Composition for thin film deposition containing a metal compound, method for producing a metal-containing thin film using the same, and metal-containing thin film produced using the same

Abstract

The present invention provides a composition for depositing a metal-containing thin film containing a metal compound, a method for manufacturing a metal-containing thin film using the composition, and a metal-containing thin film manufactured using the composition. When the composition is used, a high-quality metal-containing thin film containing uniform components can be manufactured at an improved deposition rate.

Description

[Technical Field]

[0001] The present invention relates to a composition for thin film deposition containing a metal compound, a method for producing a metal compound, a method for producing a metal-containing thin film using the same, and a metal-containing thin film produced using the same. [Background technology]

[0002] In recent years, the demand for thin-film display electronic elements such as liquid crystal displays and organic light-emitting diodes has increased sharply, leading to a demand for thin-film materials that exhibit excellent performance, including low power consumption, high resolution, and high reliability.

[0003] Silicon was previously the most commonly used thin film material for display electronic devices, but metal oxides are now being used, which have higher charge mobility and are easier to process at low temperatures than polycrystalline silicon. Metal oxides have a wide energy band gap and excellent light transmittance, and are expected to improve the uniformity and mobility of silicon, which are drawbacks of conventional silicon.

[0004] In particular, Group 13 metal oxides can be used as transparent oxide semiconductor materials and can also be applied to electrodes, conductive coating materials, etc. Among the Group 13 metals, indium and gallium are useful because they have excellent abrasion resistance and low resistance when in contact with aluminum electric wires.

[0005] When forming such metal thin films by sputtering using a sputter target, the composition of the deposited thin film is determined by the sputter target, so there is a limit to how uniform the composition of the thin film can be controlled, and it is difficult to maintain a uniform thin film composition and thickness when depositing a large area.

[0006] To overcome these problems, instead of sputtering, methods such as atomic layer deposition (ALD), chemical vapor deposition (CVD), and pulsed laser deposition (PLD) are being used to fabricate indium(III) chloride. The conventional metal precursor, indium(III) chloride, has the disadvantages of chlorine contamination during thin film deposition using methods such as atomic layer deposition, chemical vapor deposition, and pulsed laser deposition, and of requiring an external oxygen source. Furthermore, the commonly used trialkylindium(III) precursors, such as trimethylindium and triethylindium, are highly sensitive to oxygen and moisture and, because they are solids, can pose problems in controlling vapor pressure and reproducibility of uniform films.

[0007] Therefore, there is a need to develop a high-quality metal precursor that is halogen-free, has excellent thermal stability at high temperatures, and is highly volatile, in order to solve the above problems. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a composition for thin film deposition containing a metal compound that exhibits excellent volatility and thermal stability. Another object of the present invention is to provide a method for producing a metal compound.

[0009] It is another object of the present invention to provide a method for producing a thin film that can exhibit improved deposition rate and reproducibility by using the composition for thin film deposition. By using the composition for thin film deposition, the present invention provides a high-quality metal-containing thin film having a consistent composition and a uniform thickness. [Means for solving the problem]

[0010] The present invention provides a composition for thin film deposition, comprising a metal compound represented by the following Chemical Formula 1:

[0011] [Chemical formula 1] JPEG2025529153000002.jpg3040

[0012] [In the above Chemical Formula 1, M is In or Ga; --- is a single or double bond, R a ~R c are, independently of each other, C1-C7 alkyl; R1 to R8 are each independently hydrogen or C1-C7 alkyl; The aforementioned --- is a double bond, R1, R3, R5, and R7 are absent.

[0013] M in Chemical Formula 1 is In or Ga; --- is a single or double bond, and R a ~R c are each independently C1-C4 alkyl, and R1 to R8 may each independently be hydrogen or C1-C4 alkyl.

[0014] The metal compound according to one embodiment of the present invention may be represented by the following Chemical Formula 2:

[0015] [Chemical formula 2] JPEG2025529153000003.jpg2739

[0016] [In the above chemical formula 2, M is In or Ga; --- is a single or double bond, R is C1-C7 alkyl; R 11 ~R 14 are each independently hydrogen or C1-C7 alkyl.

[0017] M in the above Chemical Formula 2 is In or Ga; --- is a single or double bond, R is a C1-C4 alkyl, and R 11 ~R 14 may be, independently of each other, hydrogen or C1-C4 alkyl.

[0018] The metal compound according to one embodiment may be represented by the following Chemical Formula 3:

[0019] [Chemical formula 3] JPEG2025529153000004.jpg2637

[0020] [In the above Chemical Formula 3, M is In or Ga; R is C1-C3 alkyl; R 21 ~R 24 are each independently hydrogen or C1-C4 alkyl.

[0021] The present invention provides a method for producing a metal compound represented by the following Chemical Formula 1 according to one embodiment, specifically, the method includes the step of reacting compounds represented by the following Chemical Formulas 11 to 15 to produce the compound represented by the following Chemical Formula 1.

[0022] [Chemical formula 1] JPEG2025529153000005.jpg3040[Chemical formula 11] MX3 [Chemical formula 12] R a MgX a [Chemical formula 13] R b MgX b [Chemical formula 14] R c MgX c [Chemical formula 15] JPEG2025529153000006.jpg2231

[0023] [In the above Chemical Formula 1 and Chemical Formulas 11 to 15, M is In or Ga; --- is a single or double bond, R a ~R c are, independently of each other, C1-C7 alkyl; R1 to R8 are each independently hydrogen or C1-C7 alkyl; X, X a , X b , and X c are, independently of each other, halogen, The aforementioned --- is a double bond, R1, R3, R5, and R7 are absent.

[0024] The method for preparing a metal compound according to an embodiment of the present invention may further include, after the step of preparing the compound of Formula 1, adding a polar solvent and stirring the mixture. The amount of polar solvent to be added may be 2 to 5 equivalents relative to the compound represented by Chemical Formula 1.

[0025] The present invention provides a method for producing a metal-containing thin film using a metal compound or a composition for thin film deposition containing the same according to one embodiment. The method for producing a metal-containing thin film may include the steps of: a) increasing the temperature of a substrate mounted in a chamber; b) injecting the metal compound or a thin film deposition composition containing the metal compound into the chamber and allowing it to be adsorbed onto the substrate; and c) injecting a reaction gas into the substrate on which the metal compound or the thin film deposition composition containing the metal compound has been adsorbed, thereby producing a metal-containing thin film, and the temperature of the substrate may be 100 to 450°C.

[0026] The present invention provides a metal-containing thin film prepared using a metal compound or a composition for thin film deposition including the same according to one embodiment of the present invention. The metal-containing thin film may have a metal content of 20 to 60% by weight. [Effects of the Invention]

[0027] The composition for thin film deposition containing the metal compound of the present invention contains a metal compound having a specific structure, and thus can exhibit high volatility and have excellent thermal stability and storage stability.

[0028] The method for producing a metal compound according to one embodiment of the present invention can produce the compound of Formula 1 in high purity as well as in high yield through simple steps.

[0029] The method for manufacturing a metal-containing thin film of the present invention employs the composition for thin film deposition of the present invention, thereby exhibiting improved deposition rates and uniform step coverage for three-dimensional devices. Furthermore, the metal-containing thin film manufactured using the composition for thin film deposition of the present invention has uniform components and thickness and exhibits excellent electrical performance. [Brief explanation of the drawings]

[0030] [Figure 1] FIG. 1 shows the results of TGA analysis of Example 2 of the present invention and [(3-dimethylamino)propyl]dimethylindium (DADI). [Figure 2] FIG. 1 is a diagram showing the results of vapor pressure measurement of Example 2 of the present invention and [(3-dimethylamino)propyl]dimethylindium (DADI). [Figure 3] FIG. 1 is a graph showing the results of measuring the thermal stability of Example 2 of the present invention and [(3-dimethylamino)propyl]dimethylindium (DADI). [Figure 4] FIG. 1 is a graph showing deposition rates as a function of precursor injection time in Example 3 and Comparative Example 1. [Figure 5] FIG. 1 is a graph showing deposition rates as a function of the vapor pressure of precursors in Example 3 and Comparative Example 1. [Figure 6] FIG. 10 is a graph showing the deposition rate as a function of the temperature of the silicon substrate in Example 3 and Comparative Example 1. [Figure 7] FIG. 10 is a diagram showing deposition thicknesses according to process cycles in Example 3 and Comparative Example 1. [Figure 8]FIG. 1 shows XRD patterns of Example 3 and Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0031] Hereinafter, the composition for thin film deposition containing the metal compound of the present invention, the method for producing a metal-containing thin film using the composition, and the metal-containing thin film produced using the composition will be described in detail.

[0032] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise. Furthermore, the numerical ranges used in the present invention include the lower limit and upper limit, all values ​​within the range, increments logically derived from the form and width of the defined range, all values ​​limited therein, and all possible combinations of the upper and lower limits of numerical ranges limited in different forms. Unless otherwise specified in the specification of the present invention, values ​​outside the numerical range that may occur due to experimental error or rounding off of values ​​are also included in the defined numerical range.

[0033] The term "comprising" as used herein is an open-ended term having the same meaning as terms such as "comprising," "containing," "having," or "featuring," and does not exclude additional, unrecited elements, materials, or steps.

[0034] The number of carbon atoms described in the present invention does not include the number of carbon atoms of the substituents. For example, C1-C7 alkyl means an alkyl having 1 to 7 carbon atoms, not including the number of carbon atoms of the alkyl substituents.

[0035] The present invention will be described in detail below. In this regard, unless otherwise defined, the technical and scientific terms used have the meanings that are commonly understood by those of ordinary skill in the art to which the present invention pertains, and in the following description, descriptions of known functions and configurations that unnecessarily obscure the gist of the present invention will be omitted.

[0036] The present invention provides a composition for thin film deposition, comprising a metal compound represented by the following Chemical Formula 1:

[0037] [Chemical formula 1] JPEG2025529153000007.jpg3040

[0038] [In the above Chemical Formula 1, M is In or Ga; --- is a single or double bond, R a ~R c are, independently of each other, C1-C7 alkyl; R1 to R8 are each independently hydrogen or C1-C7 alkyl; The aforementioned --- is a double bond, R1, R3, R5, and R7 are absent.

[0039] To the extent that the metal compound represented by Formula 1 may have a chiral center, the compound may be used in optically pure form or may be provided as a diastereomeric or racemic mixture, the term "racemic mixture" meaning a mixture of equal proportions of two enantiomers.

[0040] The metal compound may have a single evaporation step at 50° C. or higher, and the residue mass at 500° C. may be 0.001 to 1 wt %, specifically 0.01 to 0.9 wt %, and more specifically 0.1 to 0.7 wt %. The metal compound has higher volatility and improved vapor pressure, and therefore can exhibit a high deposition rate. It is also a compound with improved thermal stability, excellent stability during storage, and easy to handle.

[0041] M in the above Chemical Formula 1 is In or Ga; --- is a single or double bond, and R a ~R care each independently C1-C4 alkyl, and R1 to R8 may each independently be hydrogen or C1-C4 alkyl.

[0042] In detail, in the metal compound represented by Chemical Formula 1, M is In or Ga; --- is a single or double bond, and R a ~R c are each independently a C1-C3 alkyl, and R1 to R8 may each independently be hydrogen or a C1-C3 alkyl.

[0043] The metal compound according to one embodiment of the present invention may be represented by the following Chemical Formula 2:

[0044] [Chemical formula 2] JPEG2025529153000008.jpg2739

[0045] [In the above chemical formula 2, M is In or Ga; --- is a single or double bond, R is C1-C7 alkyl; R 11 ~R 14 are each independently hydrogen or C1-C7 alkyl.

[0046] JPEG2025529153000009.jpg36170

[0047] M in the above Chemical Formula 2 is In or Ga; --- is a single or double bond, R is a C1-C4 alkyl, and R 11 ~R 14 may be, independently of each other, hydrogen or C1-C4 alkyl.

[0048] The metal compound according to one embodiment may be represented by the following Chemical Formula 3:

[0049] [Chemical formula 3] JPEG2025529153000010.jpg2637

[0050] [In the above Chemical Formula 3, M is In or Ga; R is C1-C3 alkyl; R 21 ~R 24 are each independently hydrogen or C1-C4 alkyl.

[0051] The present invention also provides a method for producing a metal compound represented by the following chemical formula 1 according to one embodiment, specifically, the method includes reacting compounds represented by the following chemical formulas 11 to 15 to produce the metal compound represented by the following chemical formula 1.

[0052] [Chemical formula 1] JPEG2025529153000011.jpg3040[Chemical formula 11] MX3 [Chemical formula 12] R a MgX a [Chemical formula 13] R b MgX b [Chemical formula 14] R c MgX c [Chemical formula 15] JPEG2025529153000012.jpg2231

[0053] [In the above Chemical Formula 1 and Chemical Formulas 11 to 15, M is In or Ga; --- is a single or double bond, R a ~R c are, independently of each other, C1-C7 alkyl; R1 to R8 are each independently hydrogen or C1-C7 alkyl; X, X a , X b , and X care, independently of each other, halogen, The aforementioned --- is a double bond, R1, R3, R5, and R7 are absent.

[0054] Specifically, the step of preparing the compound of Chemical Formula 1 may be carried out by adding a solvent to the compound represented by Chemical Formula 11, and then adding the compounds represented by Chemical Formulas 12 to 15 at 0 to 30°C, followed by reacting at 5 to 50°C for 1 to 15 hours, specifically at 10 to 40°C for 1 to 12 hours, more specifically at 15 to 35°C for 1 to 10 hours. In another embodiment, Chemical Formulas 12 to 14 may be the same compound, or may be a Grignard reagent contained in a solution of Chemical Formula 15.

[0055] The method for producing a metal compound according to one embodiment of the present invention may further include a step of adding a polar solvent and stirring the mixture after the step of reacting the compounds of Chemical Formulas 11 to 15 to produce the compound of Chemical Formula 1.

[0056] The polar solvent according to one embodiment of the present invention may be one or more selected from acetonitrile, DMSO (Dimethylsulfoxide), DMF (Dimethylformamide), and THF (Tetrahydrofuran), and may specifically be DMF (Dimethylformamide), THF (Tetrahydrofuran), or a mixture thereof, and more specifically may be THF (Tetrahydrofuran), but is not limited thereto.

[0057] Furthermore, the amount of the polar solvent according to one embodiment of the present invention may be 2 to 5 equivalents, specifically 2 to 4.5 equivalents, and more specifically 2 to 4 equivalents, relative to the compound represented by Chemical Formula 11.

[0058] During the preparation of the metal compounds, MgCl precipitate may be generated, which is considered a reaction by-product that is not easily removed by filtration due to its small particle size, requires long filtration times, and can significantly reduce the purity and yield of the final compound.

[0059] Therefore, according to the method for producing a metal compound of the present invention, when the method includes a step of adding a polar solvent to the generated MgCl precipitate, particularly a step of adding an excess amount of polar solvent, the metal compound represented by Chemical Formula 1 can be easily separated with high purity.

[0060] This is because a complex compound of polar solvent and MgCl2 is produced, which not only makes it easy to separate the by-products from the metal compound, but also results in a high purity and yield of the metal compound.

[0061] Specifically, when a polar solvent such as THF is used, MgCl2(THF) n It is expected that complex compounds of the form (n=2, 3) will be formed. Compounds formed with such complex compounds have significantly improved filterability, and it is believed that the purity and yield of the final product can be significantly improved by easily filtering and removing these complex compounds.

[0062] In the method for producing a metal compound according to one embodiment of the present invention, a polar solvent may be added to the reaction products of Chemical Formulas 11 to 15 and stirred for 0.5 to 5 hours. In addition, in the step of reacting the compounds of Chemical Formulas 11 to 15 to prepare the compound of Chemical Formula 1, any common organic solvent can be used as the solvent, and the solvent may be one or more selected from hexane, pentane, DCM (dichloromethane), benzene, and toluene, but is not limited thereto.

[0063] Each reaction in the above preparation method may be terminated after confirming that the starting materials are completely consumed by NMR. After the reaction is completed, the compound may be separated and purified by a conventional method such as extraction, distillation of the solvent under reduced pressure, or column chromatography.

[0064] The method for producing a metal compound can produce a metal compound with high yield and high purity through a mild and simple process, and is therefore easily applicable to industrial applications.

[0065] The metal compound can maintain a constant vapor pressure during the deposition process, thereby maintaining a constant composition of the thin film, thereby enabling the production of a uniform thin film with consistent components.In addition, the film has a uniform thickness and exhibits excellent step coverage, allowing the production of a thin film with excellent physical properties even in a three-dimensional device.

[0066] The present invention provides a method for producing a metal-containing thin film using a metal compound or a composition for thin film deposition containing the same according to one embodiment. The method for manufacturing a metal-containing thin film according to an embodiment of the present invention may be used to manufacture a multi-layered thin film containing different metals. The thin film may have a layered structure formed by sequentially depositing the metal compound or the composition for depositing a metal-containing thin film and a precursor of the different metal, or may be formed by depositing a mixture of the metal compound or the composition for depositing a metal-containing thin film and a precursor of the different metal.

[0067] The method for manufacturing the metal-containing thin film may include the steps of: a) increasing the temperature of a substrate mounted in a chamber; b) injecting a metal compound or the thin film deposition composition according to an embodiment of the present invention into the chamber and allowing it to be adsorbed onto the substrate; and c) injecting a reaction gas into the substrate on which the metal compound or the thin film deposition composition has been adsorbed, thereby manufacturing the metal-containing thin film.

[0068] The reactive gas may be any one or more selected from oxygen (O2), ozone (O3), water vapor (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amines, diamines, hydrogen (H2), argon (Ar), and helium (He), and the transfer gas is an inert gas and may be any one or more selected from argon (Ar), helium (He), and nitrogen (N2), specifically, but not limited to, nitrogen (N2).

[0069] Furthermore, in the method for producing a metal-containing thin film according to one embodiment of the present invention, the steps b) and c) are considered as one cycle, and the cycle may be repeated until a metal-containing thin film of the desired thickness is produced. Specifically, the cycle may be 50 to 5,000 cycles, and more specifically, the cycle may be 200 to 2,000 cycles, but is not limited to this.

[0070] The temperature of the substrate in step a) may be 100 to 450° C., specifically 150 to 300° C., and more specifically 150 to 250° C. The composition for thin film deposition according to one embodiment of the present invention can be deposited without thermal decomposition of the metal compound even at such high temperatures, thereby improving stability and productivity in the deposition process.

[0071] Furthermore, the metal-containing thin film manufactured by the method for manufacturing a metal-containing thin film has a significantly reduced content of impurities such as carbon, making it possible to manufacture a high-quality metal-containing thin film.

[0072] The substrate used in the method for manufacturing a metal-containing thin film according to an embodiment may include, but is not limited to, one or more base materials selected from glass, silicon, metallic polyester (PE), polyethyleneterephthalate (PET), polyethylenenapthalate (PEN), polycarbonate (PC), polyetherimide (PEI), polyethersulfone (PES), polyetheretherketone (PEEK), and polyimide (PI).

[0073] In step b) of the method for producing a metal-containing thin film according to an embodiment, the composition for depositing a metal-containing thin film may be filled into a stainless steel bubbler vessel and maintained at a temperature of 20 to 100°C, specifically 30 to 90°C, more specifically 40 to 70°C.

[0074] In addition, the conditions for the deposition process in step b) may be adjusted depending on the structure and thermal properties of the thin film. According to one embodiment, the metal compound supply flow rate may be adjusted to 1 to 1,000 sccm using a bubbler, the transfer gas supply flow rate may be adjusted to 1 to 5,000 sccm, and the reaction gas supply flow rate may be adjusted to 10 to 5,000 sccm. The pressure may be adjusted to a range of 0.1 to 10 Torr, and the injection time may be, but is not limited to, 0.1 to 20 seconds, preferably 0.1 to 15 seconds, and more preferably 0.1 to 10 seconds. When a metal-containing thin film is produced within the above ranges, the thickness uniformity of the thin film is significantly improved, thereby maintaining excellent step coverage even on substrates with complex shapes.

[0075] The method for manufacturing a metal-containing thin film according to an embodiment may further include purging with a carrier gas to remove any unadsorbed metal compound or a thin film deposition composition containing the same, or to remove reaction by-products and residual reaction gases generated after injection of the reaction gas.

[0076] The method for producing an indium-containing thin film according to an embodiment of the present invention may be performed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), plasma-enhanced atomic layer deposition (PEALD), or pulsed laser deposition (PLD), and preferably by atomic layer deposition (ALD), chemical vapor deposition (CVD), or metalorganic chemical vapor deposition (MOCVD).

[0077] The present invention provides a metal-containing thin film prepared using a metal compound or a composition for thin film deposition including the same according to one embodiment of the present invention, and the metal-containing thin film has uniform components and can exhibit excellent electrical performance. The metal-containing thin film may have a metal content of 20 to 60% by weight.

[0078] Hereinafter, the metal compound according to the present invention, the composition for thin film deposition containing the same, the method for manufacturing a metal-containing thin film using the same, and the metal-containing thin film manufactured using the same will be described in more detail with reference to specific examples.

[0079] However, the following examples are merely one reference for describing the present invention in detail, and the present invention is not limited thereto and may be realized in various forms. Furthermore, the terms used in the description of the present invention are merely for effectively describing specific examples and are not intended to limit the present invention.

[0080] Also, unless otherwise noted, all examples were carried out under an inert atmosphere, e.g., purified nitrogen (N) or argon (Ar), using techniques commonly known in the art for handling air-sensitive materials, e.g., "Schlenk techniques."

[0081] [Example 1] Production of indium compound (InMe3(THF)) 100 g (0.45 mol) of InCl3 was added to a 5 L three-neck flask equipped with a stirrer and a reflux condenser and then vacuum dried. 1000 ml of n-hexane was added, and 452 ml of MeMgCl (3.0 M solution in THF) was slowly added while maintaining the temperature at 10°C. The mixture was stirred at room temperature for 8 hours to produce a pale gray precipitate. The reaction mixture was then filtered, and the solvent and volatile by-products were removed from the filtrate under reduced pressure. Vacuum distillation (23°C, 0.8 Torr) yielded 37.1 g of the metal compound as a colorless liquid (35% yield).

[0082] 1 H NMR(400MHz, C6D6)δ 3.2(m, 4H), 1.1(m, 4H), -0.1(s, 9H)

[0083] [Example 2] Production of indium compound (InMe3(THF)) 100g (0.45mol) of InCl3 was added to a 5L three-neck flask equipped with a stirrer and a reflux condenser and then vacuum dried. 1000ml of n-hexane was added, and while maintaining the temperature at 10°C, 52ml of MeMgCl4 (3.0M solution in THF) was slowly added and stirred at room temperature for 8 hours. After the reaction was completed, an additional 3 equivalents of THF was added to the reaction mixture at room temperature, stirred for 2 hours, and filtered. The solvent and volatile by-products were removed from the filtrate under reduced pressure, and the mixture was subjected to vacuum distillation (23°C, 0.8 Torr) to obtain 77.3g of the metal compound as a colorless liquid (73% yield).

[0084] 1 H NMR(400MHz, C6D6)δ 3.2(m, 4H), 1.1(m, 4H), -0.1(s, 9H)

[0085] Figure 1 shows the TGA graph of the metal compound InMe3(THF) of Example 2. Comparing it with the TGA graph of [(3-dimethylamino)propyl]dimethylindium (hereinafter referred to as DADI, DOCK / CHEMICALS), which is commonly used in the deposition of indium-containing thin films, it was found that this metal compound has a single evaporation step starting at about 50°C, with the temperature at which half the weight is lost being 12°C lower than DADI, and the residual mass at 500°C was confirmed to be 0.4%. These results show that the metal compound of Example 2 of the present invention exhibits faster evaporation characteristics than DADI, evaporating at over 99% without thermal decomposition.

[0086] To confirm the improved vapor pressure characteristics of Example 2 (InMe3(THF)), the vapor pressure was measured and compared with that of DADI, as shown in Figure 2. As shown in FIG. 2, the vapor pressure measurement confirmed that the vapor pressure of Example 2 (InMe(THF)) (26°C, 1 Torr) was significantly higher than that of DADI (41°C, 1 Torr).

[0087] These results demonstrate that the use of Example 2 (InMe3(THF)) to deposit indium-containing thin films by chemical vapor deposition (CVD) or atomic layer deposition (ALD) is significantly more advantageous than conventional indium precursors.

[0088] In a glove box under an argon atmosphere, a specified volume (3 g) of Example 2 (InMe3(THF)) and DADI were placed in a sealable stainless steel container and sealed. After storing the container at a specified temperature (100°C, 120°C) and time (1 day, 4 days, 7 days), each sample was 1 The thermal stability of Example 2 (InMe3(THF)) and DADI was measured by analyzing with H NMR to confirm changes in peaks, and the results are shown in Figure 3.

[0089] As shown in Figure 3, it was found that both Example 2 (InMe3(THF)) and DADI were stable without showing any change up to 7 days at 100°C. However, at 120°C, Example 2 (InMe3(THF)) of the present invention showed no change, whereas it was confirmed that DADI began to produce by-products from the 4th day.

[0090] This shows that Example 2 (InMe3(THF)) of the present invention has significantly better stability under high temperature conditions than DADI, which is widely used for deposition of indium-containing thin films.

[0091] [Example 3] Production of indium oxide thin film Using InMe3(THF) according to Example 2 and nitrous oxide (N2O) as a reactant gas, an indium-containing oxide thin film was fabricated by plasma-enhanced atomic layer deposition (PEALD).

[0092] A silicon substrate was loaded into the deposition chamber and the temperature of the substrate was maintained at a constant temperature. A stainless steel bubbler vessel was filled with InMe3(THF) and maintained at a temperature corresponding to a constant vapor pressure.

[0093] Using argon gas as a carrier gas, the InMe3(THF) precursor was injected into the deposition chamber for a certain period of time to allow adsorption, and then purged with argon gas (600 sccm) for 3 seconds to remove the InMe3(THF) and reaction by-products remaining in the deposition chamber.

[0094] Nitrous oxide (NO) was injected as a reactive gas and an indium-containing oxide thin film was formed using plasma. After that, argon gas (600 sccm) was used for 3 seconds to purge the remaining reactive gas and reaction by-products.

[0095] The above-described process was counted as one cycle and 70 to 700 cycles were performed to manufacture an indium-containing oxide thin film, and the thickness of the deposited indium oxide thin film was measured using an ellipsometer. Table 1 below shows the deposition conditions for the indium oxide thin film.

[0096] [Comparative Example 1] Production of indium oxide thin film Metal-containing oxide thin films were fabricated by plasma-enhanced atomic layer deposition (PEALD) using DADI, which is currently widely used for the fabrication of indium-containing thin films, and nitrous oxide (N2O) as the reactive gas. The indium oxide thin film was formed in the same manner as in Example 3, except that DADI was used as the precursor. The deposition conditions for the indium oxide thin film are shown in Table 1 below.

[0097] [Table 1]

[0098] Figure 4 shows the deposition rate per cycle as a function of precursor injection time for Example 3 and Comparative Example 1. The deposition rates for Example 3 and Comparative Example 1 tend to increase as the injection time increases due to physical adsorption, but for injection times of 0.3 seconds or longer, the deposition rate saturates and barely increases. In particular, Example 3 exhibits a deposition rate that is significantly improved by more than 40% compared to Comparative Example 1.

[0099] Figure 5 shows the deposition rate per cycle as a function of the vapor pressure of the precursor for Example 3 and Comparative Example 1. It can be seen that the vapor pressure of the precursor for Example 3 and Comparative Example 1 stabilizes at 1 Torr or higher. In particular, Example 3 shows a relatively constant deposition rate even at a high vapor pressure of 12 Torr, confirming the self-limited reaction characteristic of ALD. Furthermore, as with the previous results, it can be seen that Example 3 also shows a significant improvement of 40% or more in the deposition rate as a function of vapor pressure compared to Comparative Example 1.

[0100] 6 shows the deposition rate per cycle as a function of the silicon substrate temperature for Example 3 and Comparative Example 1. As with the previous results, it can be seen that Example 3 exhibits a deposition rate that is 40% or more higher than Comparative Example 1 as a function of the silicon substrate temperature, demonstrating a significantly improved deposition rate.

[0101] Figure 7 shows the thin film thickness as a function of the process cycle for Example 3 and Comparative Example 1. It can be seen that the thickness increases linearly with increasing process cycle, confirming the self-limited reaction characteristic of ALD. Furthermore, the deposition rate, as can be seen from the slope of the graph of thickness as a function of deposition cycle, is significantly improved compared to the 0.65 Å cycle for Comparative Example 1, at 1.0 Å for Example 3.

[0102] Figure 8 shows the XRD patterns of Example 3 and Comparative Example 1. Specific deposition conditions were a silicon substrate temperature of 200°C, precursor injection for 0.5 seconds, plasma-assisted step of nitrous oxide (NO) at 400 sccm and 400 W power for 3 seconds, and purge step of argon at 600 sccm for 3 seconds each. Each thin film was formed to a thickness of approximately 350 Å by adjusting the process cycle.

[0103] It was confirmed that the deposited indium-containing oxide thin film had a cubic structure, and the composition and film density results of XPS and XRR analysis of the indium oxide thin film are shown in Table 2. As shown in Table 2, it was found that a pure indium oxide thin film was formed without any carbon or nitrogen impurities, and the film density was 7.3 g / m 3 and the bulk density is 7.2 g / m 3 was confirmed to be similar to

[0104] [Table 2]

[0105] This indicates that the metal compound according to one embodiment of the present invention is a liquid compound and has significantly improved thermal stability, high volatility, and high vapor pressure. Furthermore, when a thin film is prepared from a thin film deposition composition containing the metal compound, the deposition thickness per cycle is approximately 40% higher than that of the commercially available material [(3-dimethylamino)propyl]dimethylindium (DADI). The use of an embodiment of the present invention also indicates a significantly improved deposition rate, enabling the formation of a thin film with highly reliable uniform components.

[0106] When the composition for thin film deposition of the present invention is used, a thin film of uniform thickness can be provided for a three-dimensional device, a thin film having an appropriate composition ratio of metal and oxygen can be produced, and the process time can be reduced, allowing for very economical thin film production.

[0107] Although the present invention has been described above with specific details and limited examples and comparative examples, these are merely provided for a more general understanding of the present invention, and the present invention is not limited to the above examples. Those skilled in the art will appreciate that various modifications and variations can be made from such descriptions.

[0108] Therefore, the spirit of the present invention should not be limited to the described embodiments, and it can be said that not only the scope of the claims below, but also anything that has equivalent or equivalent modifications to the scope of these claims falls within the scope of the spirit of the present invention.

Claims

1. A composition for thin film deposition comprising a metal compound represented by the following Chemical Formula 1: [Chemical formula 1] [In the above Chemical Formula 1, M is In or Ga; --- is a single or double bond, R ａ ~R ｃ are each independently C1-C7 alkyl; R １ ~R ８ are each independently hydrogen or C1-C7 alkyl; --- is a double bond, R １ , R ３ , R ５ , and R ７ does not exist.]

2. In the formula 1, M is In or Ga; --- is a single or double bond, R ａ ~R ｃ are each independently C1-C4 alkyl; R １ ~R ８ are each independently hydrogen or C1-C4 alkyl.

3. The composition for thin film deposition according to claim 1 , wherein the metal compound is represented by the following Chemical Formula 2: [Chemical formula 2] [In the above chemical formula 2, M is In or Ga; --- is a single or double bond, R is C1-C7 alkyl; R １１ ~R １４ are each independently hydrogen or C1-C7 alkyl.

4. M in Formula 2 is In or Ga; --- is a single or double bond, R is C1-C4 alkyl; R １１ ~R １４ are each independently hydrogen or C1-C4 alkyl.

5. The composition for thin film deposition according to claim 1 , wherein the metal compound is represented by the following Chemical Formula 3: [Chemical formula 3] [In the above chemical formula 3, M is In or Ga; R is C1-C3 alkyl; R ２１ ~R ２４ are each independently hydrogen or C1-C4 alkyl.

6. A method for producing a metal compound represented by the following Chemical Formula 1, comprising the step of reacting compounds represented by the following Chemical Formulas 11 to 15 to produce a compound represented by the following Chemical Formula 1: [Chemical formula 1] [Chemical formula 11] MX ３ [Chemical formula 12] R ａ MgX ａ [Chemical formula 13] R ｂ MgX ｂ [Chemical formula 14] R ｃ MgX ｃ [Chemical formula 15] [In the above Chemical Formula 1 and Chemical Formulas 11 to 15, M is In or Ga; --- is a single or double bond, R ａ ~R ｃ are each independently C1-C7 alkyl; R １ ~R ８ are each independently hydrogen or C1-C7 alkyl; X, X ａ , X ｂ , and X ｃ are, independently of each other, halogen, --- is a double bond, R １ , R ３ , R ５ , and R ７ does not exist.]

7. The method for producing a metal compound according to claim 6 , further comprising the step of adding a polar solvent and stirring the mixture after the step of producing the compound of Chemical Formula 1.

8. 8. The method for producing a metal compound according to claim 7, wherein the polar solvent is used in an amount of 2 to 5 equivalents relative to the compound of Formula 1.

9. A method for producing a metal-containing thin film using a metal compound represented by the following Chemical Formula 1 or a composition for thin film deposition containing the same: [Chemical formula 1] In the above Chemical Formula 1, M, ---, R ａ ~R ｃ , and R １ ~R ８ is as defined in claim 1.

10. a) raising the temperature of a substrate mounted in a chamber; b) injecting the metal compound or a composition for thin film deposition containing the metal compound into the chamber and allowing it to be adsorbed onto a substrate; c) injecting a reaction gas onto the substrate onto which the metal compound or the thin film deposition composition containing the metal compound is adsorbed to form a metal-containing thin film; The method for producing a metal-containing thin film according to claim 9, comprising:

11. The method for producing a metal-containing thin film according to claim 10, wherein the temperature of the substrate is 100 to 450°C.

12. A metal-containing thin film prepared using a metal compound represented by the following Chemical Formula 1 or a composition for thin film deposition containing the same: [Chemical formula 1] In the above Chemical Formula 1, M, ---, R ａ ~R ｃ , and R １ ~R ８ is as defined in claim 1.

13. The metal-containing thin film of claim 12, wherein the metal content is 20 to 60 wt %.

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