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

Abstract

The present invention relates to a compound capable of thin film deposition and, specifically, to a novel compound applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and exhibiting excellent reactivity, volatility, and thermal stability, a method for preparing the compound, a precursor compound comprising the compound, and a method for manufacturing a thin film using the precursor compound.

Description

Novel compound, method for preparing the same, precursor compound containing the same, and method for preparing a thin film using the same

[0001] The present invention relates to a novel compound capable of forming a thin film through atomic layer deposition (ALD) and chemical vapor deposition (CVD), a method for preparing the compound, a precursor compound including the novel compound, and a method for preparing a thin film using the precursor compound.

[0002]

[0003] 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.

[0004] 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.

[0005] In order to manufacture thin films using atomic layer deposition, precursor compounds play an important role. Through the design of a new structure of a novel precursor compound with high volatility, high thermal stability, and high reactivity with various oxidizing agents, nitriding agents, or reducing agents, there is an increasing need to develop a precursor compound that is structurally stable and can form thin films over a wide temperature range (ALD window) during the ALD / CVD process.

[0006] To date, precursor compounds have been developed using various ligands, and representative known ligands include halogens, alkoxides, cyclopentadienes, beta-diketonates, amides, and amidinates. However, most known precursor compounds 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 precursor compounds that can improve the above-mentioned shortcomings and enable thin film deposition with excellent step coverage.

[0007]

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 1) Republic of Korea Patent Publication No. 10-2018-0044802

[0011]

[0012] The present invention aims to provide a novel compound applicable to atomic layer deposition (ALD) or chemical vapor deposition (CVD) and a precursor compound including the same.

[0013] In particular, the purpose is to provide a precursor compound 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.

[0014] In addition, the present invention seeks to provide a method for producing the novel compound and a method for producing a thin film using the precursor compound.

[0015] 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.

[0016]

[0017] One aspect of the present invention provides a compound represented by the following chemical formula 1.

[0018] [Chemical Formula 1]

[0019]

[0020]

[0021] In the above chemical formula 1,

[0022] M is Al, In, or Ga,

[0023] R5 and R 10 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, which is substituted or unsubstituted,

[0024] R1 to R4 and R6 to R9 are each independently hydrogen or a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0025] Another aspect of the present invention provides a precursor comprising the compound.

[0026] Another aspect of the present invention provides a method for producing a thin film, comprising the step of introducing a precursor comprising the compound into a reactor.

[0027] Another aspect of the present invention comprises a first step of reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3 to produce a compound represented by the following chemical formula 4; and

[0028] A method for producing a compound is provided, including a second step of producing a compound represented by the following chemical formula 6 by reacting a compound represented by the above chemical formula 4 with a compound represented by the following chemical formula 5.

[0029] [Chemical Formula 2]

[0030]

[0031]

[0032] [Chemical Formula 3]

[0033] MX3

[0034]

[0035] [Chemical Formula 4]

[0036]

[0037]

[0038] [Chemical Formula 5]

[0039]

[0040]

[0041] [Chemical Formula 6]

[0042]

[0043]

[0044] In the above chemical formula 2,

[0045] R 11 Inland R 21 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms, substituted or unsubstituted,

[0046] In the above chemical formulas 2 to 4 and the above chemical formula 6,

[0047] M is one selected from the group consisting of Al, In, and Ga,

[0048] X is a halogen element,

[0049] In the above chemical formula 5 and chemical formula 6,

[0050] R 27 and R 32 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, substituted or unsubstituted,

[0051] R 23 Inland R 26 and R 28 Inland R 31 are each independently hydrogen, a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0052]

[0053] The novel compound according to the present invention and the precursor compound including the novel compound have excellent reactivity, volatility and thermal stability, are liquid, and enable uniform thin film deposition with excellent properties, thereby ensuring excellent thin film properties, thickness and step coverage.

[0054] The above properties provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

[0055]

[0056] Figure 1 is a graph showing the analysis results according to thermogravimetric analysis (TGA) of the tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)gallium (GaON) compound of Synthesis Example 1 of the present application.

[0057] Figure 2 is a graph showing the results of analysis according to thermal characteristics analysis (Differential Scanning Calorimetry, DSC) of the GaON precursor compound of Synthesis Example 1 of the present invention.

[0058] Figure 3 is a graph showing the change in deposition rate according to the change in process temperature of Example 1 of the present invention.

[0059] Figure 4 is an image showing the step coverage of a gallium oxide film (Ga2O3) manufactured by Example 1 of the present invention, observed using a transmission electron microscope (TEM).

[0060] Figure 5 is a graph showing the analysis results according to the X-ray reflectometry (XRR) method of the gallium oxide film manufactured by Example 1 of the present invention.

[0061] Figure 6 is a graph showing the analysis results according to X-ray photoelectron spectroscopy (XPS) of a gallium oxide film manufactured by Example 1 of the present invention.

[0062] Figure 7 is a graph showing the results of analyzing the impurity content of a gallium oxide film manufactured by Example 1 of the present invention using a secondary ion mass spectrometer (SIMS).

[0063]

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] In this specification, “a to b” and “a~b” indicating a numerical range are defined as “a to” and “~” as ≥ a and ≤ b.

[0069] A compound according to one aspect of the present invention may be represented by the following chemical formula 1.

[0070] [Chemical Formula 1]

[0071]

[0072]

[0073] In the above chemical formula 1,

[0074] M is Al, In, or Ga,

[0075] R5 and R 10 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, which is substituted or unsubstituted,

[0076] R1 to R4 and R6 to R9 are each independently hydrogen or a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0077] In one embodiment of the present invention, preferably, R1 to R4 and R6 to R9 may each independently be hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or a combination thereof.

[0078] R1 to R4 and R6 to R9 may more preferably, independently, be hydrogen, a methyl group, an ethyl group or a combination thereof, but are not limited thereto.

[0079] More preferably, R1 to R4, R8 and R9 are methyl groups, and R6 and R7 could be hydrogen.

[0080] In one embodiment of the present invention, preferably R5 and R 10 Each independently may be 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, or a combination thereof.

[0081] R5 and R 10 More preferably, each independently may be 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, or a combination thereof, but is not limited thereto.

[0082] More preferably, R5 is a tert-butyl group, and R 10 may be a methyl group.

[0083] Examples of the compound represented by the above chemical formula 1 may include, but are not limited to, any of the following compounds:

[0084] (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)gallium;

[0085] (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)indium;

[0086] (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)aluminum.

[0087] In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be liquid at room temperature. In addition, the compound represented by Chemical Formula 1 has a low melting point and excellent volatility at low temperatures.

[0088] Another aspect of the present invention, the precursor, may include a compound represented by the above chemical formula 1.

[0089] Another aspect of the present invention provides a method for producing a thin film, comprising the step of introducing a precursor comprising a compound represented by the above chemical formula 1 into a reactor.

[0090] In one embodiment of the present invention, the step of introducing the precursor (e.g., a precursor compound for vapor deposition or a precursor composition for vapor deposition) into the reactor (chamber) may include a step of physical adsorption, chemical adsorption, or physical and chemical adsorption.

[0091] 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).

[0092] 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.

[0093] The method for manufacturing the above thin film may preferably be atomic layer deposition, but is not limited thereto.

[0094] In atomic layer deposition (ALD), the reactants must be highly volatile, stable, and highly reactive. ALD is a method in which 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 compounds, which are reactants for ALD, in a liquid state can be much more advantageous in terms of reaction speed and process efficiency than in a solid state.

[0095] In one embodiment of the present invention, the method for manufacturing the thin film may additionally include a step of introducing an oxidizing agent, a nitriding agent, a reducing agent, or a combination thereof into the reactor.

[0096] Specifically, a thin film can be manufactured using hydrogen (H2), water vapor (H2O), hydrogen peroxide vapor (H2O2), oxygen (O2), a mixture of oxygen and hydrogen (O2+H2), ozone (O3), nitrogen (N2), ammonia (NH3), hydrazine (N2H4) or a combination thereof as a reaction gas, but is not limited thereto.

[0097] For example, water vapor (H2O), oxygen (O2), ozone (O3), or a combination thereof may be used as a reaction gas to deposit an oxide thin film, and nitrogen (N2), ammonia (NH3), hydrazine (N2H4), or a combination thereof may be used as a reaction gas to deposit a nitride thin film. Additionally, hydrogen (H2) may be used as a reaction gas to deposit a metal thin film.

[0098] 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 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 or are generated by reacting with the precursor after the step of injecting the reaction gas.

[0099] 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.

[0100] In one embodiment of the present invention, the method for manufacturing the thin film may be such that the temperature of the precursor is in the range of 75°C or more and 85°C or less.

[0101] For example, the precursor compound temperature may be 77°C or more and 83°C or less, or 79°C or more and 81°C or less.

[0102] In one embodiment of the present invention, preferably, the precursor compound temperature is 80°C.

[0103] If the precursor compound temperature falls below the original range, the reaction precursor compound may not be sufficiently evaporated, and if it exceeds the original range, the reaction precursor compound may evaporate too quickly, making it impossible to precisely control the deposition process.

[0104] In one embodiment of the present invention, the method for manufacturing the thin film may have a process temperature of 120°C or more and 370°C or less.

[0105] For example, the process temperature may be 130°C or more and 360°C or less, 140°C or more and 350°C or less, 150°C or more and 340°C or less, or 160°C or more and 330°C or less. The process temperature may preferably be 170°C or more and 320°C or less.

[0106] If the process temperature falls below the specified range, the reaction rate may be insufficient, slowing the deposition rate and resulting in improper deposition. Furthermore, the precursor compound may not diffuse sufficiently, which may lead to defects or unevenness in the material and film, potentially leading to instability of the substrate or film.

[0107] If the process temperature exceeds the range of the present invention, the reaction speed may be too fast, causing impurities to be generated or the precursor compound or reaction gas to decompose, preventing proper deposition and making it difficult to form a thin film.

[0108] In one embodiment of the present invention, in the case of a method for manufacturing a thin film including a step of introducing a precursor compound into a reactor, a section (ALD window) in which the deposition rate is constant regardless of the process temperature may appear in a range of 210°C or more and 280°C or less.

[0109] For example, the ALD window may be 220°C or more and 280°C or less, 220°C or more and 270°C or less, 225°C or more and 270°C or less, 225°C or more and 265°C or less, or 230°C or more and 260°C or less.

[0110] 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 200 ℃ or more and 290 ℃ or less, the deposition rate (Growth rate per cycle GPC) may be 0.5 Å / cycle or more and 1.4 Å / cycle or less.

[0111] For example, in a process temperature range of 210 ℃ or more and 280 ℃ or less, the thin film deposition rate by the thin film manufacturing method of the present invention may be 0.6 Å / cycle or more and 1.35 Å / cycle or less, 0.65 Å / cycle or more and 1.25 Å / cycle or less, 0.65 Å / cycle or more and 1.2 Å / cycle or less, or 0.65 Å / cycle or more and 1.19 Å / cycle or less.

[0112] In one embodiment of the present invention, the method for manufacturing the thin film may have a canister temperature of -20°C or higher and 110°C or lower.

[0113] For example, the canister temperature may be 0°C or more and 105°C or less, 20°C or more and 100°C or less, 40°C or more and 95°C or less, 60°C or more and 90°C or less, 70°C or more and 80°C or less, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C. The canister temperature may preferably be 80°C.

[0114] A canister is used to supply a source gas into a chamber for reaction in a thin film manufacturing process. Typically, the canister vaporizes a precursor compound to generate a source gas, which is then supplied into the chamber.

[0115] When the canister temperature is lower than -20°C or higher than 110°C, the uniformity of the thickness of the thin film manufactured through the above-mentioned thin film manufacturing method may be significantly reduced. This is because, when the canister temperature is lower than -20°C, the amount of precursor compound supplied to the chamber is insufficient, and when the canister temperature is higher than 110°C, it may be difficult to obtain a uniform film quality due to deterioration caused by thermal energy or excessive supply of precursor compound to the chamber.

[0116] In one embodiment of the present invention, the injection time of the precursor compound may be 1 second or more and 30 seconds or less, and the injection amount of the precursor compound carrier gas may be 10 sccm or more and 1000 sccm or less.

[0117] For example, the precursor compound injection time may be 1 second or more and 29 seconds or less, 4 seconds or more and 27 seconds or less, 7 seconds or more and 25 seconds or less, 10 seconds or more and 23 seconds or less, 13 seconds or more and 21 seconds or less, or 15 seconds or more and 20 seconds or less.

[0118] 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.

[0119] If the process proceeds beyond or below the above range, it may be difficult to form an appropriate thin film. Specifically, if the precursor compound injection time is less than 1 second, the reactants necessary for thin film formation may be insufficient, preventing the formation of a thin film of appropriate thickness. Conversely, if the precursor compound injection time exceeds 30 seconds, the composition ratio of the thin film produced may become inconsistent due to impurities from residual compounds after the reaction.

[0120] In addition, if the injection amount of the precursor compound carrier gas is less than 10 sccm, the residual amount of the precursor compound as a reactant may increase, causing an improper reaction, and impurities may not be purged, causing the thin film layer to be deposited unevenly.

[0121] 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.

[0122] For example, the injection time of the reaction gas may be 2 seconds or more and 25 seconds or less, 2 seconds or more and 20 seconds or less, 3 seconds or more and 15 seconds or less, or 3 seconds or more and 10 seconds or less. The injection time of the reaction gas may preferably be 3 seconds or more and 7 seconds or less.

[0123] 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.

[0124] In addition, if the injection amount of the reaction gas is less than 50 sccm, the residual amount of the precursor compound, which is the reactant, may increase, causing an improper reaction, and impurities may be generated, causing 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.

[0125] In one embodiment of the present invention, the purge gas injection time of the first purge step is 1 second or more and 1 minute or less, the purge gas injection time of the second purge step is 10 seconds or more and 1 minute or less, and the purge gas injection amounts of the first purge step and the second purge step can each independently be 100 sccm or more and 2000 sccm or less.

[0126] For example, the purge gas injection time of the first purge step may be 3 seconds or more and 55 seconds or less, 6 seconds or more and 50 seconds or less, 9 seconds or more and 45 seconds or less, 12 seconds or more and 40 seconds or less, or 15 seconds or more and 35 seconds or less, and the purge gas injection time of the second purge step may be 10 seconds or more and 60 seconds or less, 20 seconds or more and 55 seconds or less, or 30 seconds or more and 50 seconds or less.

[0127] The purge gas injection amounts of the first purge step and the second purge step are each independently 100 sccm or more and 200 sccm or less, 100 sccm or more and 300 sccm or less, 100 sccm or more and 400 sccm or less, 100 sccm or more and 500 sccm or less, 100 sccm or more and 600 sccm or less, 100 sccm or more and 700 sccm or less, 100 sccm or more and 800 sccm or less, 100 sccm or more and 900 sccm or less, 100 sccm or more and 1000 sccm or less, 100 sccm or more and 1200 sccm or less, 100 sccm or more and 1400 sccm or less, 100 sccm or more and 1600 sccm or less, 100 sccm or more and 1800 sccm or less, 200 sccm or more and 1700 sccm or less, and 300 sccm It can be 1600 sccm or more, 400 sccm or more, 40-16 sccm or more, 1600 sccm or less, 500 sccm or more, 1600 sccm or less, 600 sccm or more, 1600 sccm or less, 700 sccm or more, 1600 sccm or less, 800 sccm or more, 1600 sccm or less, 900 sccm or more, 1600 sccm or less.

[0128] In one embodiment of the present invention, the number of repetitions of the cycle may be 10 or more.

[0129] 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.

[0130] If the process conditions for the above-described reaction gas, process temperature, precursor compound, and purge gas are not satisfied, a thin film with excellent properties cannot be obtained.

[0131] In one embodiment of the present invention, the thin film manufactured by the method for manufacturing the thin film may include an oxide film, a nitride film, a metal film, or a combination thereof.

[0132] In one embodiment of the present invention, the gallium (Ga) content of the thin film analyzed by X-ray photoelectron spectroscopy (XPS) may be 30 atomic% or more and 50 atomic% or less, and the oxygen (O) content may be 50 atomic% or more and 70 atomic% or less.

[0133] In one embodiment of the present invention, the density of the thin film analyzed by X-ray reflectometry (XRR) is 4.8 g / cm 3 It can be more than 4.9 g / cm, for example. 3 Above, 5.0 g / cm 3 or more than 5.1 g / cm 3 It could be strange.

[0134] Additionally, the density of the above thin film is 5.5 g / cm 3 It may be less than 5.4 g / cm2. For example, 5.4 g / cm2 3 Less than or equal to 5.2 g / cm 3 It could be as follows:

[0135] The roughness of the above thin film may be 0.65 nm or more and 0.78 nm or less. For example, it may be 0.67 nm or more and 0.78 nm or less, 0.7 nm or more and 0.76 nm or less, or 0.71 nm or more and 0.75 nm or less. The thin film may have excellent interface properties and corrosion resistance due to its surface properties and density.

[0136] In one embodiment of the present invention, the intensity of the secondary ion of gallium (Ga) of the thin film analyzed by secondary ion mass spectrometry (SIMS) is 1.0 x 10 4 Ideal 1.0 x 10 6Below, the intensity of the secondary ion of oxygen (O) is 1.0 x 10 4 Ideal 1.0 x 10 6 It could be as follows:

[0137] In one embodiment of the present invention, as a result of analyzing the thin film through the XPS and SIMS, it is found that it does not contain carbon impurities or the intensity of secondary ions of carbon impurities is 1.0 x 10 2 It could be as follows:

[0138] In one embodiment of the present invention, the step coverage measurement result of the thin film analyzed by transmission electron microscopy (TEM) may be 90% or more and 99% or less for B / T (Bottom / Top) in a trench with an aspect ratio of 12:1 and 90% or more and 98% or less for M / T (Middle / Top), and 80% or more and 90% or less for B / T in a trench with an aspect ratio of 40:1 and 80% or more and 90% or less for M / T.

[0139] Due to these excellent properties, a thin film deposited using the compound 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.

[0140] Another aspect of the present invention provides a method for producing a compound, comprising a first step of reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3 to produce a compound represented by the following chemical formula 4, and a second step of reacting a compound represented by the following chemical formula 4 with a compound represented by the following chemical formula 5 to produce a compound represented by the following chemical formula 6.

[0141] [Chemical Formula 2]

[0142]

[0143]

[0144] [Chemical Formula 3]

[0145] MX3

[0146]

[0147] [Chemical Formula 4]

[0148]

[0149]

[0150] [Chemical Formula 5]

[0151]

[0152]

[0153] [Chemical Formula 6]

[0154]

[0155]

[0156] In the above chemical formula 2,

[0157] R 11 Inland R 21 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms, substituted or unsubstituted,

[0158] In the above chemical formulas 2 to 4 and the above chemical formula 6,

[0159] M is one selected from the group consisting of Al, In, and Ga,

[0160] X is a halogen element,

[0161] In the above chemical formula 5 and chemical formula 6,

[0162] R 27 and R 32 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, substituted or unsubstituted,

[0163] R 23 Inland R 26 and R 28 Inland R 31are each independently hydrogen, a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 3 carbon atoms.

[0164] In one embodiment of the present invention, the compound manufactured by the manufacturing method can be used as a precursor in an atomic layer deposition (ALD) or chemical vapor deposition (CVD) process.

[0165]

[0166] 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.

[0167]

[0168] [Synthesis Example 1]

[0169] As shown in the following chemical reaction scheme 1, tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)gallium (GaON) was synthesized.

[0170]

[0171] [Chemical Reaction Formula 1]

[0172]

[0173]

[0174] [Synthesis of tetradimethylaminogallium (TDMAGa)]

[0175] 500 ml of diethylether was added to a flask containing 886 ml of 2.5 M n-butyl lithium. 100 g of dimethylamine was added under a -78 ℃ water bath. After the addition of dimethylamine was completed, the bath was stirred for 2 hours while maintaining it at -78 ℃. 500 ml of diethylether was added to a flask containing 130 g of gallium trichloride. The lithium dimethylamide suspension prepared at -78 ℃ was slowly added to the flask containing gallium trichloride. The mixture was stirred for 12 hours after the temperature was raised to room temperature. After stirring, the byproducts were removed using a Celite filter and washed with pentane solvent. After filtering, the compound was extracted using pentane solvent and the solvent was removed under reduced pressure to obtain tetradimethylamino gallium (TDMAGa).

[0176] The synthesized TDMAGa compound was a white solid compound with a yield of 90%.

[0177] The NMR measurement results of the synthesized TDMAGa compound were as follows.

[0178] 1 H-NMR (400MHz, C6D6):

[0179] δ 2.48 (s, 12H), 2.86 (s, 6H)

[0180]

[0181] [Synthesis of bis(dimethylamino)gallium chloride (Ga(NMe2)2Cl)]

[0182] A flask containing 145 g of TDMAGa was charged with 500 ml of hexane. Another flask was charged with 64 g of gallium trichloride and 500 ml of hexane. Gallium trichloride suspension was slowly added to the flask containing TDMAGa at -78 ℃. After the addition was completed, the temperature was gradually raised to room temperature and stirred for 12 hours. After the reaction was completed, the solvent was removed to obtain bis(dimethylamino)galliumchloride (Ga(NMe2)2Cl).

[0183] The synthesized Ga(NMe2)2Cl compound was a white solid compound with a yield of 100%.

[0184] The NMR measurement results of the synthesized Ga(NMe2)2Cl compound were as follows.

[0185] 1 H-NMR (400MHz, C6D6):

[0186] δ 2.34(s, 6H), 2.81(s, 6H)

[0187]

[0188] [Synthesis of (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)gallium (GaON) precursor compound]

[0189] 500 ml of tetrahydrofuran was added to a flask containing the N-(tert-butyl)-2-methoxy-2-methylpropan-1-amine ligand. 232 ml of 2.5 M n-butyl lithium was slowly added to the flask containing the ligand at -78°C using a dropping funnel. After completion of addition, the mixture was stirred for 2 hours while maintaining the bath temperature.

[0190] - Lithium-ion-bound ligand was slowly added to Ga(NMe2)2Cl dissolved in 500 ml of tetrahydrofuran in a -78 ℃ water bath. After the addition was completed, the temperature was raised to room temperature and stirred for 12 hours. After the reaction was completed, the generated byproduct was removed using a Celite filter. The filtrate was concentrated under reduced pressure and purified at 60 ℃ and 25 mTorr to obtain a liquid product.

[0191] Afterwards, the solid in the obtained liquid product 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 obtain a precursor compound of (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)gallium (GaON) with impurities removed.

[0192] The synthesized GaON precursor compound was a colorless transparent liquid compound, and the yield was 75%.

[0193] The NMR measurement results of the synthesized GaON precursor compound were as follows.

[0194] 1 H-NMR (400MHz, C6D6):

[0195] δ 0.93(s, 6H), 1.27(s, 9H), 2.79(s, 2H), 2.82(s, 3H), 2.98 (s, 12H)

[0196]

[0197] Synthesis Example 2

[0198] [Synthesis of tetradimethylaminoindium (TDMAIn)]

[0199] A compound is synthesized under the same conditions as Synthesis Example 1, except that indium trichloride is added instead of gallium trichloride.

[0200]

[0201] [Synthesis of bis(dimethylamino)indium chloride (In(NMe2)2Cl)]

[0202] A compound is synthesized under the same conditions as Synthesis Example 1, except that TDMAIn is used instead of TDMAGa and indium trichloride is used instead of gallium trichloride.

[0203]

[0204] [Synthesis of (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)indium (InON) precursor compound]

[0205] A precursor compound is synthesized under the same conditions as Synthesis Example 1, except that In(NMe2)2Cl is added instead of Ga(NMe2)2Cl.

[0206]

[0207] Synthesis Example 3

[0208] [Synthesis of tetradimethylaminoaluminum (TDMAAl)]

[0209] A compound is synthesized under the same conditions as Synthesis Example 1, except that aluminum trichloride is added instead of gallium trichloride.

[0210]

[0211] [Synthesis of bis(dimethylamino)aluminum chloride (Al(NMe2)2Cl)]

[0212] A compound is synthesized under the same conditions as Synthesis Example 1, except that TDMAAl is used instead of TDMAGa and aluminum trichloride is used instead of gallium trichloride.

[0213]

[0214] [Synthesis of (tert-butyl(2-methoxy-2-methylpropyl)amino)bis(dimethylamino)aluminum (AlON) precursor compound]

[0215] A precursor compound is synthesized under the same conditions as Synthesis Example 1, except that Al(NMe2)2Cl is added instead of Ga(NMe2)2Cl.

[0216]

[0217] [Example]

[0218] [Example 1: Fabrication of Ga2O3 thin films using atomic layer deposition (ALD)]

[0219] A gallium oxide film (Ga2O3) was prepared using a GaON precursor compound (Synthesis Example 1) using atomic layer deposition (ALD) equipment.

[0220] The substrate used in this experiment was a p-type Si wafer with a resistivity of 0.02 Ω·cm. Prior to deposition, the p-type Si wafer was ultrasonically cleaned in acetone, ethanol, and deionized water (DI water) for 10 minutes each. The native oxide film on the Si wafer was removed after immersing it in a 10% HF solution (HF:H2O=1:9) for 10 seconds. The HF-cleaned Si wafer was immediately transferred to the atomic layer deposition (ALD) chamber.

[0221] Ozone (O3) was used as the reaction gas, and was injected at a flow rate of 1,000 sccm by controlling the on / off of the pneumatic valve. Argon (Ar), an inert gas, was used to purge the precursor compound and reaction gas, and the flow rate was set to 1,500 sccm.

[0222] (Precursor compound injection for 10 seconds) - (Purge gas injection for 20 seconds) - (Reaction gas injection for 10 seconds) - (Purge gas injection for 20 seconds) were performed sequentially, and this was considered one cycle.

[0223] The precursor compound temperature is 80 ℃.

[0224] The temperature of the canister was maintained at 80°C, the process temperature was set to 170°C to 320°C, and the number of cycles was 100 to deposit a gallium oxide film.

[0225]

[0226] [Example 2: Fabrication of In2O3 thin films using atomic layer deposition (ALD)]

[0227] An indium oxide film (In2O3) was manufactured through atomic layer deposition (ALD) using the InON precursor compound synthesized in Synthesis Example 2.

[0228] A thin film was deposited under the same conditions as Example 1, except that the precursor compound was InON.

[0229]

[0230] [Example 3: Fabrication of Al2O3 thin films using atomic layer deposition (ALD)]

[0231] An aluminum oxide film (Al2O3) was manufactured through atomic layer deposition (ALD) using the AlON precursor compound synthesized in Synthesis Example 3.

[0232] A thin film was deposited under the same conditions as Example 1, except that the precursor compound was InON.

[0233]

[0234] [Evaluation example]

[0235] [Evaluation Example 1: Thermogravimetric analysis (TGA) of precursor compound]

[0236] Thermogravimetric analysis of the compound of Example 1 was performed using a TG209 F1 Libra instrument from Netzsch.

[0237] 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.

[0238] The TGA measurement results of the precursor compound (GaON) of Synthesis Example 1 are shown in Figure 1.

[0239] As a result of thermogravimetric analysis, the half-life (T) of the precursor compound of Synthesis Example 1 is as shown in Fig. 1. 1 / 2, ℃) was 179 ℃. In addition, it was confirmed that the residual amount of the precursor compound of Synthesis Example 1 at 250 ℃ was 2.0%.

[0240]

[0241] [Evaluation Example 2: Thermal Characteristics of Precursor Compounds by Differential Scanning Calorimetry (DSC)]

[0242] Thermal properties of the precursor compound (GaON) of Synthesis Example 1 were analyzed.

[0243] The results of Differential Scanning Calorimetry (DSC) measurements are shown in Fig. 2.

[0244] As a result of differential scanning calorimetry (DSC) measurement of the thermal properties of the precursor compound of Synthesis Example 1, it was confirmed that the onset and peak temperatures were 227°C and 240°C, respectively.

[0245]

[0246] [Evaluation Example 3: Measurement of the deposition rate of a thin film]

[0247] A thin film was manufactured according to Example 1 while changing the process temperature in the range of 170 ℃ to 320 ℃ under the process conditions described in Example 1 above, and the deposition rate (Growth rate per cycle, GPC) of the thin film was measured, and the results are shown in Figure 3.

[0248] The deposition rate was calculated using the following mathematical formula 1.

[0249] [Mathematical Formula 1]

[0250] Deposition rate (Å / cycle) = deposition thickness / number of ALD cycles

[0251] The deposition thickness of the above mathematical expression 1 was measured using an ellipsometer and confirmed using FE-SEM.

[0252]

[0253] As shown in Fig. 3, at a process temperature of 230 ℃ to 260 ℃, a section (ALD window) in which the deposition rate is constant regardless of the process temperature was confirmed, so it was confirmed that when the compound of Synthesis Example 1 was used as a precursor, deposition was possible by the atomic layer deposition (ALD) method and a gallium metal thin film could be manufactured.

[0254] Additionally, it was confirmed that the deposition rate (Growth rate per cycle, GPC) was 0.427 or more and 1.654 or less. It was confirmed that the deposition rate was 0.95 Å at a temperature (ALD window) of 230 ℃ to 260 ℃.

[0255] Meanwhile, as shown in Fig. 3, a section in which the process temperature and deposition rate increase proportionally at temperatures of 170 ℃ ~ 220 ℃ and 270 ℃ ~ 320 ℃ appears, confirming that it shows a similar pattern to that deposited by chemical vapor deposition (CVD). Therefore, it was confirmed that the precursor compound of the present invention can also be used in chemical vapor deposition (CVD).

[0256] That is, it was confirmed that when the compound of the present invention was used as a precursor compound for deposition and deposition was performed by ALD, a thin film with excellent properties could be formed, and deposition by CVD was also possible.

[0257]

[0258] [Evaluation Example 4: Analysis of the step coverage of a thin film]

[0259] The step coverage of the gallium oxide film (Ga2O3) manufactured according to Example 1 at a process temperature of 230 ℃ to 260 ℃ was observed and analyzed using a transmission electron microscope (TEM).

[0260] TEM images of gallium oxide films fabricated in trench structures having an aspect ratio of 12:1 or 40:1 are shown in FIG. 4.

[0261] As shown in Fig. 4, it was confirmed that the gallium oxide film deposited using the compound of Example 1 had excellent step coverage.

[0262] The step coverage measurement results by TEM showed that B / T (Bottom / Top) was 98% and M / T (Middle / Top) was 97% in a trench with an aspect ratio of 12:1, and B / T was 85% and M / T was 88% in a trench with an aspect ratio of 40:1.

[0263] Meanwhile, B / T was calculated as (average thickness of the film deposited at the bottom of the trench / average thickness of the film deposited at the top of the trench)*100. In addition, M / T was calculated as (average thickness of the film deposited at the middle of the trench / average thickness of the film deposited at the top of the trench)*100.

[0264] The bottom part of the trench refers to the part corresponding to 0% to 10% of the vertical length from the bottom of the trench, the middle part refers to the part corresponding to 10% to 90% of the vertical length from the bottom of the trench, and the top part refers to the part corresponding to 90% to 100% of the vertical length from the bottom of the trench.

[0265]

[0266] [Evaluation Example 5: Density and Roughness Analysis of Thin Films]

[0267] The density and roughness of the gallium oxide film (Ga2O3) manufactured according to Example 1 at a process temperature of 230 ℃ to 260 ℃ were analyzed using X-ray reflectometry (XRR).

[0268] The results of XRR analysis of the gallium oxide film Ga2O3 manufactured according to Example 1 at a process temperature of 230 ℃ to 260 ℃ are shown in Fig. 5.

[0269] As shown in Fig. 5, the density of the manufactured oxide film is 5.18 g / cm 3 And, it was confirmed that the roughness was 0.7368 nm.

[0270]

[0271] [Evaluation Example 6: Composition Analysis of Thin Films]

[0272] The composition and impurity content of the gallium oxide film (Ga2O3) manufactured according to Example 1 at a process temperature of 230 ℃ to 260 ℃ were analyzed using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS).

[0273] As shown in Fig. 6, the XPS depth profile measurement results showed that gallium (Ga) was 48 atomic% and oxygen (O) was 52 atomic%, while impurities such as carbon, nitrogen, and hydrogen were not detected, and the ratio of oxygen and metal was 1:1 to 1:1.5.

[0274] That is, it was confirmed that the impurities (carbon, nitrogen, hydrogen, etc.) contained in the gallium oxide film were at a negligible level.

[0275] In addition, as shown in the SIMS measurement results in Fig. 7, the intensity of the secondary ions of carbon on the oxide film surface was 1.0 x 10 2 It was confirmed that the carbon concentration was very low, which means that there was little or no carbon contamination of the oxide film.

[0276]

[0277] As examined above, the compound of the present invention has excellent thermal and ALD properties, and it was confirmed that there are almost no impurities in the thin film manufactured using the compound of the present invention.

[0278] In addition, when the compound of the present invention is used as a precursor to form a thin film, it was confirmed that it has excellent step coverage even in a trench structure having an aspect ratio of 12:1 or 40:1.

[0279] Due to these excellent properties, a thin film deposited using the compound 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.

[0280]

[0281] 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.

[0282]

[0283] The novel compound according to the present invention and the precursor compound including the novel compound have excellent reactivity, volatility and thermal stability, are liquid, and enable uniform thin film deposition with excellent properties, thereby ensuring excellent thin film properties, thickness and step coverage.

[0284] The above properties provide a precursor suitable for atomic layer deposition and chemical vapor deposition.

Claims

A compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, M is Al, In, or Ga, R5 and R 10 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, which is substituted or unsubstituted, R1 to R4 and R6 to R9 are each independently hydrogen or a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 3 carbon atoms. In the first paragraph, R1 to R4 and R6 to R9 are each independently hydrogen, a methyl group, an ethyl group, an n-propyl group or an iso-propyl group, compound. In the first paragraph, R5 and R 10 are each independently 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, or an iso-hexyl group, compound. Comprising a compound of any one of claims 1 to 3, Precursor. Comprising the step of introducing a precursor comprising a compound of any one of claims 1 to 3 into a reactor, Method for manufacturing thin films. In paragraph 5, The method for manufacturing the above thin film includes atomic layer deposition (ALD) or chemical vapor deposition (CVD). Method for manufacturing thin films. In paragraph 5, further comprising the step of introducing an oxidizing agent, a nitriding agent, a reducing agent or a combination thereof into the reactor; Method for manufacturing thin films. In paragraph 5, The above thin film includes an oxide film, a nitride film, a metal film, or a combination thereof. Method for manufacturing thin films. A first step of producing a compound represented by the following chemical formula 4 by reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3; and A second step of producing a compound represented by the following chemical formula 6 by reacting a compound represented by the above chemical formula 4 with a compound represented by the following chemical formula 5; comprising; Method for preparing a compound. [Chemical Formula 2] [Chemical Formula 3] MX3 [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] In the above chemical formula 2, R 11 Inland R 21 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 3 carbon atoms, substituted or unsubstituted, In the above chemical formulas 2 to 4 and the above chemical formula 6, M is Al, In or Ga, X is a halogen element, In the above chemical formula 5 and chemical formula 6, R 27 and R 32 are each independently hydrogen or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, substituted or unsubstituted, R 23 Inland R 26 and R 28 Inland R 31 are each independently hydrogen, a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 3 carbon atoms.

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