WO2024049150A1 - Composition pour déposer une couche mince contenant un composé métallique, procédé de fabrication d'une couche mince contenant du métal l'utilisant et couche mince contenant du métal fabriquée à l'aide de celle-ci - Google Patents

Composition pour déposer une couche mince contenant un composé métallique, procédé de fabrication d'une couche mince contenant du métal l'utilisant et couche mince contenant du métal fabriquée à l'aide de celle-ci Download PDF

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WO2024049150A1
WO2024049150A1 PCT/KR2023/012751 KR2023012751W WO2024049150A1 WO 2024049150 A1 WO2024049150 A1 WO 2024049150A1 KR 2023012751 W KR2023012751 W KR 2023012751W WO 2024049150 A1 WO2024049150 A1 WO 2024049150A1
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thin film
formula
metal
metal compound
composition
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Korean (ko)
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권용희
변태석
전상용
이상찬
임영재
이상익
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(주)디엔에프
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Definitions

  • 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 manufactured therefrom.
  • silicon was the most widely used thin film material for display electronic devices, but metal oxides, which have higher charge mobility and are easier to process at low temperatures than polycrystalline silicon, are currently being used.
  • Metal oxide has a wide energy band gap and excellent light transmittance, so it is expected to be a material that can improve uniformity and mobility, which are shortcomings of existing silicon.
  • group 13 metal oxides can be used as transparent oxide semiconductor materials and can also be applied as electrodes and conductive coating materials.
  • group 13 metals indium and gallium are useful because they have excellent resistance to wear and tear and have low resistance when contacting aluminum wires.
  • the composition of the deposited thin film is determined by the sputter target, so there is a limit to uniformly controlling the composition of the thin film, and when depositing on a large area, It is difficult to maintain uniform thin film composition and uniform thickness.
  • Indium(III) chloride a previously used metal precursor, has the disadvantage of being chlorine-contaminated and requiring an external oxygen source when depositing thin films using methods such as atomic layer deposition, chemical vapor deposition, and pulsed laser deposition.
  • trialkylindium (III) precursors such as trimethyl indium and triethyl indium, which have been widely used in the past, are very sensitive to oxygen and moisture, and since they are solid, problems may arise in terms of vapor pressure control and reproducibility of a uniform film.
  • the purpose of the present invention is to provide a composition for thin film deposition containing a metal compound exhibiting excellent volatility and thermal stability.
  • Another object of the present invention is to provide a method for producing a metal compound.
  • Another object of the present invention is to provide a method for manufacturing a thin film that can exhibit improved deposition speed and reproducibility using the composition for thin film deposition.
  • the present invention provides a high-quality metal-containing thin film having constant composition and uniform thickness by employing the composition for thin film deposition.
  • the present invention provides a composition for thin film deposition containing a metal compound represented by the following formula (1).
  • M is In or Ga
  • R a to R c are independently C1-C7 alkyl
  • R 1 to R 8 are independently hydrogen or C1-C7 alkyl
  • M in Formula 1 is In or Ga, is a single bond or a double bond, R a to R c may be independently C1-C4 alkyl, and R 1 to R 8 may be independently hydrogen or C1-C4 alkyl.
  • the metal compound according to an embodiment of the present invention may be represented by the following formula (2).
  • M is In or Ga
  • R is C1-C7alkyl
  • R 11 to R 14 are independently hydrogen or C1-C7 alkyl.
  • M in Formula 2 is In or Ga, is a single bond or a double bond, R is C1-C4 alkyl, and R 11 to R 14 may independently be hydrogen or C1-C4 alkyl.
  • the metal compound according to one embodiment may be represented by the following formula (3).
  • M is In or Ga
  • R is C1-C3 alkyl
  • R 21 to R 24 are independently hydrogen or C1-C4 alkyl.
  • the present invention provides a method for producing a metal compound represented by the following Chemical Formula 1 according to an embodiment, and specifically includes the step of reacting compounds represented by the following Chemical Formulas 11 to 15 to prepare a compound represented by the following Chemical Formula 1: do.
  • M is In or Ga
  • R a to R c are independently C1-C7 alkyl
  • R 1 to R 8 are independently hydrogen or C1-C7 alkyl
  • X, X a , X b and X c are independently halogen
  • the method for producing a metal compound according to an embodiment of the present invention may further include adding a polar solvent and stirring after preparing Formula 1 above.
  • the amount of polar solvent added may be 2 to 5 equivalents based on the compound represented by Formula 1.
  • the present invention provides a method of manufacturing a metal-containing thin film using a metal compound or a composition for thin film deposition containing the same according to an embodiment.
  • the method of manufacturing the metal-containing thin film includes the steps of a) raising the temperature of the substrate mounted in the chamber; b) injecting the metal compound or a composition for thin film deposition containing the same into the chamber and adsorbing it to the substrate, and c) injecting a reaction gas into the substrate to which the metal compound or the composition for thin film deposition containing the same is adsorbed to form a metal compound. It may include manufacturing a thin film, and the temperature of the substrate may be 100 to 450°C.
  • the present invention provides a metal-containing thin film manufactured using a metal compound or a composition for thin film deposition containing the same according to an embodiment of the present invention.
  • the metal-containing thin film may have a metal content of 20 to 60% by weight.
  • composition for thin film deposition containing the metal compound of the present invention exhibits high volatility and can have excellent thermal and storage stability by containing a metal compound having a specific structure.
  • the method for producing a metal compound according to an embodiment of the present invention not only achieves high yield through a simple process, but also produces the compound of Formula 1 with high purity.
  • the method for producing a metal-containing thin film of the present invention can exhibit improved deposition rates by employing the composition for thin film deposition of the present invention, and can provide uniform step coverage for a three-dimensional device. Additionally, a metal-containing thin film manufactured using the composition for thin film deposition of the present invention may have uniform components and uniform thickness, and may exhibit excellent electrical performance.
  • Figure 1 is a diagram showing the TGA analysis results of Example 2 of the present invention and [(3-dimethylamino)propyl]dimethylindium (DADI).
  • Figure 2 is a diagram showing the vapor pressure measurement results of Example 2 of the present invention and [(3-dimethylamino)propyl]dimethylindium (DADI).
  • Figure 3 is a diagram showing the results of measuring the thermal stability of Example 2 of the present invention and [(3-dimethylamino)propyl]dimethylindium (DADI).
  • Figure 4 is a diagram showing the deposition rate according to precursor injection time in Example 3 and Comparative Example 1.
  • Figure 5 is a diagram showing the deposition rate according to the precursor vapor pressure of Example 3 and Comparative Example 1.
  • Figure 6 is a diagram showing the deposition rate according to the silicon substrate temperature of Example 3 and Comparative Example 1.
  • Figure 7 is a diagram showing the deposition thickness according to the process cycle of Example 3 and Comparative Example 1.
  • Figure 8 is a diagram showing the XRD patterns of Example 3 and Comparative Example 1.
  • composition for thin film deposition containing the metal compound of the present invention the method for manufacturing a metal-containing thin film using the same, and the metal-containing thin film manufactured by employing the same will be described in detail.
  • the numerical range used in the present invention includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.
  • C1-C7 alkyl means alkyl with 1 to 7 carbon atoms that does not include the carbon number of the alkyl substituent.
  • the present invention provides a composition for thin film deposition containing a metal compound represented by the following formula (1).
  • M is In or Ga
  • R a to R c are independently C1-C7 alkyl
  • R 1 to R 8 are independently hydrogen or C1-C7 alkyl
  • the metal compound represented by Formula 1 can have a chiral center, the compound can be used in optically pure form or provided as a diastereomeric mixture or racemic mixture.
  • racemic mixture means a mixture of two enantiomers in equal proportions.
  • 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% by weight, specifically 0.01 to 0.9% by weight, and more specifically 0.1 to 0.7% by weight.
  • the metal compound has higher volatility and improved vapor pressure, so it can exhibit a high deposition rate. It is a compound with improved thermal stability, has excellent stability during storage, and can be easy to handle.
  • M in Formula 1 is In or Ga, is a single bond or a double bond, R a to R c may be independently C1-C4 alkyl, and R 1 to R 8 may be independently hydrogen or C1-C4 alkyl.
  • M is In or Ga, is a single bond or a double bond, R a to R c may be independently C1-C3 alkyl, and R 1 to R 8 may be independently hydrogen or C1-C3 alkyl.
  • the metal compound according to an embodiment of the present invention may be represented by the following formula (2).
  • M is In or Ga
  • R is C1-C7alkyl
  • R 11 to R 14 are independently hydrogen or C1-C7 alkyl.
  • M in Formula 2 is In or Ga, is a single bond or a double bond, R is C1-C4 alkyl, and R 11 to R 14 may independently be hydrogen or C1-C4 alkyl.
  • the metal compound according to one embodiment may be represented by the following formula (3).
  • M is In or Ga
  • R is C1-C3 alkyl
  • R 21 to R 24 are independently hydrogen or C1-C4 alkyl.
  • the present invention provides a method for producing a metal compound represented by the following Chemical Formula 1 according to an embodiment, and specifically, reacting compounds represented by the following Chemical Formulas 11 to 15 to prepare a metal compound represented by the following Chemical Formula 1: Includes.
  • M is In or Ga
  • R a to R c are independently C1-C7 alkyl
  • R 1 to R 8 are independently hydrogen or C1-C7 alkyl
  • X, X a , X b and X c are independently halogen
  • the step of preparing the compound of Formula 1 includes adding a solvent to the compound represented by Formula 11, then adding the compounds represented by Formulas 12 to 15 at 0 to 30 ° C, and then adding a solvent to the compound represented by Formula 11, and then adding a solvent to the compound represented by Formula 11 at 0 to 30 ° C.
  • the reaction may be performed for 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.
  • Formulas 12 to 14 may be the same compound, and may be a Grignard reagent contained in the solution of Formula 15.
  • the method for producing a metal compound according to an embodiment of the present invention may further include adding a polar solvent and stirring after reacting the compounds of Formulas 11 to 15 to produce the compound of Formula 1.
  • the polar solvent according to an embodiment of the present invention may be one or two or more selected from Acetonitrile, DMSO (Dimethylsulfoxide), DMF (Dimethylformamide), and THF (Tetrahydrofuran), specifically DMF (Dimethylformamide), THF (Tetrahydrofuran) or these. It may be a mixture of, and more specifically, THF (Tetrahydrofuran), but is not limited thereto.
  • the amount of the polar solvent according to an embodiment of the present invention may be 2 to 5 equivalents, specifically 2 to 4.5 equivalents, and more specifically 2 to 4 equivalents, based on the compound represented by Formula 11.
  • MgCl 2 precipitate may be generated, which is considered a reaction by-product that is not easily removed by a filter due to the small size of the particles and requires a long filtration time, which can greatly reduce the purity and yield of the final compound.
  • the metal compound represented by Formula 1 can be easily obtained with high purity. can be separated easily.
  • a polar solvent can be added to the reaction products of Formulas 11 to 15 and stirred for 0.5 to 5 hours.
  • any common organic solvent can be used as the solvent, but it can be one or two or more selected from Hexane, Pentane, DCM (Dichloromethane), Benzene, and Toluene. However, it is not limited to this.
  • Each reaction in the above production method can be terminated after confirming that the starting material is completely consumed through NMR, and after completion of the reaction, the compound is extracted through conventional methods such as extraction, distillation of the solvent under reduced pressure, and tube chromatography. A further process of separation and purification can be performed.
  • the method for producing the metal compound can produce a high-purity metal compound in high yield and can be manufactured through a mild and simple process, making it easy for industrial use.
  • the metal compound can have a constant vapor pressure during the deposition process, so the composition of the thin film is maintained constant, thereby producing a uniform thin film with constant composition.
  • the thickness of the film is uniform and excellent step coverage can be achieved, making it possible to manufacture a thin film with excellent physical properties even in a three-dimensional device.
  • the present invention provides a method of manufacturing a metal-containing thin film using a metal compound or a composition for thin film deposition containing the same according to an embodiment.
  • the method of manufacturing a metal-containing thin film according to an embodiment of the present invention can produce a thin film with a multi-layer structure containing a different metal, by sequentially depositing the metal compound or a composition for depositing a metal-containing thin film and a precursor of the different metal. It may have a laminated structure, and may be deposited by mixing the metal compound or composition for metal-containing thin film deposition with a precursor of a different metal.
  • the method of manufacturing the metal-containing thin film includes a) raising the temperature of the substrate mounted in the chamber; b) injecting a metal compound or the thin film deposition composition according to an embodiment of the present invention into the chamber and adsorbing it on a substrate; and c) injecting a reaction gas into the substrate to which the metal compound or the thin film deposition composition is adsorbed. It may include manufacturing a metal-containing thin film.
  • the reaction gases include oxygen (O 2 ), ozone (O 3 ), water vapor (H 2 O), hydrogen peroxide (H 2 O 2 ), nitrogen monoxide (NO), nitrous oxide (N 2 O), and nitrogen dioxide (NO 2 ). , ammonia (NH 3 ), nitrogen (N 2 ), hydrazine (N 2 H 4 ), amine, diamine, hydrogen (H 2 ), argon (Ar), and helium (He).
  • the transport gas is an inert gas and may be any one or two or more selected from argon (Ar), helium (He), and nitrogen (N 2 ), and may specifically be nitrogen (N 2 ), but is limited thereto. It doesn't work.
  • the method for manufacturing a metal-containing thin film according to an embodiment of the present invention uses steps b) and c) as one cycle, and the cycle can be repeatedly performed until a metal-containing thin film of the desired thickness is manufactured. It may be 50 to 5,000 cycles, and more specifically, 200 to 2,000 cycles, but is not limited thereto.
  • 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 an embodiment of the present invention can be deposited without thermal decomposition of the metal compound even at a temperature as high as the above temperature, and thus stability and productivity can be improved during the deposition process.
  • the content of impurities such as carbon in the metal-containing thin film produced by the above-mentioned metal-containing thin film manufacturing method is surprisingly reduced, so that a high-quality metal-containing thin film can be produced.
  • the substrate used in the method of manufacturing a metal-containing thin film according to an embodiment is glass, silicon, metal polyester (PE), polyethyleneterephthalate (PET), polyethylene napthalate (PEN), and polycarbohydrate.
  • One or more substrates selected from polycarbonate (PC), polyetherimide (PEI), polyethersulfone (PES), polyetheretherketone (PEEK), and polyimide (PI) It may include, but is not limited to this.
  • step b) of the method for producing a metal-containing thin film the composition for metal-containing thin film deposition is filled into a stainless steel bubbler container and heated at 20 to 100 ° C, specifically 30 to 90 ° C, more specifically 40 to 70 ° C. can be maintained at a temperature of
  • the conditions of the deposition process in step b) can be adjusted depending on the structure and thermal characteristics of the thin film.
  • the input flow rate of the metal compound is a bubbler type in the range of 1 to 1000 sccm
  • the input flow rate of the transport gas is 1 to 5000 sccm
  • the input flow rate of the reaction gas is 10 to 5000 sccm
  • the pressure is in the range of 0.1 to 10 torr. It can be adjusted, 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 is not limited thereto.
  • a method of manufacturing a metal-containing thin film according to an embodiment includes purging with a transport gas to remove unadsorbed metal compounds or a composition for thin film deposition containing the same, or to remove reaction by-products and remaining reaction gas generated after injection of the reaction gas.
  • a purge step may be further included.
  • the method for manufacturing an indium-containing thin film is atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), and plasma enhanced chemical vapor deposition. It may be performed by PECVD, plasma enhanced atomic layer deposition (PEALD), or pulsed laser deposition (PLD), and is preferably performed by atomic layer deposition (ALD), chemical vapor deposition (CVD), or metal organic chemical vapor deposition (MOCVD). ) may be performed.
  • the present invention provides a metal-containing thin film manufactured using a metal compound or a composition for thin film deposition containing the same according to an embodiment of the present invention, and the metal-containing thin film has uniform components and can exhibit excellent electrical performance. there is.
  • the metal-containing thin film may have a metal content of 20 to 60% by weight.
  • the metal compound according to the present invention 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 will be described in more detail through specific examples.
  • Figure 1 shows a TGA graph of the metal compound InMe 3 (THF) of Example 2, and [(3-dimethylamino)propyl]dimethylindium (hereinafter DADI, DOCK/CHEMICALS), which is commonly used in the deposition of existing indium-containing thin films.
  • DADI [(3-dimethylamino)propyl]dimethylindium
  • the metal compound has a single evaporation step from about 50 °C
  • the temperature of the 1/2 weight loss portion is 12 °C lower than that of DADI
  • the residue mass at 500 °C is 0.4%. It was confirmed. From the above results, it can be seen that the metal compound of Example 2 of the present invention exhibits faster vaporization characteristics than DADI and vaporizes more than 99% without thermal decomposition.
  • Example 2 InMe 3 (THF)
  • DADI vapor pressure
  • Example 2 InMe 3 (THF) will be very advantageous over existing indium precursors when depositing an indium-containing thin film by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • Example 2 InMe 3 (THF)
  • DADI DADI
  • Example 2 InMe 3 (THF)
  • DADI DADI
  • Example 2 (InMe 3 (THF)) of the present invention has significantly superior stability under high temperature conditions compared to DADI, which is widely used for indium-containing thin film deposition.
  • An indium-containing oxide thin film was manufactured by plasma-enhanced atomic layer deposition (PEALD) using InMe 3 (THF) according to Example 2 and nitrous oxide (N 2 O) as a reaction gas.
  • PEALD plasma-enhanced atomic layer deposition
  • THF InMe 3
  • N 2 O nitrous oxide
  • a silicon substrate was loaded into the deposition chamber, and the temperature of the substrate was maintained at a constant temperature.
  • InMe 3 (THF) was filled in a stainless steel bubbler container and maintained at a temperature corresponding to a certain vapor pressure.
  • the InMe 3 (THF) precursor was injected into the deposition chamber for a certain period of time and adsorbed. Afterwards, purging was performed for 3 seconds using argon gas (600 sccm) to remove InMe 3 (THF) and reaction by-products remaining in the deposition chamber.
  • argon gas 600 sccm
  • An indium-containing oxide thin film was formed using plasma while injecting nitrous oxide (N 2 O) as a reaction gas. Afterwards, purging was performed for 3 seconds using argon gas (600 sccm) to remove residual reaction gas and reaction by-products.
  • nitrous oxide N 2 O
  • purging was performed for 3 seconds using argon gas (600 sccm) to remove residual reaction gas and reaction by-products.
  • An indium-containing oxide thin film was manufactured by performing 70 to 700 cycles of the above-described processes as 1 cycle, 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.
  • a metal-containing oxide thin film was manufactured by plasma-enhanced atomic layer deposition (PEALD) using DADI, which is currently widely used in the production of indium-containing thin films, and nitrous oxide (N 2 O) as a reaction gas.
  • PEALD plasma-enhanced atomic layer deposition
  • DADI nitrous oxide
  • An indium oxide thin film was formed in the same manner as in Example 3 except that DADI was used as the precursor, and the deposition conditions for the indium oxide thin film are shown in Table 1 below.
  • Figure 4 shows the deposition rate per cycle according to the precursor injection time of Example 3 and Comparative Example 1.
  • the deposition rate of Example 3 and Comparative Example 1 shows a tendency to increase due to physical adsorption as the injection time increases, but it can be seen that the deposition rate is saturated at an injection time of 0.3 seconds or more and the deposition rate hardly increases. .
  • Example 3 shows a deposition rate that is significantly improved by more than 40% compared to Comparative Example 1.
  • Figure 5 shows the deposition rate per cycle according to the vapor pressure of the precursors of Example 3 and Comparative Example 1. It can be seen that the vapor pressure of the precursor of Example 3 and Comparative Example 1 is stabilized at 1 Torr or more. In particular, Example 3 shows a relatively constant deposition rate even at a high vapor pressure of 12 Torr, showing self-limiting reaction (self-limiting reaction), which is a characteristic of ALD. Self-limited reaction) can be confirmed. In addition, similar to the previous results, it can be seen that Example 3 showed a significantly improved result of more than 40% compared to Comparative Example 1 in terms of deposition rate according to vapor pressure.
  • Figure 6 shows the deposition rate per cycle according to the silicon substrate temperature of Example 3 and Comparative Example 1. Similar to the previous results, it can be confirmed that Example 3 showed a significantly improved deposition rate by 40% more than Comparative Example 1 in terms of deposition rate depending on the silicon substrate temperature.
  • Figure 7 shows the thickness of the thin film according to the process cycle in Example 3 and Comparative Example 1. It can be seen that the thickness increases linearly as the process cycle increases, and from this, the self-limited reaction, which is a characteristic of ALD, can be confirmed.
  • the deposition rate which can be confirmed by the slope in the graph of the thickness according to the deposition cycle, is 1.0 ⁇ cycle in Example 3, which shows a significantly improved deposition rate compared to the 0.65 ⁇ cycle in Comparative Example 1.
  • 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, a plasma step using 400 sccm of nitrous oxide (N 2 O) and a power of 400 W for 3 seconds, and a purging step using 600 sccm of argon. Each proceeded for 3 seconds.
  • the thickness of each thin film was approximately 350 ⁇ and was formed by adjusting the process cycle.
  • Table 2 shows the results of each composition and thin film density through XPS and XRR analysis of the indium oxide thin film. As shown in Table 2, it can be seen that a pure indium oxide thin film without carbon or nitrogen impurities was formed, and the density of the thin film was 7.3 g/m 3 , which was confirmed to be similar to the bulk density of 7.2 g/m 3 It has been done.
  • the metal compound according to an embodiment of the present invention is a liquid compound and has surprisingly improved thermal stability, high volatility, and high vapor pressure.
  • the deposition thickness per cycle is about 40% higher than that of [(3-dimethylamino)propyl]dimethyl indium (DADI), a commercial material.
  • DADI [(3-dimethylamino)propyl]dimethyl indium
  • composition for thin film deposition of the present invention it is possible to provide a thin film of uniform thickness for a three-dimensional device, it is possible to manufacture a thin film showing an appropriate composition ratio of metal and oxygen, and the time consumption of the process can be greatly reduced. It is possible to economically manufacture thin films.

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Abstract

La présente invention concerne une composition contenant un métal pour déposer une couche mince contenant un composé métallique, un procédé de fabrication d'une couche mince contenant du métal l'utilisant et une couche mince contenant du métal fabriquée à l'aide de celle-ci, et la présente invention permet la fabrication d'une couche mince contenant un métal de haute qualité qui a des composants uniformes déposés à une vitesse améliorée.
PCT/KR2023/012751 2022-09-02 2023-08-29 Composition pour déposer une couche mince contenant un composé métallique, procédé de fabrication d'une couche mince contenant du métal l'utilisant et couche mince contenant du métal fabriquée à l'aide de celle-ci WO2024049150A1 (fr)

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KR1020220111582A KR20240032512A (ko) 2022-09-02 2022-09-02 금속 화합물을 포함하는 박막증착용 조성물, 이를 이용한 금속 함유 박막의 제조방법 및 이를 이용하여 제조된 금속 함유 박막
KR10-2022-0111582 2022-09-02

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Citations (4)

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Publication number Priority date Publication date Assignee Title
US4464233A (en) * 1981-11-25 1984-08-07 The Secretary Of State For Defense In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Preparation of adducts which may be used in the preparation of compound semiconductor materials
US20120231611A1 (en) * 2009-09-02 2012-09-13 L'air Liquide Societe Anonyme Pour L'exploitation Des Procedes Georges Claude Dihalide germanium(ii) precursors for germanium-containing film depositions
CN104587939A (zh) * 2015-01-07 2015-05-06 安徽亚格盛电子新材料有限公司 常温直接制备三氯化镓-四氢呋喃溶液的装置
KR20210052305A (ko) * 2019-10-30 2021-05-10 솔브레인 주식회사 인듐 전구체 화합물, 이를 이용한 박막의 제조 방법 및 이로부터 제조된 기판

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KR102029071B1 (ko) 2016-11-21 2019-10-07 한국화학연구원 13족 금속 전구체, 이를 포함하는 박막증착용 조성물 및 이를 이용하는 박막의 제조방법

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US4464233A (en) * 1981-11-25 1984-08-07 The Secretary Of State For Defense In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Preparation of adducts which may be used in the preparation of compound semiconductor materials
US20120231611A1 (en) * 2009-09-02 2012-09-13 L'air Liquide Societe Anonyme Pour L'exploitation Des Procedes Georges Claude Dihalide germanium(ii) precursors for germanium-containing film depositions
CN104587939A (zh) * 2015-01-07 2015-05-06 安徽亚格盛电子新材料有限公司 常温直接制备三氯化镓-四氢呋喃溶液的装置
KR20210052305A (ko) * 2019-10-30 2021-05-10 솔브레인 주식회사 인듐 전구체 화합물, 이를 이용한 박막의 제조 방법 및 이로부터 제조된 기판

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CHEN Y.-J., ET AL.: "CHEMICAL VAPOR DEPOSITION OF COCA AND PTGA2 THIN FILMS FROM MIXED-METALORGANOMETALLIC COMPOUNDS.", APPLIED PHYSICS LETTERS, AMERICAN INSTITUTE OF PHYSICS, 2 HUNTINGTON QUADRANGLE, MELVILLE, NY 11747, vol. 55., no. 26., 25 December 1989 (1989-12-25), 2 Huntington Quadrangle, Melville, NY 11747, pages 2760 - 2762., XP000127427, ISSN: 0003-6951, DOI: 10.1063/1.102370 *

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