

[0130] [Example of evaluation] Evaluation Example 1: NMR Measurement Using Varian 400MHz, the composition of the example was analyzed. 1 1H NMR was measured. As shown in Figure 2, the NMR measurement results of the compositions in the examples confirmed that the ratio of the Methyl H peak δ-0.06 (s, 6H) of In to the Methyl H peak δ-0.16 (s, 6H) of Ga was 3:1, which is the same as the molar ratio of the compound in Synthesis Example 4 to the compound in Synthesis Example 5.

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

[0132] A 50 μL alumina crucible was used, with each sample being 10 mg in volume. The temperature was increased from 30°C to 500°C at a rate of 10°C / min for measurement.

[0133] The TGA measurement results for the compositions of the examples are shown in Figure 3.

[0134] Thermogravimetric analysis results, as shown in Figure 3, show that the half-life (T) of the composition of the example is 1 / 2The temperature (°C) was 161.9°C. Furthermore, it was confirmed that the residual amount of the example composition was 3.0 wt% at 200°C and 1.8 wt% at 300°C.

[0135] Evaluation Example 3: Compositional Analysis of Oxide Films 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 a 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 confirmed that the ratio of indium to gallium in the indium gallium oxide film deposited using the composition of the example was 3.2:1. Furthermore, oxygen-deficiency bonds accounted for 4.3%, oxygen-hydrogen bonds for 8.9%, while oxygen-metal (indium or gallium) bonds accounted for 86.8%. This confirmed that oxygen was mostly bonded to indium or gallium (O-Metal) rather than to oxygen-deficiency bonds (O-deficiency) or hydrogen bonds (OH).

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

[0139] In other words, it was confirmed that the ratio of indium and gallium atoms contained in the indium gallium oxide film produced by the ALD window was determined by the mixing ratio of the indium precursor compound (synthesis example 4) and the gallium precursor compound (synthesis example 5) in the composition. Furthermore, it was confirmed that the impurities (carbon, nitrogen, hydrogen, etc.) contained in the indium gallium oxide film were at negligible levels.

[0140] Evaluation Example 4: Crystalline and Density Analysis of Oxide Films The crystallinity and density of indium gallium oxide films deposited using the compositions of the examples were analyzed by X-ray diffraction (XRD) and X-ray reflectometry (XRR).

[0141] Figure 5 shows the XRD analysis results of 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, indicating that the microstructure of the oxide film was nanocrystalline, close to amorphous. At a process temperature of 280°C, several sharp peaks appeared, including (211), (222), (431), (440), and (622), indicating that the microstructure of the oxide film was polycrystalline. The polycrystalline oxide film was confirmed to be in the cubic Ia-3 space group by referring to ICDD card (00-006-0316).

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

[0144] As shown in Figure 6, the density of the oxide film deposited at a process temperature of 100°C is 6.18 g / cm³. 3and the density of the oxide film deposited at a process temperature of 280 °C was 6.88 g / cm 3 It was confirmed that it was. Also, the roughness of the oxide film deposited at a process temperature of 100 °C was 6.31 Å, and it was confirmed that 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 increased, the crystallinity of the thin film increased, the density also increased, and ultimately the density of the thin film increased.

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

[0147] Fig. 7(a) shows a TEM photograph of an indium gallium oxide film deposited at a process temperature of 280 °C and manufactured with a trench structure having 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] Fig. 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, and the ratio of indium and gallium atoms in the indium gallium oxide film in the ALD window matches the mixing ratio of the indium precursor compound and gallium precursor compound in the composition, confirming that there are almost no impurities in the thin film. Furthermore, it was confirmed that it has excellent step coverage even in a trench structure with an aspect ratio of 40:1.

[0152] Due to these excellent properties, thin films deposited using the composition of the present invention are expected to be used in the active layer of oxide thin-film transistors (TFTs) in display devices in the future, and can be used as channels or the like in the manufacturing of memory semiconductors.

[0153] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or altered forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be interpreted as being included within the scope of the present invention.

Claims

1. It comprises a first compound represented by the following chemical formula 1, and a second compound represented by the following chemical formula 2, The molar ratio of the first compound to the second compound is 1:1 to 5:

1. Composition: 【Chemistry 1】 In the aforementioned chemical formula 1, R 1 and R 2 is a methyl group; R 3 is a tert-butyl group; R 8 and R 9 is a methyl group; R 4 ~R 7 It is hydrogen. 【Chemistry 2】 In the aforementioned chemical formula 2, R 13 and R 14 is a methyl group; R 15 is a tert-butyl group; R 20 and R 21 is a methyl group; R 16 ~R 19 It is hydrogen.

2. A composition comprising the composition described in claim 1, Precursor composition for vapor deposition.

3. The step includes introducing the vapor deposition precursor composition described in claim 2 into a chamber, A method for manufacturing thin films.

4. The method for manufacturing the thin film according to claim 3, wherein the method for manufacturing the thin film includes atomic layer deposition (ALD) or chemical vapor deposition (CVD).

5. The method further includes the step of injecting a compound containing oxygen (O) atoms as a reaction 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 ) one or more of the following are selected. The method for manufacturing a thin film according to claim 3.

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