WO2016108398A1 - Précurseur organique du groupe 13 et procédé de dépôt de couche mince l'utilisant - Google Patents

Précurseur organique du groupe 13 et procédé de dépôt de couche mince l'utilisant Download PDF

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WO2016108398A1
WO2016108398A1 PCT/KR2015/009872 KR2015009872W WO2016108398A1 WO 2016108398 A1 WO2016108398 A1 WO 2016108398A1 KR 2015009872 W KR2015009872 W KR 2015009872W WO 2016108398 A1 WO2016108398 A1 WO 2016108398A1
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precursor
formula
organic group
group
carbon atoms
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Korean (ko)
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이근수
이영민
김상민
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Eugenetech Materials Co Ltd
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Eugenetech Materials Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3414—Deposited materials, e.g. layers characterised by the chemical composition being group IIIA-VIA materials
    • H10P14/3416—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium 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
    • C23C16/06—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3434—Deposited materials, e.g. layers characterised by the chemical composition being oxide semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6336—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
    • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69391—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing aluminium, e.g. Al2O3

Definitions

  • the present invention relates to an organic group 13 precursor and a thin film deposition method using the same, and in detail, an aluminum precursor capable of effectively forming an aluminum-containing film, an aluminum-containing film deposition method using the same, a gallium precursor that can effectively form a gallium-containing film, and It relates to a gallium-containing film deposition method using the same.
  • MOC metal oxide devices
  • Precursors containing a Group 13 element have been spotlighted as precursors having excellent stability and conductivity, and precursors for thin film deposition.
  • precursors containing Group 13 elements are actively utilized in metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) processes.
  • MOCVD metal organic chemical vapor deposition
  • ALD atomic layer deposition
  • the precursor containing the Group 13 element supplied must be thermally stable and have a high vapor pressure at low temperatures.
  • An object of the present invention is to provide an aluminum precursor capable of effectively forming an aluminum containing film and an aluminum containing film deposition method using the same.
  • Another object of the present invention is to provide a gallium precursor capable of effectively forming a gallium-containing film and a method for depositing a gallium-containing film using the same.
  • An organic group 13 precursor according to an embodiment of the present invention is represented by the following ⁇ Formula 1>.
  • M is any one selected from metal elements belonging to the Group 13 element on the periodic table
  • L 1 and L 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms
  • R 1 and R 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 2>.
  • L 1 and L 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms. And any one selected from a cycloalkyl group having 3 to 6 carbon atoms.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 3>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 4>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 5>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 6>.
  • R 1 and R 2 are connected to each other to form a cyclic amine group having 3 to 6 carbon atoms with the nitrogen atom to which R 1 and R 2 are bonded.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 7>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 8>.
  • L 1 and L 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms. And any one selected from a cycloalkyl group having 3 to 6 carbon atoms.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 9>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 10>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 11>.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 12>.
  • R 1 and R 2 are connected to each other to form a cyclic amine group having 3 to 6 carbon atoms with the nitrogen atom to which R 1 and R 2 are bonded.
  • the organic group 13 precursor may be represented by the following ⁇ Formula 13>.
  • a thin film deposition method includes a deposition process for depositing a thin film on a substrate using the organic group 13 precursor.
  • the deposition process may be performed by an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • the chemical vapor deposition may include a metal organic chemical vapor deposition (MOCVD).
  • MOCVD metal organic chemical vapor deposition
  • the deposition process includes a loading step of loading a substrate into the chamber; A heating step of heating the substrate loaded in the chamber; A supplying step of supplying the organic group 13 precursor to the inside of the chamber loaded with the substrate; A compound layer forming step of adsorbing the organic Group 13 precursor onto the substrate to form an organic Group 13 compound layer; And forming a group 13 element-containing film on the substrate by applying thermal energy, plasma, or electrical bias to the substrate.
  • the substrate may be heated to a temperature range of 50 ⁇ 800 °C.
  • the organic group 13 precursor may be heated to a temperature range of 20 to 100 ° C. and supplied onto the substrate.
  • At least one carrier gas selected from argon (Ar), nitrogen (N 2 ), helium (He), and hydrogen may be mixed with the organic group 13 precursor and supplied to the substrate.
  • the Group 13 element-containing film may be an aluminum film or a gallium film.
  • the supplying step may further include a reaction gas supplying step of supplying at least one reaction gas selected from among water vapor (H 2 O), oxygen (O 2 ), and ozone (O 3 ) onto the substrate.
  • a reaction gas supplying step of supplying at least one reaction gas selected from among water vapor (H 2 O), oxygen (O 2 ), and ozone (O 3 ) onto the substrate.
  • the group 13 element-containing film may be an aluminum oxide film or a gallium oxide film.
  • the supplying step further includes a reaction gas supplying step of supplying at least one reaction gas selected from ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ) and nitrogen (N 2 ) onto the substrate. can do.
  • a reaction gas supplying step of supplying at least one reaction gas selected from ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ) and nitrogen (N 2 ) onto the substrate. can do.
  • the Group 13 element-containing film may be an aluminum nitride film or a gallium nitride film.
  • An organic group 13 precursor and an effect of thin film deposition using the same according to an embodiment of the present invention are as follows.
  • the organic group 13 precursor according to an embodiment of the present invention has a small boiling point but has a high boiling point, and thus is present in a liquid state at room temperature, and has excellent thermal stability.
  • the organic group 13 precursor according to the embodiment of the present invention has a strong affinity with the silicon substrate and the metal atom because it includes the nitrogen atom and the organic group 13 atom having an unshared electron pair in one molecular structure.
  • the temperature window of the deposition process can be narrowed.
  • Organic Group 13 precursor according to an embodiment of the present invention has a non-explosive, non-flammable properties, it is easy to maintain, repair and manage the equipment during deposition of the Group 13 element-containing film using it.
  • the group 13 element-containing film is deposited using the organic group 13 precursor according to an embodiment of the present invention
  • the number of molecules of the organic group 13 precursor adsorbed per unit area of the lower structure increases, so that deposition density and deposition uniformity are improved. Therefore, step coverage of the Group 13 element-containing film is improved.
  • the vapor deposition precursor since the vapor deposition precursor has a lower vapor pressure than trimethylaluminum (TMA), it is possible to control the deposition rate during thin film deposition.
  • TMA trimethylaluminum
  • the organic group 13 element-containing film can be effectively deposited using the organic group 13 precursor according to one embodiment of the present invention.
  • 1 is a graph showing the thermal analysis test results of diethylamino diethylaluminum.
  • 3 is a graph showing the thermal analysis test results of ethylmethylamino diethylaluminum.
  • 5 is a graph showing the thermal analysis test results of dimethylamino diethylgallium.
  • 6 is a graph showing the thermal analysis test results of pyrrolidino diethylgallium.
  • FIG. 7 is a graph showing the results of ICP-AES component analysis of an aluminum-containing film deposited using diethylamino diethylaluminum.
  • FIG. 8 is a graph showing the results of ASE component analysis of an aluminum containing film deposited using diethylamino diethyl aluminum.
  • FIG. 9 is a graph showing the growth rate per cycle with respect to the process temperature of the aluminum containing film deposited using diethylamino diethyl aluminum.
  • FIG. 10 is a graph showing the film thickness per cycle of an aluminum containing film deposited using diethylamino diethylaluminum.
  • 11 is a graph showing the results of ICP-AES component analysis of an aluminum-containing film deposited using dimethylamino diethylaluminum.
  • FIG. 12 is a graph showing ASE component analysis results of an aluminum-containing film deposited using dimethylamino diethyl aluminum.
  • FIG. 13 is a graph showing growth rate per cycle versus process temperature of an aluminum-containing film deposited using dimethylamino diethylaluminum.
  • FIG. 14 is a graph showing the film thickness per cycle of an aluminum containing film deposited using dimethylamino diethylaluminum.
  • FIG. 15 is a graph showing ICP-AES component analysis results of an aluminum-containing film deposited using pyrrolidino diethyl aluminum.
  • FIG. 16 is a graph showing ASE component analysis results of an aluminum-containing film deposited using pyrrolidino diethyl aluminum.
  • 17 is a graph showing the film thickness of a film containing aluminum deposited using pyrrolidino diethyl aluminum.
  • the present invention relates to an organic group 13 precursor and a thin film deposition method using the same, it will be described embodiments of the present invention by using the following formula and experimental examples.
  • the embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below.
  • An organic group 13 precursor according to an embodiment of the present invention is represented by the following ⁇ Formula 1>.
  • M is any one selected from metal elements belonging to the Group 13 element on the periodic table
  • L 1 and L 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms
  • R 1 and R 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms.
  • trimethylaluminum is widely used as a precursor to form an aluminum-containing film. Since trimethylaluminum (TMA) is used in many fields besides thin film deposition, there are advantages in that it is easy to supply raw materials, has a very high vapor pressure, and is thermally stable. However, since trimethylaluminum (TMA) has a very high vapor pressure, it is not possible to control the deposition rate of the thin film, and there is a risk of fire due to spontaneous ignition even when only a very small amount is exposed to air. In addition, since trimethylaluminum (TMA) is a compound consisting only of aluminum and carbon, carbon, which is an impurity, is generated during thin film deposition, thereby degrading the quality of the thin film.
  • the present invention seeks to provide an organic Group 13 precursor that can complement the disadvantages of such trimethylaluminum (TMA) and effectively deposit an aluminum containing film.
  • TMA trimethylaluminum
  • the precursor for depositing an aluminum thin film according to an embodiment of the present invention is represented by the following ⁇ Formula 2>.
  • L 1 and L 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms. And any one selected from a cycloalkyl group having 3 to 6 carbon atoms.
  • Substituents L 1 , L 2 , R 1 and R 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 2> may be an alkyl group having 2 carbon atoms, which is represented by the following ⁇ Formula 3>.
  • Substituents L 1 and L 2 of the precursor for aluminum thin film deposition represented by ⁇ Formula 2> may be an alkyl group having 2 carbon atoms, and substituents R 1 and R 2 may be alkyl groups having 1 carbon number. This is represented by the following ⁇ Formula 4>.
  • Substituents L 1 , L 2, and R 1 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 2> may be an alkyl group having 2 carbon atoms, and the substituent R 2 may be an alkyl group having 1 carbon atoms. This is represented by the following ⁇ Formula 5>.
  • Substituents R 1 and R 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 2> may be connected to each other, and R 1 and R 2 may have 3 to 6 carbon atoms together with the nitrogen atom to which R 1 and R 2 are bonded. Cyclic amine groups can be formed. This is represented by the following ⁇ Formula 6>.
  • Substituents L 1 and L 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 6> may be an alkyl group having 2 carbon atoms, and R 1 and R 2 may have 4 carbon atoms together with a nitrogen atom having R 1 and R 2 bonded thereto.
  • the cyclic amine group of can be formed. This is represented by the following ⁇ Formula 7>.
  • the present invention is to provide an organic Group 13 precursor capable of effectively depositing a gallium-containing film.
  • Gallium thin film deposition precursor according to an embodiment of the present invention is represented by the following formula (8).
  • L 1 and L 2 are each independently selected from an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms. And any one selected from a cycloalkyl group having 3 to 6 carbon atoms.
  • Substituents L 1 , L 2 , R 1 and R 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 8> may be an alkyl group having 2 carbon atoms, which is represented by the following ⁇ Formula 9>.
  • Substituents L 1 and L 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 8> may be an alkyl group having 2 carbon atoms, and substituents R 1 and R 2 may be alkyl groups having 1 carbon number. This is represented by the following ⁇ Formula 10>.
  • Substituents L 1 , L 2, and R 1 of the precursor for aluminum thin film deposition represented by ⁇ Formula 8> may be an alkyl group having 2 carbon atoms, and the substituent R 2 may be an alkyl group having 1 carbon number. This is represented by the following formula (11).
  • Substituents R 1 and R 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 8> may be connected to each other, and R 1 and R 2 may have 3 to 6 carbon atoms together with the nitrogen atom to which R 1 and R 2 are bonded. Cyclic amine groups can be formed. This is represented by the following formula (12).
  • Substituents L 1 and L 2 of the precursor for depositing an aluminum thin film represented by ⁇ Formula 12> may be an alkyl group having 2 carbon atoms, and R 1 and R 2 may have 4 carbon atoms together with a nitrogen atom having R 1 and R 2 bonded thereto.
  • the cyclic amine group of can be formed. This is represented by the following formula (13).
  • DSC differential scanning calorimetry
  • TGA thermogravimetric analysis
  • DSC Differential scanning calorimetry
  • TGA thermogravimetric analysis
  • Heating profile heating from 30 ° C. to 350 ° C. at a heating rate of 10 ° C./min
  • FIG. 1 shows the DSC thermal curves and TGA thermal curves obtained through the thermal analysis test results in one diagram.
  • the thermal curves indicated by dotted lines indicate the results obtained from the DSC test, and the thermal curves indicated by solid lines Results obtained from the TGA test are shown.
  • the pyrolysis temperature of the DSC test was designated as the temperature at the point where the heat flow amount of the DSC heat curve decreases and then suddenly rises again.
  • the pyrolysis temperature of diethylamino diethylaluminum is about 237.12 ° C., and the residual component amount is about 1.613% of the initial weight.
  • the diethylamino diethylaluminum of the present invention is excellent in thermal stability, it can be confirmed that the residue is small.
  • FIG. 2 shows the DSC thermal curves and the TGA thermal curves obtained through the thermal analysis test results in one diagram, and shows the results obtained from the DSC test of the thermal curves indicated by dotted lines. Results obtained from the TGA test are shown.
  • the pyrolysis temperature of the DSC test was designated as the temperature at which the DSC heat curve decreases when the heat flow rate increases and then suddenly rises again. As shown in FIG. 2, the pyrolysis temperature of dimethylamino diethylaluminum is about 192.79 ° C., and the residual amount is about 2.100% of the initial weight.
  • the dimethylamino diealkylaluminum of the present invention is excellent in thermal stability, it can be confirmed that the residue is small.
  • FIG. 3 shows the DSC thermal curves and the TGA thermal curves obtained through the thermal analysis test results in one drawing.
  • the thermal curves indicated by dotted lines indicate the results obtained from the DSC test, and the thermal curves indicated by solid lines Results obtained from the TGA test are shown.
  • the pyrolysis temperature of the DSC test was designated as the temperature at the point where the heat flow amount of the DSC heat curve decreases and then suddenly rises again. As shown in FIG.
  • the thermal decomposition temperature of ethylmethylamino diethylaluminum is about 217.04 ° C., and the residual amount of the residue is about 1.218% based on the initial weight. Therefore, the ethylmethylamino diethylaluminum of the present invention is excellent in thermal stability, it can be confirmed that the residue is small.
  • FIG. 4 shows the DSC thermal curves and the TGA thermal curves obtained through the thermal analysis test results in one diagram.
  • the thermal curves indicated by dotted lines indicate the results obtained by the DSC test, and the thermal curves indicated by solid lines Results obtained from the TGA test are shown.
  • the pyrolysis temperature of the DSC test was designated as the temperature at the point where the heat flow amount of the DSC heat curve decreases and then suddenly rises again.
  • the pyrolytico diethylaluminum pyrolysis temperature is about 217.04 ° C., and the residual amount is about 1.218% based on the initial weight. Therefore, the pyrrolidino diethyl aluminum of the present invention is excellent in thermal stability, it can be confirmed that the residue is small.
  • FIG. 5 shows the DSC thermal curves and the TGA thermal curves obtained through the thermal analysis test results in one diagram, and the thermal curves indicated by dotted lines show the results obtained from the DSC test, and the thermal curves indicated by solid lines Results obtained from the TGA test are shown.
  • the pyrolysis temperature of the DSC test was designated as the temperature at the point where the heat flow amount of the DSC heat curve decreases and then suddenly rises again.
  • the thermal decomposition temperature of dimethylamino diethylgallium was found to be 198.74 ° C., and T1 / 2 was 178.83 ° C.
  • the residual component amount (residue) after the temperature is raised to 350 °C is about 3.2% of the initial weight.
  • the dimethylamino diethylgallium of the present invention is excellent in thermal stability, it can be confirmed that the residue is small.
  • FIG. 6 shows the DSC thermal curves and the TGA thermal curves obtained through the thermal analysis test results in one drawing.
  • the thermal curves indicated by dotted lines show the results obtained from the DSC test, and the thermal curves indicated by solid lines Results obtained from the TGA test are shown.
  • the pyrolysis temperature of the DSC test was designated as the temperature at the point where the heat flow amount of the DSC heat curve decreases and then suddenly rises again.
  • pyrolidino diethylgallium had a thermal decomposition temperature of 229.28 ° C. and T1 / 2 of 251.31 ° C.
  • the residual component amount (residue) remaining after the temperature is raised to 350 °C is about 3.466% of the initial weight. Therefore, the pyrrolidino diethylgallium of the present invention is excellent in thermal stability, it can be confirmed that the residue is small.
  • the organic Group 13 precursor according to an embodiment of the present invention has a small boiling point but has a high boiling point and thus exists in a liquid state at room temperature, and has excellent thermal stability.
  • a nitrogen atom and an aluminum or gallium atom having an unshared electron pair are included in one molecular structure, it exhibits a strong affinity with a silicon substrate and a metal atom.
  • the thin film deposition method includes a deposition process of depositing an aluminum-containing film or a gallium-containing film on a substrate by using the aforementioned organic group 13 precursor.
  • the deposition process may be performed by an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, and the chemical vapor deposition (CVD) may be performed by an organic metal chemical deposition process (Metal Organic). Chemical Vapor Deposition, MOCVD).
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • MOCVD Metal Organic
  • the deposition process may include a loading step (S100) of loading a substrate into a chamber providing a space in which a process for the substrate is performed, a heating step (S200) of heating a substrate loaded in the chamber, and a chamber loaded with a substrate.
  • a loading step (S100) of loading a substrate into a chamber providing a space in which a process for the substrate is performed a heating step (S200) of heating a substrate loaded in the chamber, and a chamber loaded with a substrate.
  • the supply step (S300) of supplying the organic group 13 precursor according to an embodiment of the present invention the compound layer for adsorbing the supplied organic group 13 precursor on the substrate to form an organic aluminum compound layer or organic gallium compound layer Forming step (S400) and the film forming step (S500) of forming an aluminum-containing or gallium-containing film by applying thermal energy, plasma or electrical bias to the substrate on which the organic aluminum compound layer or organic gallium compound layer is formed.
  • the substrate may be heated to a temperature range of 50 to 800 ° C.
  • the organic group 13 precursor may be heated to a temperature range of 20 to 100 ° C. and supplied onto the substrate.
  • the organic group 13 precursor and one or more carrier gases selected from argon (Ar), nitrogen (N 2 ), helium (He) and hydrogen according to an embodiment of the present invention may be mixed and supplied onto the substrate. have.
  • the deposition process is performed by supplying only the mixture of the organic group 13 precursor and the carrier gas on the substrate according to an embodiment of the present invention, an aluminum film or gallium film is deposited on the substrate.
  • the organic group 13 precursor according to an embodiment of the present invention is supplied onto a substrate, and oxygen-based reaction gases such as water vapor (H 2 O), oxygen (O 2 ), and ozone (O 3 ) are supplied. It can supply on a board
  • the oxygen-based reaction gas may be supplied onto the substrate together with the organic Group 13 precursor according to the embodiment of the present invention, or may be supplied onto the substrate separately from the organic Group 13 precursor according to the embodiment of the present invention.
  • a metal aluminum oxide film or a gallium oxide film, a hafnium gallium oxide film, such as an aluminum oxide film, a hafnium aluminum oxide film, a zirconium aluminum oxide film, and a titanium aluminum oxide film A metal gallium oxide film such as a zirconium gallium oxide film and a titanium gallium oxide film can be formed.
  • the organic group 13 precursor according to an embodiment of the present invention is supplied onto a substrate, and ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ), and nitrogen (N 2 ) A nitrogen-based reaction gas such as this can be supplied onto the substrate.
  • the nitrogen-based reaction gas may be supplied onto the substrate together with the organic Group 13 precursor according to the embodiment of the present invention, or may be supplied onto the substrate separately from the organic Group 13 precursor according to the embodiment of the present invention.
  • a metal aluminum nitride film such as an aluminum nitride film, a hafnium aluminum nitride film, a zirconium aluminum nitride film, and a titanium aluminum nitride film or a gallium nitride film, a hafnium gallium nitride film
  • a metal gallium nitride film such as a zirconium gallium nitride film and a titanium gallium nitride film, may be formed.
  • the organic group 13 precursor according to an embodiment of the present invention is a bubbling method, a vapor phase mass flow controller method, a direct liquid injection (DLI) method, It may be supplied onto the substrate by a liquid transfer method for dissolving and transferring in an organic solvent, but is not necessarily limited to these methods.
  • a liquid transfer method for dissolving and transferring in an organic solvent but is not necessarily limited to these methods.
  • the excess organic group 13 which is not adsorbed on the substrate by supplying a first purge gas selected from an inert gas such as argon (Ar), nitrogen (N 2 ), and helium (He) into the chamber.
  • a first purge gas selected from an inert gas such as argon (Ar), nitrogen (N 2 ), and helium (He) into the chamber.
  • the first purge step S410 may be performed to remove the precursor, and in the first purge step S410, the first purge gas may be supplied into the chamber in less than 1 minute.
  • a second purge for supplying a second purge gas selected from an inert gas such as argon (Ar), nitrogen (N 2 ), and helium (He) to the chamber to remove excess reaction gas and by-products.
  • Step S510 may be performed, and in the second purge step S510, the second purge gas may be introduced into the chamber in less than 1 minute.
  • a thin film deposition method using an organic group 13 precursor according to an embodiment of the present invention will be described in detail with reference to the following examples.
  • the following examples are presented to aid the understanding of the present invention, and the scope of the present invention is not limited to the following examples.
  • An argon (Ar) gas having a flow rate of 250 sccm was used as a carrier gas, and the diethylamino diethylaluminum compound was supplied at a feed rate of 0.02 g per minute using a LMF (Liguid Flow Meter).
  • the temperature of the feed pipe for supplying the diethylamino diethylaluminum compound into the chamber was maintained at a temperature range of 180 to 185 ° C.
  • the process pressure in the chamber was adjusted to 0.3 torr, and the process conditions were controlled so that the diethylamino diethylaluminum compound gas contacted the substrate alternately with O 2 .
  • the deposition process used a cycle of supplying diethylamino diethylaluminum compound gas for 1 second, argon (Ar) gas supply for 1 second, O 2 gas supply for 0.2 second, and plasma application, and argon (Ar) gas for 1 second.
  • the aluminum-containing film deposited by the deposition process was confirmed by ICP-AES, ASE component analysis.
  • FIG. 7 is a graph showing ICP-AES component analysis results of the aluminum-containing film deposited by the deposition process
  • FIG. 8 is a graph showing ASE component analysis results of the aluminum-containing film deposited by the deposition process.
  • C residual carbon
  • FIG. 9 is a graph showing the growth rate per cycle with respect to the process temperature of the aluminum-containing film deposited by the deposition process
  • Figure 10 is a graph showing the film thickness per cycle of the aluminum-containing film deposited by the deposition process.
  • the growth rate (Growth Per Cycle, GPC) is 0.75 ⁇ 0.8 kHz level. Since the growth rate per cycle (GPC) of trimethylaluminum (TMA) in the same temperature range is about 1.0 kW, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention when using trimethylaluminum (TMA) It can be seen that the growth rate per cycle (GPC) is low.
  • the aluminum-containing film thickness deposited by the deposition process increases linearly as the deposition cycle proceeds. Therefore, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention can easily adjust the thickness of the thin film according to the control of the deposition cycle.
  • dimethylamino diethylaluminum compound obtained in Experimental Example 2 was used as a precursor, and the deposition process was performed at a process temperature of 400 ° C. in the chamber.
  • the dimethylamino diethylaluminum compound was vaporized in a container made of stainless steel, and the vaporization temperature of the vaporizer was set to 130 ° C.
  • Argon (Ar) gas having a flow rate of 250 sccm was used as the carrier gas, and the dimethylamino diethylaluminum compound was supplied at a feed rate of 0.02 g per minute using an LMF (Liguid Flow Meter).
  • LMF Liguid Flow Meter
  • the temperature of the feed tube for supplying the dimethylamino diethylaluminum compound into the chamber was maintained in the temperature range of 135 ⁇ 140 °C.
  • the process pressure in the chamber was adjusted to 0.3 torr, and the process conditions were controlled so that the dimethylamino diethylaluminum compound gas contacted the substrate alternately with O 2 .
  • the deposition process used a cycle of supplying dimethylamino diethylaluminum compound gas for 0.8 seconds, argon (Ar) gas supply for 1 second, O 2 gas supply and plasma application for 1 second, and argon (Ar) gas for 1 second.
  • the aluminum-containing film deposited by the deposition process was confirmed by ICP-AES, ASE component analysis.
  • FIG. 11 is a graph showing ICP-AES component analysis results of the aluminum-containing film deposited by the deposition process
  • Figure 12 is a graph showing the ASE component analysis results of the aluminum-containing film deposited by the deposition process.
  • C residual carbon
  • FIG. 13 is a graph showing the growth rate per cycle with respect to the process temperature of the aluminum-containing film deposited by the deposition process
  • Figure 14 is a graph showing the film thickness per cycle of the aluminum-containing film deposited by the deposition process.
  • the growth rate (Growth Per Cycle, GPC) is 0.75 ⁇ 0.8 kHz level. Since the growth rate per cycle (GPC) of trimethylaluminum (TMA) in the same temperature range is about 1.0 kW, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention when using trimethylaluminum (TMA) It can be seen that the growth rate per cycle (GPC) is low.
  • the thickness of the aluminum-containing film deposited by the deposition process increases linearly as the deposition cycle progresses. Therefore, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention can easily adjust the thickness of the thin film according to the control of the deposition cycle.
  • the process pressure in the chamber was adjusted to 0.3 torr, and the process conditions were controlled such that the pyrrolidino diethylaluminum compound gas contacted the substrate alternately with O 2 .
  • the deposition process used a cycle of supplying pyrrolidino diethylaluminum compound gas for 0.6 seconds, argon (Ar) gas supply for 2 seconds, O 2 gas supply and plasma application for 1 second, and argon (Ar) gas for 0.5 seconds.
  • the aluminum-containing film deposited by the deposition process was confirmed by ICP-AES, ASE component analysis.
  • FIG. 15 is a graph showing ICP-AES component analysis results of an aluminum-containing film deposited by the deposition process
  • FIG. 16 is a graph showing ASE component analysis results of an aluminum-containing film deposited by the deposition process.
  • C residual carbon
  • FIG. 17 is a graph showing the film thickness of the aluminum-containing film deposited by the deposition process with respect to the process temperature based on 200 cycles.
  • a growth rate per cycle (GPC) is about 0.4 ⁇ s. Since the growth rate per cycle (GPC) of trimethylaluminum (TMA) in the same temperature range is about 1.0 kW, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention when using trimethylaluminum (TMA) It can be seen that the growth rate per cycle (GPC) is low. Therefore, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention can easily adjust the thickness of the thin film according to the control of the deposition cycle.
  • GPC growth rate per cycle

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Abstract

Un précurseur organique du groupe 13 selon un mode de réalisation de la présente invention est indiqué par (R1R2N) M (L1L2), dans lequel M est sélectionné parmi les métaux qui appartiennent aux éléments du groupe 13 dans le tableau périodique des éléments, L1 et L2 sont indépendamment sélectionnés parmi un groupe alkyle ayant de 1 à 6 atomes de carbone ou un groupe cycloalkyle ayant de 3 à 6 atomes de carbone, et R1 et R2 sont indépendamment sélectionnés parmi un groupe alkyle ayant de 1 à 6 atomes de carbone ou un groupe cycloalkyle ayant de 3 à 6 atomes de carbone.
PCT/KR2015/009872 2014-12-31 2015-09-21 Précurseur organique du groupe 13 et procédé de dépôt de couche mince l'utilisant Ceased WO2016108398A1 (fr)

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KR1020150058809A KR20160082321A (ko) 2014-12-31 2015-04-27 알루미늄 박막 증착용 전구체 및 이를 이용한 박막 증착 방법

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CN107619419A (zh) * 2016-07-14 2018-01-23 三星电子株式会社 铝化合物以及使用其形成薄膜和制造集成电路器件的方法
CN115279940A (zh) * 2020-02-24 2022-11-01 Up化学株式会社 铝前体化合物、其制备方法和使用其形成含铝膜的方法

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JPS62276832A (ja) * 1986-05-26 1987-12-01 Hitachi Ltd 被膜形成方法およびそれを用いた半導体装置の製造方法
JPH02217473A (ja) * 1988-02-29 1990-08-30 Natl Res Dev Corp 窒化アルミニウムフィルムの形成方法
US5209952A (en) * 1989-03-09 1993-05-11 Merck Patent Gesellschaft Mit Beschraenkter Haftung Use of organometallic compounds to deposit thin films from the gas phase
KR950001217B1 (ko) * 1986-09-16 1995-02-14 메르크 파텐트 게젤샤프트 미트 베슈랭크터 하프퉁 박막형성방법
US20130330936A1 (en) * 2011-02-07 2013-12-12 Technische Universiteit Eindhoven METHOD OF DEPOSITION OF Al2O3/SiO2 STACKS, FROM ALUMINIUM AND SILICON PRECURSORS

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JPS62276832A (ja) * 1986-05-26 1987-12-01 Hitachi Ltd 被膜形成方法およびそれを用いた半導体装置の製造方法
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