Composition for thin film deposition containing metal compound, method for manufacturing metal-containing thin film using same, and metal-containing thin film

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 by the method, with which a high-quality metal-containing thin film containing a uniform component 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 preparing the metal compound, a method for manufacturing a metal-containing thin film using the composition, and a metal-containing thin film manufactured using the composition. Background Art

[0002] In recent years, the demand for thin-film display electronic components such as liquid crystal displays and organic light-emitting diodes has increased dramatically, and with it has arisen a demand for thin-film materials that have low power consumption, high pixel count, high reliability, and excellent performance.

[0003] In the past, silicon was the most widely used thin film material for display electronic components, but now metal oxides are used, which have higher charge mobility and are easier to process at low temperatures than polysilicon. Metal oxides have a wide energy band gap and excellent light transmittance, so they are expected to improve uniformity and mobility, which are the shortcomings of conventional silicon.

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

[0005] When a metal film as described above is formed by sputtering using a sputtering target, the composition of the deposited film is determined by the sputtering target, so there are limitations in uniformly adjusting the composition of the film, and when depositing over a large area, it is difficult to maintain uniform film composition and uniform thickness.

[0006] Therefore, in order to overcome the above problems, methods such as atomic layer deposition (ALD), chemical vapor deposition (CVD) and pulsed laser deposition (PLD) are used to replace sputtering for manufacturing. Indium chloride (III) used as a metal precursor in the past may be contaminated by chlorine when thin film deposition is performed by atomic layer deposition, chemical vapor deposition and pulsed laser deposition, and there is a disadvantage of requiring an external oxygen source. In addition, trialkyl indium (III) precursors such as trimethyl indium and triethyl indium, which were widely used in the past, are very sensitive to oxygen and moisture, and because they are solid, problems may arise in terms of vapor pressure regulation and the reproducibility of uniform films.

[0007] Therefore, as a substance that can solve the above-mentioned problems, it is necessary to develop a high-quality metal precursor that does not contain halogen, has excellent thermal stability at high temperatures, and has high volatility. Summary of the invention

[0008] Problem that the invention aims to solve

[0009] An object of the present invention is to provide a composition for thin film deposition, which contains a metal compound showing excellent volatility and thermal stability.

[0010] Another object of the present invention is to provide a method for preparing the metal compound.

[0011] Another object of the present invention is to provide a method for manufacturing a thin film, which can show improved deposition rate and reproducibility using the composition for thin film deposition.

[0012] The present invention provides a high-quality metal-containing thin film which uses the composition for thin film deposition to have a prescribed composition and exhibit a uniform thickness.

[0013] Means used to solve problems

[0014] The present invention provides a composition for thin film deposition, which includes a metal compound represented by the following Chemical Formula 1.

[0015] [Chemical formula 1]

[0016]

[0017] [In the chemical formula 1,

[0018] M is In or Ga;

[0019] is a single bond or a double bond;

[0020] R a To R c are independently C1-C7 alkyl;

[0021] R1 to R8 are independently hydrogen or C1-C7 alkyl;

[0022] When the When it is a double bond, R1, R3, R5 and R7 do not exist.]

[0023] M in the chemical formula 1 may be In or Ga, is a single bond or a double bond, R a To R c are independently C1-C4 alkyl, and R1 to R8 are independently hydrogen or C1-C4 alkyl.

[0024] The metal compound according to one embodiment of the present invention may be represented by the following Chemical Formula 2.

[0025] [Chemical formula 2]

[0026]

[0027] [In the chemical formula 2,

[0028] M is In or Ga;

[0029] is a single bond or a double bond;

[0030] R is a C1-C7 alkyl group;

[0031] R 11 To R 14 are independently hydrogen or C1-C7 alkyl.]

[0032] M in the chemical formula 2 may be In or Ga. is a single bond or a double bond, R is a C1-C4 alkyl group, R 11 To R 14 are independently hydrogen or C1-C4 alkyl.

[0033] The metal compound according to one embodiment may be represented by Chemical Formula 3 below.

[0034] [Chemical formula 3]

[0035]

[0036] [In the chemical formula 3,

[0037] M is In or Ga;

[0038] R is a C1-C3 alkyl group;

[0039] R 21 To R 24 are independently hydrogen or C1-C4 alkyl.]

[0040] The present invention provides a method for preparing a metal compound represented by the following Chemical Formula 1 according to one embodiment, specifically comprising the following steps: preparing a compound represented by the following Chemical Formula 1 by reacting compounds represented by the following Chemical Formulas 11 to 15.

[0041] [Chemical formula 1]

[0042]

[0043] [Chemical formula 11]

[0044] MX3

[0045] [Chemical formula 12]

[0046] R a MgX a

[0047] [Chemical formula 13]

[0048] R b MgX b

[0049] [Chemical formula 14]

[0050] R c MgX c

[0051] [Chemical formula 15]

[0052]

[0053] [In the chemical formula 1 and chemical formulas 11 to 15,

[0054] M is In or Ga;

[0055] is a single bond or a double bond;

[0056] R a To R c are independently C1-C7 alkyl;

[0057] R1 to R8 are independently hydrogen or C1-C7 alkyl;

[0058] X, X a , X b and X c are independently halogen;

[0059] When the is a double bond, then R1, R3, R5 and R7 do not exist.]

[0060] According to an embodiment of the present invention, the method for preparing a metal compound may further include, after the step of preparing the chemical formula 1, a step of adding a polar solvent and stirring.

[0061] The amount of the polar solvent fed may be 2 to 5 equivalents relative to the compound represented by Chemical Formula 1.

[0062] The present invention provides a method for manufacturing a metal-containing thin film using a metal compound or a composition for thin film deposition including the same according to one embodiment.

[0063] The method for manufacturing the metal-containing film may include: step a), heating a substrate installed in a chamber, step b), injecting the metal compound or a composition for thin film deposition containing the metal compound into the chamber to adsorb it onto the substrate, and step c), injecting a reaction gas into the substrate adsorbed with the metal compound or the composition for thin film deposition containing the metal compound to manufacture the metal-containing film; and the temperature of the substrate may be 100 to 450°C.

[0064] The present invention provides a metal-containing thin film produced using the metal compound according to one embodiment of the present invention or a composition for thin film deposition containing the same.

[0065] The metal content of the metal-containing film may be 20 to 60 wt %.

[0066] Effects of the Invention

[0067] The thin film deposition composition containing a metal compound of the present invention exhibits high volatility by containing a metal compound having a specific structure, and can have excellent thermal stability and storage stability.

[0068] According to the method for preparing a metal compound according to one embodiment of the present invention, a high yield can be obtained through a simple process, and the compound of Chemical Formula 1 can be prepared with high purity.

[0069] The method for manufacturing a metal-containing thin film of the present invention can show an improved deposition rate by using the thin film deposition composition of the present invention, and can provide a uniform step coverage for a three-dimensional device. In addition, the metal-containing thin film manufactured using the thin film deposition composition of the present invention can have a uniform composition and a uniform thickness, and can show excellent electrical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 It is a graph showing the TGA analysis results of Example 2 of the present invention and [(3-dimethylamino)propyl)dimethylindium] (DADI).

[0071] Figure 2 It is a graph showing the results of vapor pressure measurement of Example 2 of the present invention and [(3-dimethylamino)propyl)dimethylindium] (DADI).

[0072] Figure 3 It is a graph showing the measurement results of thermal stability of Example 2 of the present invention and [(3-dimethylamino)propyl)dimethylindium] (DADI).

[0073] Figure 4 is a graph showing deposition rates according to changes in precursor injection time of Example 3 and Comparative Example 1.

[0074] Figure 5 is a graph showing deposition rates according to changes in precursor vapor pressures of Example 3 and Comparative Example 1.

[0075] Figure 6 3 is a graph showing the deposition rate according to the change of the silicon substrate temperature according to Example 3 and Comparative Example 1.

[0076] Figure 7 3 is a graph showing the deposition thickness according to the process cycles of Example 3 and Comparative Example 1.

[0077] Figure 8 It is a figure which shows the XRD spectrum of Example 3 and Comparative Example 1. DETAILED DESCRIPTION

[0078] Hereinafter, the composition for thin film deposition containing a metal compound, the method for producing a metal-containing thin film using the same, and the metal-containing thin film produced using the same according to the present invention will be described in detail.

[0079] Unless otherwise indicated herein, a single quantity form used in the present invention may be construed as including a plural quantity form.

[0080] In addition, the numerical range used in the present invention includes: the lower limit value and the upper limit value and all values ​​within the range; the increment that can be logically derived based on the form and amplitude of the defined range; all values ​​of double definition; and all possible combinations of the upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in the description of the present invention, the numerical values ​​that may exceed the numerical range due to experimental errors or rounding of numerical values ​​are also included in the defined numerical range.

[0081] The term “comprising” described in the present invention is an open description having a meaning equivalent to expressions such as “having”, “containing”, “having” or “characterized by”, and does not exclude elements, materials or processes that are not additionally listed.

[0082] The number of carbon atoms described in the present invention does not include the number of carbon atoms of the substituent. As an example, a C1-C7 alkyl group refers to an alkyl group having 1 to 7 carbon atoms excluding the number of carbon atoms of the substituent of the alkyl group.

[0083] Hereinafter, the present invention will be described in detail. At this time, if there is no other definition in the technical terms and scientific terms used, they have the meanings generally understood by ordinary technicians in the technical field to which the present invention belongs, and in the following description, the description of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.

[0084] The present invention provides a composition for thin film deposition, which includes a metal compound represented by the following Chemical Formula 1.

[0085] [Chemical formula 1]

[0086]

[0087] [In the chemical formula 1,

[0088] M is In or Ga;

[0089] is a single bond or a double bond;

[0090] R a To R c are independently C1-C7 alkyl;

[0091] R1 to R8 are independently hydrogen or C1-C7 alkyl;

[0092] When the When it is a double bond, R1, R3, R5 and R7 do not exist.]

[0093] The metal compound represented by the chemical formula 1 may have a chiral center, so the compound may be used in the form of an optically pure compound or provided as a diastereomeric mixture or a racemic mixture. The term "racemic mixture" refers to a mixture of two enantiomers in the same ratio.

[0094] The metal compound may have a single evaporation step at a temperature of 50° C. or higher, and may have a residual mass of 0.001 to 1 wt %, specifically 0.01 to 0.9 wt %, and more specifically 0.1 to 0.7 wt % at 500° C. The metal compound has higher volatility and improved vapor pressure, may exhibit a high deposition rate, and may have excellent stability during storage and be easy to handle because it is a compound with more improved thermal stability.

[0095] M in the chemical formula 1 may be In or Ga, is a single bond or a double bond, R a To R c are independently C1-C4 alkyl, and R1 to R8 are independently hydrogen or C1-C4 alkyl.

[0096] Specifically, in the metal compound represented by the chemical formula 1, M may be In or Ga, is a single bond or a double bond, R a To R c are independently C1-C3 alkyl, and R1 to R8 are independently hydrogen or C1-C3 alkyl.

[0097] The metal compound according to one embodiment of the present invention may be represented by the following Chemical Formula 2.

[0098] [Chemical formula 2]

[0099]

[0100] [In the chemical formula 2,

[0101] M is In or Ga;

[0102] is a single bond or a double bond;

[0103] R is a C1-C7 alkyl group;

[0104] R 11 To R 14 are independently hydrogen or C1-C7 alkyl.]

[0105] In the chemical formula 2, when When it is a single key, There is R in each carbon of the ring 11 To R 14 and unlabeled single hydrogen, when When there is a double bond, only the R 11 To R 14 .

[0106] M in the chemical formula 2 may be In or Ga. is a single bond or a double bond, R is a C1-C4 alkyl group, R 11 To R 14 are independently hydrogen or C1-C4 alkyl.

[0107] The metal compound according to one embodiment may be represented by Chemical Formula 3 below.

[0108] [Chemical formula 3]

[0109]

[0110] [In the chemical formula 3,

[0111] M is In or Ga;

[0112] R is a C1-C3 alkyl group;

[0113] R 21 To R 24 are independently hydrogen or C1-C4 alkyl.]

[0114] In addition, the present invention provides a method for preparing a metal compound represented by the following Chemical Formula 1 according to one embodiment, specifically comprising the following steps: preparing the metal compound represented by the following Chemical Formula 1 by reacting compounds represented by the following Chemical Formulas 11 to 15.

[0115] [Chemical formula 1]

[0116]

[0117] [Chemical formula 11]

[0118] MX3

[0119] [Chemical formula 12]

[0120] R a MgX a

[0121] [Chemical formula 13]

[0122] R b MgX b

[0123] [Chemical formula 14]

[0124] R c MgX c

[0125] [Chemical formula 15]

[0126]

[0127] [In the chemical formula 1 and chemical formulas 11 to 15,

[0128] M is In or Ga;

[0129] is a single bond or a double bond;

[0130] R a To R c are independently C1-C7 alkyl;

[0131] R1 to R8 are independently hydrogen or C1-C7 alkyl;

[0132] X, X a , X b and X c are independently halogen;

[0133] When the is a double bond, then R1, R3, R5 and R7 do not exist.]

[0134] Specifically, the step of preparing the compound of Chemical Formula 1 is as follows: after adding a solvent to the compound represented by Chemical Formula 11, adding compounds represented by Chemical Formulas 12 to 15 at 0 to 30° C., and then reacting at 5 to 50° C. for 1 to 15 hours, specifically, at 10 to 40° C. for 1 to 12 hours, and more specifically, at 15 to 35° C. for 1 to 10 hours.

[0135] In another embodiment, Chemical Formula 12 to Chemical Formula 14 may be the same compound, and may be the Grignard reagent contained in the solution of Chemical Formula 15.

[0136] According to an embodiment of the present invention, the method for preparing a metal compound may further include, after reacting the compounds of Chemical Formulas 11 to 15 to produce the compound of Chemical Formula 1, adding a polar solvent and stirring.

[0137] According to one embodiment of the present invention, the polar solvent can be one or more selected from acetonitrile, dimethylsulfoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF), specifically, it can be dimethylformamide (DMF), tetrahydrofuran (THF) or a mixture thereof, more specifically, it can be tetrahydrofuran (THF), but is not limited thereto.

[0138] In addition, 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.

[0139] During the preparation of the metal compound, MgCl2 precipitate may be generated. Due to its small particle size, it is not easy to be removed by a filter and requires a long filtration time. Therefore, it is regarded as a reaction by-product that may greatly reduce the purity and yield of the final compound.

[0140] Therefore, according to the method for preparing the metal compound of the present invention, if it includes the step of adding a polar solvent to the generated MgCl2 precipitate, and in particular, includes the step of adding an excess amount of polar solvent, the metal compound represented by the chemical formula 1 with high purity can be easily separated.

[0141] This is considered to be due to the formation of a complex of the polar solvent and MgCl2, so that the separation of the by-product and the metal compound becomes easy, and the purity and yield of the metal compound are high.

[0142] Specifically, when a polar solvent such as THF is used, the formation of MgCl2(THF) is expected. n (n=2,3) complex. It can be confirmed that the compound formed into a complex has significantly improved filterability, so that the complex can be easily filtered and removed, thereby significantly improving the purity and yield of the final product.

[0143] In the method for preparing the metal compound according to one embodiment of the present invention, a polar solvent may be added to the reaction products of Chemical Formula 11 to Chemical Formula 15 to stir for 0.5 to 5 hours.

[0144] In addition, in the step of reacting the chemical formulas 11 to 15 to prepare the compound of the chemical formula 1, the solvent can be any common organic solvent, and can be one or more selected from hexane, pentane, dichloromethane (DCM), benzene and toluene, but is not limited thereto.

[0145] Each reaction of the preparation method can be terminated after confirming complete consumption of the starting material by NMR, and after the reaction is completed, a process of separating and purifying the compound can be performed by a common method such as an extraction process, a process of distilling the solvent under reduced pressure, and column chromatography.

[0146] The method for preparing the metal compound can prepare a high-purity metal compound with a high yield, and can be prepared through a mild and simple process, so that it can be easily used in industrialization.

[0147] The metal compound may have a certain vapor pressure during the deposition process to keep the composition of the film constant, thereby preparing a film with a constant and uniform composition. In addition, since the film thickness is uniform and can show excellent step coverage, a film that shows excellent physical properties even in a three-dimensional device can be prepared.

[0148] The present invention provides a method for manufacturing a metal-containing thin film using a metal compound or a composition for thin film deposition including the same according to one embodiment.

[0149] According to a method for manufacturing a metal-containing film according to one embodiment of the present invention, a film having a multilayer structure containing heterogeneous metals can be manufactured. The structure can be stacked by sequentially depositing the metal compound or the metal-containing film deposition composition and the heterogeneous metal precursor, and can be deposited by mixing the metal compound or the metal-containing film deposition composition and the heterogeneous metal precursor.

[0150] The method for manufacturing the metal-containing film may include: step a), heating a substrate installed in a chamber; step b), injecting a metal compound according to an embodiment of the present invention or the composition for thin film deposition into the chamber to adsorb it onto the substrate; and step c), injecting a reaction gas into the substrate adsorbed with the metal compound or the composition for thin film deposition to manufacture the metal-containing film.

[0151] The reaction gas can 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). The transport gas is an inert gas and can be any one or more selected from argon (Ar), helium (He) and nitrogen (N2), specifically nitrogen (N2), but not limited to.

[0152] In addition, the method for manufacturing a metal-containing film according to an embodiment of the present invention can take step b) and step c) as a cycle, and repeatedly perform the cycle until a metal-containing film of a desired thickness is manufactured. Specifically, it can be 50 to 5000 cycles, more specifically, it can be 200 to 2000 cycles, but is not limited thereto.

[0153] 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 achieve deposition without thermal decomposition of the metal compound even at a temperature as high as the above temperature, thereby improving stability and productivity during the deposition process.

[0154] Furthermore, the content of impurities such as carbon in the metal-containing thin film manufactured by the method for manufacturing the metal-containing thin film is unexpectedly reduced, so that a high-quality metal-containing thin film can be manufactured.

[0155] According to one embodiment, the substrate used in the manufacturing method of the metal-containing film may include one or more substrates selected from glass, silicon, metal polyester (Polyester, PE), polyethylene terephthalate (Polyethyleneterephthalate, PET), polyethylene napthalate (Polyethylenenapthalate, PEN), polycarbonate (Polycarbonate, PC), polyetherimide (Polyetherimide, PEI), polyethersulfone (Polyethersulfone, PES), polyetheretherketone (Polyetheretherketone, PEEK) and polyimide (Polyimide, PI), but is not limited to these.

[0156] In step b) of the method for manufacturing a metal-containing film according to one embodiment, the composition for depositing a metal-containing film is filled into a stainless steel bubbling container and can be maintained at a temperature of 20 to 100° C., specifically, 30 to 90° C., and more specifically, 40 to 70° C.

[0157] In addition, the conditions of the deposition process as step b) can be adjusted according to the structure and thermal characteristics of the film. According to one embodiment, the input flow rate of the metal compound can be 1 to 1000 sccm using a bubbling container type, the input flow rate of the delivery gas is 1 to 5000 sccm, the input flow rate of the reaction gas is 10 to 5000 sccm, the pressure can be adjusted in the range of 0.1 to 10 torr, and the injection time can be 0.1 to 20 seconds, preferably, 0.1 to 15 seconds, more preferably, 0.1 to 10 seconds, but not limited to this. When a metal-containing film is manufactured within the range, the uniformity of the thickness of the film can be greatly improved, so that excellent step coverage can be maintained even on a substrate of a complex shape.

[0158] According to one embodiment, the method for manufacturing a metal-containing thin film may further include a purging step in which a delivery gas is used to purge in order to remove unadsorbed metal compounds or a composition for thin film deposition containing the metal compounds or to remove reaction byproducts and residual reaction gases generated after the reaction gases are injected.

[0159] According to an embodiment of the present invention, a method for manufacturing an indium-containing thin film can be performed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic 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). Preferably, it can be performed by atomic layer deposition (ALD), chemical vapor deposition (CVD) or metal-organic chemical vapor deposition (MOCVD).

[0160] The present invention provides a metal-containing thin film manufactured using a metal compound according to one embodiment of the present invention or a composition for thin film deposition containing the same, and the metal-containing thin film may have a uniform composition and exhibit excellent electrical properties.

[0161] The metal content of the metal-containing film may be 20 to 60 wt %.

[0162] Hereinafter, the metal compound and 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 therefrom according to the present invention are described in more detail through specific examples.

[0163] However, the following embodiments are only for reference to explain the present invention in detail, and the present invention is not limited thereto and can be implemented in various forms. In addition, the terms used for explanation in the present invention are only for effectively describing specific embodiments and are not intended to limit the present invention.

[0164] Furthermore, unless otherwise stated, all examples were performed under a non-reactive atmosphere, such as purified nitrogen (N2) or argon (Ar), using techniques for handling air-sensitive substances generally known in the art, such as "Schlenk techniques".

[0165] Example 1: Preparation of Indium Compound (InMe3(THF))

[0166] After 100 g (0.45 mol) of InCl3 was added to a 5L three-necked flask including a stirrer and a reflux device (condenser), vacuum drying was performed. After 1000 ml of n-hexane was added, the temperature was maintained at 10°C, and 452 ml (3.0 M THF solution) of MeMgCl was slowly added, and then stirred at room temperature for 8 hours to generate a light gray precipitate. The reactant was then filtered, and then the solvent and volatile by-products of the filtrate were removed under reduced pressure, and vacuum distillation (23°C, 0.8 torr) was performed to obtain 37.1 g of a colorless liquid metal compound (yield 35%).

[0167] 1 H NMR (400MHz, C6D6) δ3.2 (m, 4H), 1.1 (m, 4H), -0.1 (s, 9H).

[0168] Example 2: Preparation of Indium Compound (InMe3(THF))

[0169] After 100 g (0.45 mol) of InCl3 was added to a 5L three-necked flask including a stirrer and a reflux device (condenser), vacuum drying was performed. After 1000 ml of n-hexane was added, the temperature was maintained at 10°C, and 452 ml (3.0 M THF solution) of MeMgCl was slowly added, and then stirred at room temperature for 8 hours. After the reaction was completed, 3 equivalents of THF were further added to the reactant at room temperature, stirred for 2 hours, filtered, and then the solvent and volatile by-products of the filtrate were removed under reduced pressure, and vacuum distillation (23°C, 0.8 torr) was performed to obtain 77.3 g of a colorless liquid metal compound (yield 73%).

[0170] 1 H NMR (400MHz, C6D6) δ3.2 (m, 4H), 1.1 (m, 4H), -0.1 (s, 9H).

[0171] Figure 1The TGA chart of the metal compound InMe3 (THF) of Example 2 is shown. By comparing it with the TGA chart of [(3-dimethylamino)propyl]dimethylindium (hereinafter referred to as DADI, DOCK / CHEMICALS) commonly used in the existing indium-containing thin film deposition, it can be seen that the metal compound has a single evaporation step starting from about 50° C., the temperature at the 1 / 2 weight reduction point is 12° C. lower than that of DADI, and the residual mass is confirmed to be 0.4% at 500° C. According to the results, the metal compound of Example 2 of the present invention shows a faster vaporization feature than DADI, and more than 99% of it is vaporized without thermal decomposition.

[0172] To confirm the improved vapor pressure properties of Example 2 (InMe3(THF)), the vapor pressure was measured and compared with that of DADI and is shown in Figure 2 .

[0173] like Figure 2 As shown, as the vapor pressure measurement results confirm, the vapor pressure of Example 2 (InMe3(THF)) (26°C@1 torr) is significantly improved compared to the vapor pressure of DADI (41°C@1 torr).

[0174] From this result, it can be seen that when Example 2 (InMe3(THF)) is used to deposit an indium-containing thin film by chemical vapor deposition (CVD) or atomic layer deposition (ALD), it is more advantageous than existing indium precursors.

[0175] A specified volume (3 g) of Example 2 (InMe3(THF)) and DADI were placed in a sealable stainless steel container in an argon atmosphere glove box, sealed, and stored under specified temperature (100°C, 120°C) and time (1 day, 4 days, 7 days). 1 The thermal stability of Example 2 (InMe3(THF)) and DADI was measured by H NMR analysis and confirmed by the method of peak change, which is shown in Figure 3 .

[0176] like Figure 3 As shown, under the condition of 100°C, both Example 2 (InMe3(THF)) and DADI showed no change until the 7th day, indicating a stable state. However, under the condition of 120°C, Example 2 (InMe3(THF)) of the present invention showed no change, while DADI was confirmed to produce by-products from the 4th day.

[0177] It can be seen that compared with DADI which is widely used in the deposition of indium-containing thin films, Example 2 (InMe3(THF)) of the present invention has significantly superior stability under high temperature conditions.

[0178] [Example 3] Preparation of Indium Oxide Thin Film

[0179] An indium-containing oxide film was manufactured by plasma enhanced atomic layer deposition (PEALD) using InMe3(THF) according to Example 2 and nitrous oxide (N2O) as a reaction gas.

[0180] A silicon substrate is installed inside a deposition chamber, and the temperature of the substrate is maintained at a certain temperature. A stainless steel bubbling container is filled with InMe3(THF), and the temperature is maintained at a temperature corresponding to a certain vapor pressure.

[0181] Argon (Ar) was used as a delivery gas, and the InMe3(THF) precursor was injected into the deposition chamber for a certain period of time to allow it to be adsorbed. Then, 600 sccm of argon (Ar) was used for 3 seconds to purge the InMe3(THF) and reaction byproducts remaining in the deposition chamber.

[0182] While injecting nitrous oxide (N2O) as a reaction gas, a plasma is used to form an indium-containing oxide film. Then, argon (Ar) gas is purged for 3 seconds with 600 sccm to remove residual reaction gas and reaction byproducts.

[0183] The above process was performed 70 to 700 times as 1 cycle to produce an indium-containing oxide film, and the thickness of the deposited indium oxide film was measured using an ellipsometer.

[0184] The deposition conditions of the indium oxide thin film are shown in Table 1 below.

[0185] [Comparative Example 1] Production of Indium Oxide Thin Film

[0186] In the manufacture of the indium-containing thin film, DADI, which is currently widely used, is used, and the metal oxide-containing thin film is manufactured by plasma enhanced atomic layer deposition (PEALD) using nitrous oxide (N2O) as a reaction gas.

[0187] An indium oxide thin film was formed in the same manner as in Example 3 except that DADI was used as a precursor. The deposition conditions of the indium oxide thin film are shown in Table 1 below.

[0188] Table 1

[0189]

[0190]

[0191] Figure 4 The deposition rate per cycle according to the change of the precursor injection time of Example 3 and Comparative Example 1 is shown. It can be seen that the deposition rate of Example 3 and Comparative Example 1 shows a tendency to increase as the injection time increases due to physical adsorption, but at an injection time of more than 0.3 seconds, the deposition rate hardly increases due to saturation. In particular, it can be seen that Example 3 shows a significantly improved deposition rate of more than 40% compared with Comparative Example 1.

[0192] Figure 5 The deposition rate per cycle of the vapor pressure of the precursors of Example 3 and Comparative Example 1 is shown. It can be seen that the vapor pressure of the precursors of Example 3 and Comparative Example 1 becomes stable above 1 torr, and in particular, Example 3 shows a relatively constant deposition rate even at a high vapor pressure of 12 torr, thereby confirming the self-limiting reaction that is a characteristic of ALD. In addition, similar to the previous results, it can be seen that Example 3 shows a significant improvement of more than 40% in terms of the deposition rate based on the vapor pressure compared to Comparative Example 1.

[0193] Figure 6 The deposition rate per cycle according to the change in silicon substrate temperature is shown for Example 3 and Comparative Example 1. As with the previous results, Example 3 showed a result of 40% or more in terms of the deposition rate according to the silicon substrate temperature compared to Comparative Example 1, thereby confirming that a significantly improved deposition rate was shown.

[0194] Figure 7 The thickness of the film according to the process cycle in Example 3 and Comparative Example 1 is shown. It can be seen that the thickness increases linearly as the process cycle increases, and thus the self-limited reaction (Self-limited reaction) as a characteristic of ALD can be confirmed. In addition, in the thickness graph according to the deposition cycle, in terms of the deposition rate confirmed based on the slope, Example 3 is 1.0 cycle, which is significantly improved compared to 0.65 cycles of Comparative Example 1.

[0195] Figure 8 The XRD patterns of Example 3 and Comparative Example 1 are shown. The specific deposition conditions are: the temperature of the silicon substrate is 200°C, the precursor is injected for 0.5 seconds, the step of using plasma is performed for 3 seconds under the conditions of 400 sccm of nitrous oxide (N2O) and 400W of power, and the purge step is performed for 3 seconds with 600 sccm of argon. The thickness of each film is formed by adjusting the process cycle to about 350.

[0196] It was confirmed that the deposited indium oxide film had a cubic structure, and in Table 2, the results of the components and film density were shown by X-ray photoelectron spectroscopy (XPS) and X-ray reflectivity (XRR) analysis of the indium oxide film. As shown in Table 2, it can be seen that a pure indium oxide film containing no impurities such as carbon or nitrogen is formed, and the density of the film is confirmed to be 7.3 g / m 3 , and the density of the bulk state is 7.2g / m 3 resemblance.

[0197] Table 2

[0198]

[0199] It can be seen that the metal compound according to one embodiment of the present invention is a liquid compound with surprisingly improved thermal stability, high volatility and high vapor pressure. In addition, if a thin film is manufactured using a composition for thin film deposition containing the metal compound, the deposition thickness per cycle is about 40% higher than that of [(3-dimethylamino)propyl]dimethylindium (DADI), which is a commonly used substance. Therefore, it can be seen that when using an embodiment of the present invention, a very significant deposition rate can be exhibited, and a highly reliable thin film showing a uniform composition can be formed.

[0200] The thin film deposition composition of the present invention can provide a thin film of uniform thickness to a three-dimensional device, and can produce a thin film showing an appropriate metal and oxygen composition ratio, and can reduce the time consumption of the process, thereby making it possible to produce a thin film very economically.

[0201] As described above, in the present invention, specific matters and limited embodiments and comparative examples are described, but this is only provided to help a more comprehensive understanding of the present invention. The present invention is not limited to the above-mentioned embodiments, and any person skilled in the art in the field to which the present invention belongs can make various modifications and variations based on such descriptions.

[0202] Therefore, the idea of ​​the present invention should not be limited to the illustrated embodiments, and it can be said that not only the scope of the claims but also all modifications equivalent or equivalent to these claims belong to the scope of the idea of ​​the present invention.

Claims

1. A composition for thin film deposition, characterized in that The composition for thin film deposition includes a metal compound represented by the following Chemical Formula 1, [Chemical formula 1] In the chemical formula 1, M is In or Ga; is a single bond or a double bond; R a To R c are independently C1-C7 alkyl; R1 to R8 are independently hydrogen or C1-C7 alkyl; when If it is a double bond, R1, R3, R5 and R7 do not exist.

2. The composition for thin film deposition according to claim 1, characterized in that M in the chemical formula 1 is In or Ga; is a single bond or a double bond; R a To R c are independently C1-C4 alkyl; R1 to R8 are independently hydrogen or C1-C4 alkyl.

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

4. The composition for thin film deposition according to claim 3, characterized in that M in the chemical formula 2 is In or Ga; is a single bond or a double bond; R is a C1-C4 alkyl group; R 11 To R 14 are independently hydrogen or C1-C4 alkyl.

5. The composition for thin film deposition according to claim 1, characterized in that: The metal compound is represented by the following chemical formula 3: [Chemical formula 3] In the chemical formula 3, M is In or Ga; R is a C1-C3 alkyl group; R 21 To R 24 are independently hydrogen or C1-C4 alkyl.

6. A method for preparing a metal compound represented by the following chemical formula 1, characterized in that: The preparation method comprises the following steps: The compounds represented by the following Chemical Formulas 11 to 15 are reacted to prepare the compound of the following Chemical Formula 1, [Chemical formula 1] [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] In the chemical formula 1 and chemical formulas 11 to 15, M is In or Ga, is a single bond or a double bond, R a To R c are independently C1-C7 alkyl, R1 to R8 are independently hydrogen or C1-C7 alkyl, X, X a , X b and X c are independently halogen; when If it is a double bond, R1, R3, R5 and R7 do not exist.

7. The method for preparing a metal compound according to claim 6, characterized in that: After the step of preparing the compound of Chemical Formula 1, the method further comprises: A step of adding a polar solvent and stirring.

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

9. A method for manufacturing a metal-containing film, characterized in that: The manufacturing method uses 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 chemical formula 1, M. R a To R c , R1 to R8 are the same as defined in claim 1.

10. The method for manufacturing a metal-containing thin film according to claim 9, characterized in that: include: Step a), heating the substrate installed in the chamber; Step b), injecting the metal compound or a composition for thin film deposition containing the metal compound into the chamber to adsorb the metal compound onto the substrate; and Step c) injecting a reaction gas into the substrate adsorbed with the metal compound or the composition for thin film deposition containing the metal compound to produce a metal-containing thin film.

11. The method for manufacturing a metal-containing thin film according to claim 10, characterized in that: The temperature of the substrate is 100 to 450°C.

12. A metal-containing film, characterized in that: The metal-containing thin film is manufactured 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 chemical formula 1, M. R a To R c , R1 to R8 are the same as defined in claim 1.

13. The metal-containing film according to claim 12, characterized in that: The metal content of the metal-containing film is 20 to 60 wt %.

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