Novel compound, precursor composition comprising same, and method for manufacturing thin film using same

Abstract

The present invention relates to a precursor composition for vapor deposition capable of depositing a thin film through vapor deposition and, specifically, to: a novel compound that can be applied to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and has excellent reactivity, volatility, and thermal stability; a precursor composition comprising the novel compound; and a method for manufacturing a thin film using the precursor composition.

Description

Novel composition, precursor composition comprising same, and method for producing thin film using same

[0001] The present invention relates to a novel composition capable of forming a thin film through vapor deposition, a precursor composition comprising the novel composition, and a method for manufacturing a thin film using the precursor composition.

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

[0003] Chemical vapor deposition (CVD) or atomic layer deposition (ALD) are used to manufacture metal and metal oxide thin films. ALD, in particular, enables the formation of desired thin films by sequentially injecting and removing reactants into a chamber, allowing for easy composition control and the formation of films with uniform thickness. Furthermore, ALD offers excellent step coverage, allowing for the uniform growth of thin films on complex and sophisticated devices.

[0004] Precursors play a crucial role in the manufacture of thin films using atomic layer deposition (ALD), requiring high volatility, high thermal stability, and high reactivity within the chamber. To date, precursor development has been conducted using a variety of ligands, with representative ligands known to exist including halogens, alkoxides, cyclopentadienes, beta-diketonates, amides, and amidinates. However, most known precursors are solid compounds, have low volatility or stability, or can cause problems such as impurity contamination during thin film deposition. Therefore, there is a need to develop novel precursors with superior properties that overcome the aforementioned shortcomings.

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

[0006] Indium gallium oxide (IGO) is a ternary n-type oxide semiconductor, and it has excellent channel mobility and light transmittance, making it very useful for transparent thin film transistors (TFTs). In addition, IGO exhibits a two-order of magnitude change in resistance between an amorphous structure with high resistance and a cubic structure with low resistance. Due to these characteristics, IGO is considered a suitable material for phase change memory (PCM) devices that can be operated at low power.

[0007] [Prior Art Literature]

[0008] [Patent Document]

[0009] (Patent Document 1) Republic of Korea Publication No. 10-2023-0074580

[0010] The present invention aims to provide a novel composition applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and a precursor composition including the same.

[0011] In particular, the purpose is to provide a precursor composition that is liquid, has excellent thermal stability and volatility, excellent ALD characteristics, has almost no impurities, enables thin film deposition with excellent step coverage, and enables uniform thin film deposition over a wide temperature range.

[0012] In addition, the present invention seeks to provide a method for manufacturing a thin film using the precursor composition.

[0013] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0014] One aspect of the present invention 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:

[0015]

[0016] [Chemical Formula 1]

[0017]

[0018]

[0019] In the above chemical formula 1,

[0020] R1 and R2 are each independently hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR9, or NR 10 R 11 And,

[0021] R3 and R8 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms,

[0022] R4 to R7 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms,

[0023] R9 to R 11 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0024]

[0025] [Chemical Formula 2]

[0026]

[0027]

[0028]

[0029] In the above chemical formula 2,

[0030] R 12 and R 13 each independently represents hydrogen, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 20 , or NR 21 R 22 And,

[0031] R 14 and R 19 are, each independently, hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms,

[0032] R 15 Inland R 18 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms,

[0033] R 20 Inland R 22 are, each independently, hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0034] Another aspect of the present invention provides a precursor composition for vapor deposition comprising the composition.

[0035] Another aspect of the present invention provides a method for manufacturing a thin film, comprising the step of introducing the precursor composition for vapor deposition into a chamber.

[0036] Another aspect of the present invention provides a thin film manufactured by the method for manufacturing the thin film.

[0037] The composition according to the present invention is a liquid, has excellent ALD characteristics, enables uniform thin film deposition, and thus enables securing a thin film with almost no impurities and excellent step coating characteristics.

[0038] The above properties provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

[0039] In addition, a thin film deposited using the composition of the present invention is expected to be utilized as an active layer of an oxide thin film transistor (TFT) in a future display device, and can be used as a channel, etc., in the manufacture of memory semiconductors.

[0040] FIG. 1(a) is a graph showing the change in deposition rate according to the change in precursor injection time in the production of an indium gallium oxide film of Manufacturing Example 1 of the present invention, FIG. 1(b) is a graph showing the change in deposition rate according to the change in reaction gas injection time in the production of an indium gallium oxide film of Manufacturing Example 2 of the present invention, and FIG. 1(c) is a graph showing the change in deposition rate according to the change in process temperature in the production of an indium gallium oxide film of Manufacturing Example 3 of the present invention.

[0041] Figure 2 is a graph showing the NMR measurement results of a composition having a DMION and DMGON ratio of 3:1 in the present invention.

[0042] Figure 3 is a graph showing the analysis results according to thermogravimetric analysis (TGA) of a composition having a DMION and DMGON ratio of 3:1 in the present example.

[0043] Figure 4 is a graph and table showing the results of measuring the XPS depth profile of an indium gallium oxide film with a thickness of 20 nm deposited at a process temperature of 310°C.

[0044] FIG. 5 is a graph and table showing the results of analysis according to X-ray diffractometry (XRD) of an indium gallium oxide film deposited using a composition having a DMION and DMGON ratio of 3:1 of the present example at process temperatures of 100°C and 310°C.

[0045] FIG. 6 is a graph and table showing the analysis results according to X-ray reflectometry (XRR) of an indium gallium oxide film deposited using a composition having a DMION and DMGON ratio of 3:1 of the present invention at process temperatures of 100°C and 310°C.

[0046] Fig. 7(a) is a photograph of an indium gallium oxide film deposited at a process temperature of 310°C and manufactured in a trench structure with an aspect ratio of 40:1, taken using a transmission electron microscope (TEM), and Fig. 7(b) is a photograph showing the result of mapping the indium gallium oxide film using energy dispersive X-ray spectrometry (EDS).

[0047] Hereinafter, the functions and effects of the invention will be described in more detail through specific examples. However, these examples are provided merely as examples of the invention and do not define the scope of the invention.

[0048] Prior to this, the terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0049] Accordingly, the configuration of the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent all of the technical ideas of the present invention, so it should be understood that various equivalents and modified examples that can replace them may exist at the time of filing this application.

[0050] In this specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise," "include," or "have" should be understood to indicate the presence of a feature, number, step, component, or combination thereof, but not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0051] In this specification, “a to b” and “a~b” indicating a numerical range are defined as “a to” and “~” as ≥ a and ≤ b.

[0052]

[0053] A composition according to one aspect of the present invention may include a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2.

[0054]

[0055] [Chemical Formula 1]

[0056]

[0057]

[0058] In the above chemical formula 1,

[0059] R1 and R2 are each independently hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR9, or NR 10 R 11 And,

[0060] R3 and R8 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms,

[0061] R4 to R7 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms,

[0062] R9 to R 11 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0063]

[0064] [Chemical Formula 2]

[0065]

[0066]

[0067] In the above chemical formula 2,

[0068] R 12 and R 13 each independently represents hydrogen, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 20 , or NR 21 R 22 And,

[0069] R 14 and R 19 are, each independently, hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms,

[0070] R 15 Inland R 18 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms,

[0071] R 20 Inland R 22 are, each independently, hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0072]

[0073] In one embodiment of the present invention, preferably R1, R2, R 12 and R 13are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, OH, OMe, OEt, O n Pr, O i Pr group, NH2 group, NHMe group, NHEt group, NH n Prgi, NH i Pr stage, NMe2 stage, NMeEt stage, NMe n Pr machine, NMe i Pr phase, NEt2 phase, NEt n Pr, NEt i Pr, N n Pr2 group, N n Pr i Pr group, and N i It can be any one selected from the group consisting of Pr2 groups. The Me is methyl, the Et is ethyl, and the n Pr is n-profile, and i Pr is iso-profile.

[0074] R1, R2, R 12 and R 13 More preferably, each independently may 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, but is not limited thereto.

[0075] More preferably, R1, R2, R 12 and R 13 may be a methyl group.

[0076] In one embodiment of the present invention, preferably R3, R8, R 14 and R 19 may 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, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a neo-pentyl group, a sec-pentyl group, a tert-pentyl group, a hexyl group, an iso-hexyl group, and isomers thereof.

[0077] R3, R8, R 14 and R 19 More preferably, it 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.

[0078] More preferably, R3 and R 14 is a tert-butyl group, and R8 and R 19 may be a methyl group.

[0079] In one embodiment of the present invention, preferably R4 to R7 and R 15 Inland R 18 Each independently may 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.

[0080] R4 to R7 and R 15 Inland R 18 More preferably, each independently may be any one selected from the group consisting of hydrogen, a methyl group, and an ethyl group, but is not limited thereto.

[0081] More preferably, R4, R5, R 15 and R 16 can be hydrogen, R6, R7, R 17 and R 18 may be a methyl group.

[0082] In one embodiment of the present invention, preferably R9 to R 11 and R 20 Inland R 22 , each independently, may 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.

[0083] In one embodiment of the present invention, the molar ratio of the first compound and the second compound included in the composition may be 1:1 to 5:1.

[0084] 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.

[0085] If the molar ratio of the first compound and the second compound is outside the range of the present invention, it may be difficult to form a thin film with a desired atomic ratio when depositing the thin film.

[0086] In one embodiment of the present invention, the composition comprising the first compound and the second compound may be liquid at room temperature. In addition, the composition has a low melting point and excellent volatility at low temperatures.

[0087] A precursor composition for vapor deposition according to one aspect of the present invention may include any one of the above compositions.

[0088] A method for manufacturing a thin film according to one aspect of the present invention may include a step of introducing the precursor composition for vapor deposition into a chamber.

[0089] In one embodiment of the present invention, the step of introducing the precursor composition for vapor deposition into the chamber may include a step of physical adsorption, chemical adsorption, or physical and chemical adsorption.

[0090] 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).

[0091] 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.

[0092] The method for manufacturing the above thin film may preferably be atomic layer deposition, but is not limited thereto.

[0093] In atomic layer deposition (ALD), the reactants must be highly volatile, stable, and highly reactive. In ALD, reactant materials are supplied separately, and a thin film less than a monolayer is grown through surface reaction during a single deposition cycle. The ligands of the reactant materials adsorbed on the substrate are removed through a chemical reaction with other reactant materials supplied later. When heating the precursor composition, which is the reactant for ALD, in a liquid state can be much more advantageous in terms of reaction speed and process efficiency than in a solid state.

[0094] In one embodiment of the present invention, the method for manufacturing the thin film may further include a step of injecting a compound (or mixture) containing oxygen (O) atoms as a reaction gas.

[0095] Specifically, an oxide thin film can be deposited using at least one selected from water vapor (H2O), hydrogen peroxide vapor (H2O2), oxygen (O2), a mixture of oxygen and hydrogen (O2+H2), and ozone (O3) as a reaction gas, but is not limited thereto.

[0096] In one embodiment of the present invention, when the method for manufacturing 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 byproducts that do not react with the precursor composition or are generated by reacting with the precursor composition after the step of injecting the reaction gas.

[0097] The above purge step helps the precursor move on the substrate, ensures that the inside of the reactor has an appropriate pressure for deposition, and also releases impurities present inside the reactor to the outside. That is, a process of purging the inside of the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) before and after the supply of the reaction gas may be additionally performed.

[0098] In one embodiment of the present invention, the method for manufacturing the thin film may have a process temperature of 50°C or more and 500°C or less.

[0099] For example, the process temperature may be 60°C or more and 480°C or less, 70°C or more and 460°C or less, 80°C or more and 440°C or less, 90°C or more and 350°C or less, 90°C or more and 315°C or less, 95°C or more and 310°C or less, or 100°C or more and 310°C or less.

[0100] If the process temperature falls below the range of the present invention, the reaction rate may be insufficient, slowing the deposition rate and hindering proper deposition. If the process temperature exceeds the range of the present invention, the reaction rate may be too rapid, generating impurities or decomposing precursors or reactant gases, hindering proper deposition and hindering thin film formation.

[0101] In one embodiment of the present invention, when the method for manufacturing a thin film of the present invention is used to introduce the precursor composition for vapor deposition into a chamber, a section (ALD window) in which the deposition rate is constant regardless of the process temperature can be displayed in a range of 95°C or more and 315°C or less.

[0102] For example, the ALD window may be 95°C or more and 310°C or less, 100°C or more and 315°C or less, or 100°C or more and 310°C or less.

[0103] In one embodiment of the present invention, when a thin film is deposited by the thin film manufacturing method of the present invention at a process temperature in the range of 90 ℃ or more and 400 ℃ or less, the deposition rate may be 0.7 Å / cycle or more and 1.4 Å / cycle or less.

[0104] For example, in a process temperature range of 95 ℃ or more and 315 ℃ or less, the thin film deposition rate by the thin film manufacturing method of the present invention may be 0.7 Å / cycle or more and 1.00 Å / cycle or less, 0.7 Å / cycle or more and 0.95 Å / cycle or less, 0.73 Å / cycle or more and 0.95 Å / cycle or less, 0.75 Å / cycle or more and 0.96 Å / cycle or less, or 0.75 Å / cycle or more and 0.95 Å / cycle or less.

[0105] In one embodiment of the present invention, the method for manufacturing the thin film may have a canister temperature of 30°C or more and 100°C or less.

[0106] For example, the canister temperature may be 35°C or higher and 95°C or lower, 40°C or higher and 90°C or lower, 45°C or higher and 85°C or lower, 50°C or higher and 80°C or lower, 55°C or higher and 75°C or lower, 60°C or higher and 70°C or lower, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C. The canister temperature may preferably be 65°C.

[0107] A canister is used to supply a source gas into a chamber for reaction in a thin film manufacturing method. Typically, the canister vaporizes a precursor composition to generate a source gas, which is then supplied into the chamber.

[0108] When the canister temperature is less than 30°C or more than 100°C, the uniformity of the thickness of the thin film manufactured through the above thin film manufacturing method may be significantly reduced. This is because, when the canister temperature is less than 30°C, the amount of 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 heat energy or excessive supply of the precursor composition to the chamber.

[0109] In one embodiment of the present invention, 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 carrier gas may be 10 sccm or more and 1000 sccm or less.

[0110] For example, the precursor composition injection time may be 1 second or more and 27 seconds or less, 2 seconds or more and 24 seconds or less, 3 seconds or more and 15 seconds or less, or 3 seconds or more and 12 seconds or less.

[0111] The purge gas injection amount of 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.

[0112] If the process is performed beyond or below the above range, it may be difficult to form an appropriate thin film.

[0113] Specifically, if the injection time of the precursor composition falls below the range of the present invention, the reactants necessary for forming a thin film may be insufficient, preventing the formation of a thin film of an appropriate thickness. On the other hand, if the injection time of the precursor composition exceeds the range of the present invention, the composition ratio of the thin film produced may become inconsistent due to impurities resulting from residual compounds after the reaction.

[0114] In addition, if the injection amount of the precursor composition carrier gas is below the range of the present invention, the residual amount of the precursor composition as a reactant may increase, causing an inappropriate reaction, and impurities may not be purged, causing the thin film layer to be deposited unevenly.

[0115] 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 amount of the reaction gas may be 50 sccm or more and 3000 sccm or less.

[0116] For example, the injection time of the reaction gas may be 2 seconds or more and 27 seconds or less, 3 seconds or more and 24 seconds or less, 4 seconds or more and 21 seconds or less, 5 seconds or more and 19 seconds or less, 6 seconds or more and 17 seconds or less, 7 seconds or more and 15 seconds or less, or 5 seconds or more and 15 seconds or less.

[0117] In addition, the reaction gas injection amount may be, for example, 100 sccm or more and 2500 sccm or less, 300 sccm or more and 2000 sccm or less, 500 sccm or more and 1500 sccm or less, 700 sccm or more and 1300 sccm or less, or 900 sccm or more and 1100 sccm or less.

[0118] In addition, if the injection amount of the reaction gas is less than 50 sccm, the residual amount of the precursor composition, which is the reactant, may increase, resulting in an improper reaction and the generation of impurities, which may cause the thin film layer to be deposited unevenly. On the other hand, if the injection amount of the reaction gas exceeds 3000 sccm, impurities due to the reaction gas compound may be generated.

[0119] In one embodiment of the present invention, the purge gas injection time may be 1 second or more and 1 minute or less, and the purge gas injection amount may be 100 sccm or more and 4000 sccm or less.

[0120] For example, the purge gas injection time of 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.

[0121] The above purge gas injection amount is 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 less, 100 sccm or more and 1800 sccm or less, 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 less, 100 sccm or more and 3300 sccm or less, 100 sccm or more and 3600 sccm or less, 100 sccm 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, It may be 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.

[0122] In one embodiment of the present invention, the number of repetitions of the cycle may be 10 or more.

[0123] For example, the number of repetitions of the above 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, 100,000 or more, and 1,000,000 or less.

[0124] If the process conditions for the above-described reaction gas, process temperature, precursor composition, and purge gas are not satisfied, a thin film with excellent properties cannot be obtained.

[0125] A thin film according to one aspect of the present invention can be manufactured by the above thin film manufacturing method.

[0126] In one embodiment of the present invention, 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.

[0127] In one embodiment of the present invention, a thin film (In) analyzed by X-ray photoelectron spectroscopy (XPS) x Ga y O z ) may have an atomic % ratio of indium and gallium (x:y) of 1:1 to 5:1. For example, the atomic % ratio of indium and 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 and gallium of the indium gallium oxide thin film may be the same as the molar ratio of the first compound and the second compound.

[0128] In one embodiment of the present invention, the indium (In) content of the thin film analyzed by X-ray photoelectron spectroscopy (XPS) may be 25 atomic% or more and 40 atomic% or less, the gallium (Ga) content may be 7 atomic% or more and 20 atomic% or less, and the oxygen (O) content may be 50 atomic% or more and 60 atomic% or less.

[0129] In one embodiment of the present invention, 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.

[0130] In one embodiment of the present invention, the phase of the thin film analyzed by X-ray diffractometry (XRD) may be nanocrystalline or polycrystalline.

[0131] In one embodiment of the present invention, the density of the thin film analyzed by X-ray reflectometry (XRR) is 6.0 g / cm 3 It can be more than 6.1 g / cm2. For example, 3 Above, 6.2 g / cm 3 Above, 6.3 g / cm 3 or 6.4 g / cm 3 It could be strange.

[0132] Additionally, the density of the above thin film is 7.0 g / cm 3 It may be less than 6.95 g / cm, for example. 3 It could be as follows:

[0133] The roughness of the above thin film may be 5 Å or more and 9.5 Å or less. For example, it may be 5.6 Å or more and 9.2 Å or less, 5.6 Å or more and 7.5 Å or less, or 5.6 Å or more and 7.0 Å or less. The thin film may have excellent interface properties and corrosion resistance due to the surface properties and density thereof.

[0134] Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples.

[0135]

[0136] [Synthesis example]

[0137] Synthesis Example 1: Synthesis of dimethylchloroindium (In(CH3)2Cl)

[0138] Trimethyl indium and pentane were placed in a Schlenk flask, and the solution was cooled to -20°C. Trichloro indium was slowly added to the solution, stirred for 30 minutes, and then the temperature was gradually increased and stirred at room temperature to obtain dimethyl chloro indium (In(CH3)2Cl).

[0139] The synthesis method of dimethylchloroindium (In(CH3)2Cl) is as shown in the following formula 1.

[0140]

[0141] [Formula 1]

[0142]

[0143]

[0144] Synthesis Example 2: Synthesis of dimethylchlorogallium (Ga(CH3)2Cl)

[0145] Trimethyl gallium and pentane were placed in a Schlenk flask, and the solution was cooled to -20°C. Trichloro gallium was slowly added to the solution, stirred for 30 minutes, and then the temperature was gradually increased and stirred at room temperature to obtain dimethylchloro gallium (Ga(CH3)2Cl).

[0146] The synthesis method of dimethylchlorogallium (Ga(CH3)2Cl) is as shown in the following formula 2.

[0147]

[0148] [Formula 2]

[0149]

[0150]

[0151] Synthesis Example 3: In(CH3)2[CH3OC(CH3)2CH2N t Synthesis of Bu](DMION) precursor compound

[0152] After adding n-butyl lithium (2.5 M in hexane) to a Schlenk flask, cool to -20 ℃ and add ligand [CH3OC(CH3)2CH2NH t Bu] was diluted in pentane or hexane and slowly added. After adding everything, the temperature of the flask was gradually increased, and a solution was prepared by stirring 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 solid in the solution was filtered out, and the solvent was removed using a vacuum to secure a pale yellow liquid, and the obtained liquid was vacuum distilled to remove impurities In(CH3)2[CH3OC(CH3)2CH2N t Bu] precursor compound was obtained.

[0153] Synthetic In(CH3)2[CH3OC(CH3)2CH2N tBu] The precursor compound is a transparent liquid compound.

[0154]

[0155] Synthetic In(CH3)2[CH3OC(CH3)2CH2N t The method for synthesizing the precursor compound is as shown in the following formula 3.

[0156]

[0157] [Formula 3]

[0158]

[0159]

[0160] Synthetic In(CH3)2[CH3OC(CH3)2CH2N t The NMR measurement results of the precursor compound are as follows.

[0161]

[0162] 1 H-NMR (C6D6):

[0163] δ 2.93 In(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 2H)

[0164] δ 2.62 In(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 3H)

[0165] δ 1.26 In(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 9H)

[0166] δ 0.97 In(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 6H)

[0167] δ 0.04 In(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 6H)

[0168]

[0169] Synthesis Example 4: Ga(CH3)2[CH3OC(CH3)2CH2N t Synthesis of Bu](DMGON) precursor compound

[0170] After adding n-butyl lithium (2.5 M in hexane) to a Schlenk flask, cool to -20 ℃ and add ligand [CH3OC(CH3)2CH2NH t Bu] was diluted in pentane or hexane and slowly added. After adding everything, the temperature of the flask was gradually increased and a solution was prepared by stirring 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 stirred at room temperature for 18 hours. Then, the solid in the solution was filtered out and the solvent was removed using a vacuum to secure a pale yellow liquid, and the obtained liquid was vacuum distilled to remove impurities to obtain Ga(CH3)2[CH3OC(CH3)2CH2N t Bu] precursor compound was obtained.

[0171] Synthetic Ga(CH3)2[CH3OC(CH3)2CH2N t Bu] The precursor compound is a transparent liquid compound.

[0172]

[0173] Ga(CH3)2[CH3OC(CH3)2CH2N t The method for synthesizing the precursor compound is as shown in the following formula 4.

[0174]

[0175] [Formula 4]

[0176]

[0177]

[0178] Synthetic Ga(CH3)2[CH3OC(CH3)2CH2N t The NMR measurement results of the precursor compound are as follows.

[0179]

[0180] 1 H-NMR (C6D6):

[0181] δ 2.82 Ga(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 2H)

[0182] δ 2.62 Ga(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 3H)

[0183] δ 1.28 Ga(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 9H)

[0184] δ 0.93 Ga(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 6H)

[0185] δ -0.04 Ga(CH3)2[CH3OC(CH3)2CH2N t Bu], s, 6H)

[0186]

[0187] [Example]

[0188] Example: Preparation of composition

[0189] In(CH3)2[CH3OC(CH3)2CH2N t Bu] precursor compound (synthesis example 3, DMION) and Ga(CH3)2[CH3OC(CH3)2CH2N t Bu] The precursor compound (Synthesis Example 4, DMGON) was mixed in a molar ratio of 3:1 to prepare the composition of the example.

[0190]

[0191] [Manufacturing example]

[0192] Manufacturing Examples 1 to 3: Manufacturing of indium gallium oxide films using atomic layer deposition (ALD)

[0193] Indium gallium thin film (In) was prepared by atomic layer deposition (ALD) using the composition of the example (DMION:DMGON=3:1). x Ga y O z ) was manufactured.

[0194] The substrate used in this experiment is 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 through a dry oxidation process.

[0195] 200 g / m as reaction gas 3 Ozone (O3) of a concentration was used, which was generated from 1,000 sccm of oxygen gas. Argon (Ar), an inert gas, was used to act as a carrier for the precursor and to purge the precursor and reaction gas. The flow rate of the carrier argon was 300 sccm, and the flow rate of the purge argon was 1,500 sccm.

[0196]

[0197] [Manufacturing Example 1]

[0198] (Precursor injection for x seconds) - (Purge gas injection for 10 seconds) - (Reactant gas injection for 12 seconds) - (Purge gas injection for 10 seconds) were performed sequentially, and this was considered one cycle.

[0199] In supplying the indium gallium mixed precursor composition of Manufacturing Example 1, the x seconds were set to 3 to 12 seconds, the process temperature was set to 100°C or 310°C, and the number of cycles was set to 100 to deposit an indium gallium oxide film.

[0200] Specific process conditions are shown in Table 1 below.

[0201]

[0202] Manufacturing Example Precursor Injection Time (sec) Precursor Purge Time (sec) Reaction Gas Injection Time (sec) Reaction Gas Purge Time (sec) Process Temperature (℃) Number of Cycles (cycles) 1-13 10 12 10 100 100 1-25 1-37 1-4 10 1-5 12 1-63 3 10 1-75 1-87 1-9 10 1-10 12

[0203]

[0204] In the production of the indium gallium oxide film of Manufacturing Example 1, the change in deposition rate according to the change in precursor injection time is shown in Fig. 1(a).

[0205]

[0206] As shown in Fig. 1(a), at a process temperature of 100°C, the deposition rate increased from 0.75 Å / cycle to 0.82 Å / cycle as the precursor injection time increased from 3 seconds to 10 seconds, and after 10 seconds, the deposition rate was constant, confirming the self-limited reaction, which is a characteristic of atomic layer deposition (ALD).

[0207] In addition, as shown in Fig. 1(a), at a process temperature of 310°C, the deposition rate increased from 0.79 Å / cycle to 0.92 Å / cycle as the precursor injection time increased from 3 seconds to 10 seconds, and the deposition rate was constant after 10 seconds, confirming the self-limited reaction, which is a characteristic of atomic layer deposition (ALD).

[0208]

[0209] [Manufacturing Example 2]

[0210] (Precursor injection for 10 seconds) - (Purge gas injection for 10 seconds) - (Reaction gas injection for y seconds) - (Purge gas injection for 10 seconds) were performed sequentially, and this was considered one cycle.

[0211] In the supply of the reaction gas of Manufacturing Example 2, the y seconds was set to 5 to 15 seconds, the process temperature was set to 100 ℃ or 310 ℃, and the number of cycles was set to 100 to deposit an indium gallium oxide film.

[0212] Specific process conditions are shown in Table 2 below.

[0213]

[0214] Manufacturing Example Precursor Injection Time (sec) Precursor Purge Time (sec) Reaction Gas Injection Time (sec) Reaction Gas Purge Time (sec) Process Temperature (℃) Number of Cycles (cycles) 2-110 105 10100 100 2-272 3102 4122 515 2-65 3102 772 8102 9122 1015

[0215]

[0216] In the production of the indium gallium oxide film of Manufacturing Example 2, the change in deposition rate according to the change in reaction gas injection time is shown in Fig. 1(b).

[0217]

[0218] As shown in Fig. 1(b), at a process temperature of 100 ℃, the deposition rate increased from 0.79 Å / cycle to 0.81 Å / cycle as the reaction gas injection time increased from 5 seconds to 7 seconds, and after 7 seconds, the deposition rate was constant, confirming the self-limited reaction, which is a characteristic of atomic layer deposition (ALD).

[0219] In addition, as shown in Fig. 1(b), at a process temperature of 310 ℃, the deposition rate was constant at 0.92 Å / cycle from the reaction gas injection time of 3 seconds, confirming the self-limited reaction, which is a characteristic of atomic layer deposition (ALD).

[0220]

[0221] [Manufacturing Example 3]

[0222] (Precursor injection for 10 seconds) - (Purge gas injection for 10 seconds) - (Reactant gas injection for 12 seconds) - (Purge gas injection for 10 seconds) were performed sequentially, and this was considered one cycle.

[0223] The process temperature of Manufacturing Example 3 was set to 100 ℃ to 400 ℃, and the number of cycles was 100 to deposit an indium gallium oxide film.

[0224] Specific process conditions are shown in Table 3 below.

[0225]

[0226] Manufacturing Example Precursor Injection Time (sec) Precursor Purge Time (sec) Reaction Gas Injection Time (sec) Reaction Gas Purge Time (sec) Process Temperature (℃) Number of Cycles (cycles) 3-110 101 210 100 100 3-21 303 31 603 41 903 52 203 62 503 72 803 83 103 93 403 103 703 11400

[0227]

[0228] In the production of the indium gallium oxide film of Manufacturing Example 3, the change in deposition rate according to the change in process temperature is shown in Figure 1(c).

[0229]

[0230] As shown in Fig. 1(c), the deposition rate was maintained constant at 0.75 Å / cycle to 0.91 Å / cycle at process temperatures of 100 ℃ to 310 ℃, confirming that the ALD window (a section in which the deposition rate is constant regardless of the process temperature) when the composition of the example was used was 100 ℃ to 310 ℃. As the process temperature increased from 340 ℃ to 400 ℃, the deposition rate significantly increased from 1.09 Å / cycle to 1.33 Å / cycle.

[0231] It was confirmed that the refractive index was maintained at 2.04 regardless of the process temperature.

[0232]

[0233] [Evaluation example]

[0234] Evaluation Example 1: NMR Measurement

[0235] Using Varian 400 MHz, the composition of the example with a DMION and DMGON ratio of 3:1 1 H NMR was measured.

[0236] 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) and Ga's Methyl H peak δ -0.16 (s, 6H) was 3:1, the same as the molar ratio of the compound of Synthesis Example 3 and the compound of Synthesis Example 4.

[0237]

[0238] Evaluation Example 2: Thermogravimetric analysis (TGA)

[0239] Thermogravimetric analysis of the composition having a DMION and DMGON ratio of 3:1 in the example was performed using a TG209 F1 Libra instrument from Netzsch.

[0240] An alumina crucible with a capacity of 50 μL was used, and the amount of all samples was 10 mg. Measurements were made by increasing the temperature from 30 ℃ to 500 ℃ at a rate of 10 ℃ / min.

[0241] The TGA measurement results of the composition having a DMION and DMGON ratio of 3:1 in the example are shown in Fig. 3.

[0242] As a result of thermogravimetric analysis, the half-life (T) of the composition having a DMION and DMGON ratio of 3:1 in the example is shown in Fig. 3. 1 / 2 , ℃) was 132.6 ℃. In addition, it was confirmed that the residual amount of the composition having a DMION and DMGON ratio of 3:1 at 200 ℃ was 2.8 wt%, and the residual amount at 300 ℃ was 2.7 wt%.

[0243]

[0244] Evaluation Example 3: Analysis of the composition of the oxide film

[0245] The composition and impurity content of the indium gallium oxide film deposited using a composition having a DMION and DMGON ratio of 3:1 in the example were analyzed using X-ray photoelectron spectroscopy (XPS).

[0246]

[0247] The XPS depth profile measurement results of the 20 nm thick indium gallium oxide film deposited at a process temperature of 310 ℃ are shown in Fig. 4.

[0248] As shown in Fig. 4, the XPS depth profile measurement results showed that indium (In) was 31.0 atomic%, gallium (Ga) was 11.8 atomic%, and oxygen (O) was 57.2 atomic%, while no impurities such as carbon, nitrogen, or hydrogen were detected, and the ratio of oxygen to metal was 1.34.

[0249] That is, it was confirmed that the ratio of indium and gallium atoms included in the indium gallium oxide film manufactured in the ALD window followed the mixing ratio of the indium precursor compound (Synthesis Example 3) and the gallium precursor compound (Synthesis Example 4) of the composition. In addition, it was confirmed that the impurities (carbon, nitrogen, hydrogen, etc.) included in the indium gallium oxide film were at a negligible level.

[0250]

[0251] Evaluation Example 4: Crystallinity and density analysis of oxide films

[0252] The crystallinity and density of the indium gallium oxide film deposited using a composition having a DMION and DMGON ratio of 3:1 in the example were analyzed using X-ray diffractometry (XRD) and X-ray reflectometry (XRR).

[0253]

[0254] The XRD analysis results of the indium gallium oxide film deposited using the composition having a DMION and DMGON ratio of 3:1 at process temperatures of 100 ℃ and 310 ℃ are shown in Fig. 5.

[0255] At a process temperature of 100 ℃, a broad peak appeared, indicating that the microstructure of the oxide film was nanocrystalline, close to amorphous. In addition, at a process temperature of 310 ℃, several sharp peaks, such as (211) peak, (222) peak, (431) peak, (440) peak, and (622) peak, appeared, indicating that the microstructure of the oxide film was polycrystalline. As a result of confirming with reference to the ICDD card (00-006-0316), it was confirmed that the polycrystalline oxide film was in the Ia-3 space group of the cubic crystal system.

[0256]

[0257] The results of XRR analysis of an indium gallium oxide film deposited using a composition having a DMION and DMGON ratio of 3:1 at process temperatures of 100°C and 310°C are shown in Fig. 6.

[0258] As shown in Fig. 6, the density of the oxide film deposited at a process temperature of 100 ℃ is 6.45 g / cm 3 And, the density of the oxide film deposited at the process temperature of 310 ℃ is 6.91 g / cm 3 It was confirmed that the roughness of the oxide film deposited at a process temperature of 100 ℃ was 6.70 Å, and the roughness of the oxide film deposited at a process temperature of 310 ℃ was 5.80 Å.

[0259]

[0260] That is, it was confirmed that as the process temperature increased, the crystallinity of the thin film increased, and the density also increased, ultimately increasing the density of the thin film.

[0261]

[0262] Evaluation Example 5: Analysis of the step coverage of the oxide film

[0263] The step coverage of the indium gallium oxide film deposited using a composition having a DMION and DMGON ratio of 3:1 was analyzed through transmission electron microscope (TEM) observation and energy dispersive X-ray spectrometry (EDS).

[0264]

[0265] Figure 7(a) shows a TEM photograph of an indium gallium oxide film deposited at a process temperature of 310°C and manufactured in a trench structure with an aspect ratio of 40:1.

[0266] 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.

[0267]

[0268] Figure 7(b) shows the EDS mapping results of the indium gallium oxide film.

[0269] As shown in Fig. 7(b), it was confirmed that indium and gallium atoms were uniformly distributed within the indium gallium oxide film deposited using the composition having a DMION and DMGON ratio of 3:1 of the example.

[0270]

[0271] As described above, the composition of the present invention has excellent ALD characteristics, and it was confirmed that 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 of the composition, and that almost no impurities exist in the film. In addition, it was confirmed that it has excellent step coverage even in a trench structure with an aspect ratio of 40:1.

[0272] Due to these excellent properties, a thin film deposited using the composition of the present invention is expected to be utilized 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, etc., in the manufacture of memory semiconductors.

[0273]

[0274] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0275] The composition according to the present invention is a liquid, has excellent ALD characteristics, enables uniform thin film deposition, and thus enables securing a thin film with almost no impurities and excellent step coating characteristics.

[0276] The above properties provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

[0277] In addition, a thin film deposited using the composition of the present invention is expected to be utilized as an active layer of an oxide thin film transistor (TFT) in a future display device, and can be used as a channel, etc., in the manufacture of memory semiconductors.

Claims

1. A compound comprising a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2. Composition: [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are, each independently, hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR9, or NR 10 R 11 And, R3 and R8 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, R9 to R 11 are, each independently, hydrogen, or a linear or branched hydrocarbon group having 1 to 3 carbon atoms. [Chemical formula 2] In the above chemical formula 2, R 12 and R 13 Silver, each independently, hydrogen, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, OR 20 , or NR 21 R 22 And, R 14 and R 19 are, each independently, hydrogen, or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, R 15 Inland R 18 are, each independently, hydrogen, or a linear or branched hydrocarbon group having 1 to 3 carbon atoms, R 20 Inland R 22 are, each independently, hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.

2. In paragraph 1, R1, R2, R 12 and R 13 are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, OH, OMe, OEt, O n Pr, O i Pr group, NH2 group, NHMe group, NHEt group, NH n Prgi, NH i Pr stage, NMe2 stage, NMeEt stage, NMe n Prgi, NMe i Pr, NEt2, NEt n Prgi, NET i Pr, N n Pr2, N n Pr i Pr, and N i One selected from the group consisting of Pr2 groups, Composition. (Me above is methyl, Et above is ethyl, and n Pr is the n-profile, and i Pr is iso-profile.) 3. In paragraph 1, R3, R8, R 14 and R 19 is, each independently, 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, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a neo-pentyl group, a sec-pentyl group, a tert-pentyl group, a hexyl group, an iso-hexyl group, and isomers thereof. Composition.

4. In paragraph 1, R4 to R7 and R 15 Inland R 18 each independently represents one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group and an iso-propyl group, Composition.

5. In paragraph 1, R9 to R 11 and R 20 Inland R 22 is, each independently, one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group and an iso-propyl group, Composition.

6. In paragraph 1, The molar ratio of the first precursor and the second precursor is 1:1 to 5:1, Composition.

7. A composition comprising any one of claims 1 to 6, A precursor composition for vapor deposition.

8. A step of introducing a precursor composition for vapor deposition according to Article 7 into a chamber, Method for manufacturing a thin film.

9. In paragraph 8, The method for manufacturing the above thin film includes atomic layer deposition (ALD) or chemical vapor deposition (CVD).

10. In paragraph 8, Further comprising a step of injecting a compound containing oxygen (O) atoms as a reaction gas, The above reaction gas is at least one selected from water vapor (H2O), hydrogen peroxide vapor (H2O2), oxygen (O2), a mixture of oxygen and hydrogen (O2+H2), and ozone (O3). Method for manufacturing a thin film.

11. Manufactured by the thin film manufacturing method of Article 8, pellicle.

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