WO2024253146A1 - 金属モリブデン膜を有する基板及び該基板の製造方法 - Google Patents

金属モリブデン膜を有する基板及び該基板の製造方法 Download PDF

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WO2024253146A1
WO2024253146A1 PCT/JP2024/020632 JP2024020632W WO2024253146A1 WO 2024253146 A1 WO2024253146 A1 WO 2024253146A1 JP 2024020632 W JP2024020632 W JP 2024020632W WO 2024253146 A1 WO2024253146 A1 WO 2024253146A1
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Prior art keywords
substrate
film
atoms
molybdenum film
gas
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English (en)
French (fr)
Japanese (ja)
Inventor
佑真 土手
亜紀応 菊池
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority to KR1020267000761A priority patent/KR20260021747A/ko
Publication of WO2024253146A1 publication Critical patent/WO2024253146A1/ja
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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
    • C23C16/06—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
    • C23C16/08—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 metal halides
    • C23C16/14—Deposition of only one other metal element
    • 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
    • C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4485—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation without using carrier gas in contact with the source material
    • 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
    • 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
    • C23C16/52—Controlling or regulating the coating process
    • 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
    • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
    • H10P14/42—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials using a gas or vapour

Definitions

  • This disclosure relates to a substrate having a metal molybdenum film and a method for manufacturing the substrate.
  • tungsten films are used as wiring formed on substrates such as semiconductor wafers (hereafter simply referred to as wafers) that are to be processed.
  • Tungsten films formed as wiring usually have a barrier metal layer such as TiN provided along the tungsten film to prevent silicon atoms from surrounding silicon-based compounds from diffusing and forming silicide.
  • the wiring is composed of a tungsten film and barrier metal layers provided on both sides of the tungsten film along the tungsten film.
  • the wiring is composed of three layers stacked in this order: a barrier metal layer, a tungsten film, and a barrier metal layer.
  • the wiring width needs to be miniaturized as memory density increases.
  • the proportion of the barrier metal layer in the wiring increases and the proportion of the tungsten film, which is a conductive layer, decreases, which can increase the electrical resistance of the wiring and reduce the performance and reliability of the device.
  • a barrier metal layer is required, so in order to accommodate miniaturization of the wiring width, it is important to use a metal film that does not require a barrier metal layer.
  • the present inventors focused on a metal molybdenum film as a metal film that does not require a barrier metal layer.
  • Patent Document 1 discloses a film formation process in which a gas containing a molybdenum precursor and a reducing agent is supplied to a substrate to form a metal molybdenum film on the substrate.
  • a gas containing a molybdenum precursor and a reducing agent is supplied to a substrate to form a metal molybdenum film on the substrate.
  • the molybdenum precursor only various compounds are disclosed as the molybdenum precursor, and it cannot be said that detailed studies have been conducted.
  • the present disclosure aims to solve the above-mentioned problem newly discovered by the present inventors and provide a method for manufacturing a substrate having a metal molybdenum film while suppressing damage to the underlying layer.
  • molybdenum oxyhalides such as compounds consisting of only molybdenum, halogen and oxygen.
  • some types of molybdenum oxyhalides have high impurity (oxygen atom) content in the metal molybdenum film and high electrical resistivity, and therefore cannot be used as a good wiring material.
  • MoO2Cl2 and Mo4O11I have a high ratio of O to Mo, so that the content of oxygen atoms remaining in the metal molybdenum film is high, while MoOX4 (X is a halogen) has a low ratio of O to Mo, so that the content of oxygen atoms remaining in the metal molybdenum film can be reduced.
  • the present disclosure (1) relates to a method for producing a substrate having a metallic molybdenum film, including a film formation step of supplying a gas containing gaseous MoOF4 and a gas containing a gaseous reducing agent to a substrate and forming a metallic molybdenum film on the substrate.
  • the present disclosure (2) relates to a method for manufacturing a substrate according to the present disclosure (1), in which the temperature of the substrate is 25°C to 800°C in the film formation process.
  • the present disclosure (3) relates to a method for producing a substrate according to the present disclosure (1) or (2), in which the content of oxygen atoms in the metal molybdenum film is less than 1.0 ⁇ 10 20 atoms/cm 3 .
  • the present disclosure (4) relates to a method for manufacturing a substrate according to any one of the present disclosures (1) to (3), in which the reducing agent is at least one selected from the group consisting of hydrogen, monomethylsilane, dimethylsilane, and trimethylsilane.
  • the present disclosure (5) relates to the method for producing a substrate according to any one of the present disclosures (1) to (4), wherein in the film formation step, the outermost surface of the substrate is at least one selected from the group consisting of Si, SiO 2 , SiN, AlO x , HfO x , ZrO x , TiN, TaN, Ti, Co, Ru, Ta and W.
  • the present disclosure (6) relates to a method for manufacturing a substrate according to any one of the present disclosures (1) to (5), in which the gas pressure is 0.1 Pa to 10 kPa.
  • the present disclosure (7) relates to a method for producing a substrate according to any one of the present disclosures (1) to (6), comprising a MoOF4 gas preparation step of heating and/or reducing pressure on solid MoOF4 to prepare the gaseous MoOF4 .
  • the present disclosure (8) relates to a method for manufacturing a substrate according to any one of the present disclosures (1) to (7), in which a gas containing gaseous MoOF 4 and a gas containing a gaseous reducing agent are simultaneously supplied in the film formation step.
  • the present disclosure (9) relates to a method for manufacturing a substrate according to any one of the present disclosures (1) to (7), in which a gas containing gaseous MoOF 4 and a gas containing a gaseous reducing agent are alternately supplied in the film formation step.
  • the present disclosure (10) relates to a method for manufacturing a semiconductor device, the method comprising the steps of :
  • the content of fluorine atoms in the film is less than 1.0 ⁇ 10 17 atoms/cm 3
  • the present invention relates to a substrate having a metal molybdenum film having a chlorine atom content of less than 1.0 ⁇ 10 17 atoms/cm 3 .
  • the present disclosure (11) relates to a substrate having the metallic molybdenum film according to the present disclosure (10), in which the content of carbon atoms in the film is less than 1.0 ⁇ 10 17 atoms/cm 3 .
  • the present disclosure (12) relates to a substrate having a metal molybdenum film as described in the present disclosure (10) or (11), in which the interface between the metal molybdenum film and the outermost surface of the substrate has a ten-point average roughness of 20 nm or less when observed at 50,000 times magnification.
  • the present disclosure (13) relates to a method for manufacturing a semiconductor device, the method comprising the steps of :
  • the content of fluorine atoms in the film is less than 1.0 ⁇ 10 15 atoms/cm 3
  • the present invention relates to a substrate having the metal molybdenum film according to the present disclosure (10), in which the content of chlorine atoms in the film is less than 1.0 ⁇ 10 15 atoms/cm 3 .
  • the present disclosure (14) relates to a substrate having the metallic molybdenum film according to the present disclosure (13), in which the content of carbon atoms in the film is less than 1.0 ⁇ 10 15 atoms/cm 3 .
  • the present disclosure relates to a substrate having a metal molybdenum film according to the present disclosure (13) or (14), in which the interface between the metal molybdenum film and the outermost surface of the substrate has a ten-point average roughness of 2 nm or less when observed at 50,000 times magnification.
  • the method for producing a substrate according to the present disclosure is a method for producing a substrate having a metallic molybdenum film, comprising a film formation step of supplying a gas containing gaseous MoOF4 and a gas containing a gaseous reducing agent to a substrate and forming a metallic molybdenum film on the substrate. Since MoOF4 is used as a molybdenum precursor, a substrate having a metallic molybdenum film with a low content of impurities (oxygen atoms, chlorine atoms) can be produced while suppressing damage to the substrate.
  • impurities oxygen atoms, chlorine atoms
  • the substrate of the present disclosure is a substrate having a metallic molybdenum film in which the content of oxygen atoms in the film is less than 1.0 ⁇ 1020 atoms/ cm3 , the content of fluorine atoms in the film is less than 1.0 ⁇ 1017 atoms/ cm3 , and the content of chlorine atoms in the film is less than 1.0 ⁇ 1017 atoms/ cm3 , and therefore is a substrate having a metallic molybdenum film with low electrical resistivity.
  • FIG. 2 is a schematic diagram showing an example of a film forming apparatus that can be used in the substrate manufacturing method of the present disclosure.
  • X to Y in the explanation of a numerical range means from X to Y, unless otherwise specified.
  • X to Y in the explanation of a numerical range means from X to Y, unless otherwise specified.
  • 1 to 5% by mass means "1% by mass to 5% by mass.”
  • the substrate of the present disclosure is a substrate having a metallic molybdenum film with an oxygen atom content of less than 1.0 ⁇ 10 20 atoms/cm 3 , and is therefore a substrate having a metallic molybdenum film with low electrical resistivity.
  • the substrate of the present disclosure is preferably a substrate having a metallic molybdenum film in which the content of oxygen atoms in the film is less than 1.0 ⁇ 10 20 atoms/cm 3 , the content of fluorine atoms in the film is less than 1.0 ⁇ 10 17 atoms/cm 3 , and the content of chlorine atoms in the film is less than 1.0 ⁇ 10 17 atoms/cm 3 , and more preferably a substrate having a metallic molybdenum film in which the content of oxygen atoms in the film is less than 1.0 ⁇ 10 15 atoms/cm 3 , the content of fluorine atoms in the film is less than 1.0 ⁇ 10 15 atoms/cm 3 , and the content of chlorine atoms in the film is less than 1.0 ⁇ 10 15 atoms/cm 3.
  • metal molybdenum film means a metal film of molybdenum.
  • the content of oxygen atoms in the metal molybdenum film is less than 1.0 ⁇ 10 20 atoms/cm 3 , preferably less than 1.0 ⁇ 10 17 atoms/cm 3 , more preferably less than 1.0 ⁇ 10 15 atoms/cm 3 , and particularly preferably less than 1.0 ⁇ 10 14 atoms/cm 3 , and the lower limit is not particularly limited, but is, for example, 1.0 ⁇ 10 10 atoms/cm 3 or more. This tends to result in a metal molybdenum film with lower electrical resistivity (higher electrical conductivity).
  • the content of each atom in the metal molybdenum film is measured by secondary ion mass spectrometry (SIMS).
  • SIMS secondary ion mass spectrometry
  • atoms/ cm3 means the density of the number of atoms (e.g., oxygen atoms) present in a space.
  • the metallic molybdenum film may be formed using MoOF4 as a molybdenum precursor.
  • the content of fluorine atoms in the metal molybdenum film is preferably less than 1.0 ⁇ 10 17 atoms/cm 3 , more preferably less than 1.0 ⁇ 10 15 atoms/cm 3 , and particularly preferably less than 1.0 ⁇ 10 14 atoms/cm 3 , and the lower limit is not particularly limited, but is, for example, 1.0 ⁇ 10 10 atoms/cm 3. This tends to result in a metal molybdenum film with lower electrical resistivity.
  • the content of chlorine atoms in the metal molybdenum film is preferably less than 1.0 ⁇ 10 17 atoms/cm 3 , more preferably less than 1.0 ⁇ 10 15 atoms/cm 3 , and particularly preferably less than 1.0 ⁇ 10 14 atoms/cm 3 , and the lower limit is not particularly limited, but is, for example, 1.0 ⁇ 10 10 atoms/cm 3. This tends to result in a metal molybdenum film with lower electrical resistivity.
  • the carbon atom content in the metal molybdenum film is preferably less than 1.0 ⁇ 10 17 atoms/cm 3 , more preferably less than 1.0 ⁇ 10 15 atoms/cm 3 , and particularly preferably less than 1.0 ⁇ 10 14 atoms/cm 3 , and the lower limit is not particularly limited, but is, for example, 1.0 ⁇ 10 10 atoms/cm 3. This tends to result in a metal molybdenum film with lower electrical resistivity.
  • the metallic molybdenum film may be formed using MoOF4 as a molybdenum precursor.
  • MoOF4 molybdenum precursor
  • carbonyl molybdenum such as a compound having molybdenum and a carbonyl group as a molybdenum precursor
  • the carbon atom content in the film tends to be large, resulting in a metallic molybdenum film with a higher electrical resistivity.
  • the electrical conductivity of the metal molybdenum film at 25° C. is preferably 1.0 ⁇ 10 4 S/cm or more, more preferably 1.0 ⁇ 10 5 S/cm or more, and although there is no particular upper limit, it is, for example, 5.0 ⁇ 10 6 S/cm or less. This tends to result in a metal molybdenum film with lower electrical resistivity.
  • the electrical conductivity of the metal molybdenum film is measured by a four-terminal method. Note that the measured electrical conductivity includes that of the substrate surface (e.g., TiN), so the electrical conductivity of the metal molybdenum film is calculated by subtracting the electrical conductivity of the substrate surface.
  • the metal molybdenum film may be formed using MoOF4 as a molybdenum precursor.
  • the thickness (amount of film formed) of the metal molybdenum film is, for example, preferably 0.1 nm to 10 ⁇ m, more preferably 1 nm to 2 ⁇ m, which tends to provide better electrical conductivity.
  • the thickness of the metal molybdenum film means the thickness of the metal molybdenum film formed on the substrate (the length in the normal direction from the substrate surface) and means the average value of measurements taken at multiple locations.
  • the thickness of the metal molybdenum film (amount of film formed) is measured from a cross-sectional image taken with a scanning electron microscope (SEM).
  • the width of the metal molybdenum film is preferably 0.5 nm to 100 nm, more preferably 0.8 nm to 50 nm, and even more preferably 1 nm to 10 nm. Since the electrical resistivity of a metal film depends on the width (wiring width), particularly in a narrow wiring width of several nm to several tens of nm, the electrical resistance due to remaining impurities in the film increases, which may lead to an increase in electrical resistivity, so that when the width of the metal molybdenum film is within the above numerical range, the effects of the present disclosure tend to be more favorably obtained.
  • the width of the metallic molybdenum film means the width of the metallic molybdenum film formed on the substrate (the length in the direction perpendicular to the thickness direction in a cross section perpendicular to the extending direction of the film), and means the average value when measured at multiple points.
  • the width of the metallic molybdenum film is measured from a surface image taken by a scanning electron microscope (SEM).
  • a substrate having a metal molybdenum film means that the metal molybdenum film is formed on the substrate, and the metal molybdenum film may be formed on a pattern formed on the substrate. In addition, other layers such as an underlayer may be present between the substrate and the metal molybdenum film.
  • the metal molybdenum film is preferably used as wiring formed on the substrate.
  • the substrate (substrate on which the metal molybdenum film is formed) is not particularly limited, and for example, a silicon wafer is usually used, but is not limited thereto.
  • a silicon wafer is usually used, but is not limited thereto.
  • substrates for semiconductor devices such as SiO 2 , SiN, AlO x , HfO x , ZrO x , TiN, TaN, Ti, Co, Ru, Ta, and W can be mentioned.
  • the substrate may be subjected to surface treatment such as silane coupling treatment, silazane treatment, formation of an organic thin film, and SAM treatment (Self Assembled Monolayer).
  • the substrate may have a metal or metal oxide film, and specifically, it may be a substrate of a semiconductor device having a metal or metal oxide film in its structure, or a substrate on which a metal or metal oxide is formed during the patterning process of the semiconductor device.
  • the outermost surface of the substrate is preferably at least one selected from the group consisting of Si, SiO2 , SiN, AlOx , HfOx , ZrOx, TiN, TaN, Ti, Co, Ru, Ta and W, more preferably at least one selected from the group consisting of Si , SiO2 , TiN, TaN, Ti, Co, Ru and Ta, and even more preferably at least one selected from the group consisting of Si, TiN, TaN, Ti and Ta, which are likely to cause damage to the underlayer when molybdenum halide is used.
  • These materials may be used alone or in combination of two or more.
  • AlO x means an oxide of aluminum, and other similar terms have the same meaning.
  • the ten-point average roughness of the interface between the metal molybdenum film and the outermost surface of the substrate when observed at 50,000 times magnification is preferably 20 nm or less, more preferably 10 nm or less, even more preferably 5 nm or less, and particularly preferably 2 nm or less.
  • the use of MoOF4 can suppress damage to the base, so that the outermost surface of the substrate can be maintained smooth.
  • the ten-point average roughness can be measured by the method described in the Examples.
  • the silicon may be polycrystalline or monocrystalline.
  • the shape and size of the substrate are not particularly limited.
  • the method for manufacturing a substrate of the present disclosure is a method for manufacturing a substrate having a metal molybdenum film, which includes a film formation step of supplying a gas containing gaseous MoOF 4 and a gas containing a gaseous reducing agent to a substrate and forming a metal molybdenum film on the substrate. Since MoOF 4 is used as a molybdenum precursor, a substrate having a metal molybdenum film with a low content of impurities (oxygen atoms, fluorine atoms, chlorine atoms) can be manufactured while suppressing damage to the base. Thus, the method for manufacturing a substrate of the present disclosure is characterized by using a specific molybdenum precursor, so the film formation device and film formation method used are not particularly limited.
  • MoO2Cl2 and Mo4O11I have a large ratio of O to Mo, so the content of oxygen atoms remaining in the metal molybdenum film is large, while MoOF4 has a small ratio of O to Mo, so the content of oxygen atoms remaining in the metal molybdenum film can be reduced.
  • gas means a gaseous state, and is a concept including a material that is gaseous at normal temperature and pressure, a vaporized solid, and a vaporized liquid.
  • molybdenum precursor refers to a compound that can react with a reducing agent to form a metallic molybdenum film.
  • FIG. 1 is a schematic diagram showing an example of a film forming apparatus that can be used in the substrate manufacturing method of the present disclosure.
  • the film forming apparatus 100 has an airtight processing vessel 110, in which a mounting part 111 is arranged to horizontally support the objects (wafers) 112, 113, and 114 to be processed, which are substrates to be processed.
  • the mounting part 111 is made of a material that is resistant to corrosion, such as Ni.
  • a heating means 160 is connected to the mounting part 111 and the ceiling wall of the processing vessel 110, and a heater power source (not shown) is connected to the heating means 160. Meanwhile, a thermometer (not shown) is provided near the upper surface of the mounting part 111, and a signal from the thermometer is transmitted to a heater controller (not shown).
  • the heater controller then sends a command to the heater power source (not shown) in response to the signal from the thermometer, controls the heating of the heating means 160, and controls the objects (wafers) 112, 113, and 114 to a predetermined temperature.
  • the mounting part 111 can be raised and lowered by a lifting mechanism (not shown).
  • the thermometer may be installed to measure the temperature of the inner wall of the processing vessel 110, and the heater control may control the wall of the processing vessel 110 to a predetermined temperature.
  • the molybdenum precursor supply unit 130 has a film-forming raw material tank (not shown) that contains the molybdenum precursor, which is a film-forming raw material.
  • a heater (not shown) is provided around the film-forming raw material tank, and the film-forming raw material in the film-forming raw material tank can be heated to an appropriate temperature (e.g., 50°C to 150°C) to vaporize the molybdenum precursor as necessary.
  • the molybdenum precursor supply unit 130 supplies the molybdenum precursor gas into the processing vessel 110 via the valve 131, the flow rate control means 132, and the pipes 121 and 133.
  • the molybdenum precursor gas may be diluted with an inert gas.
  • the reducing agent supply unit 140 has a reducing agent tank (not shown) that contains the reducing agent, which is a film-forming raw material.
  • a heater (not shown) is provided around the reducing agent tank, and the reducing agent in the reducing agent tank can be heated to an appropriate temperature (e.g., 70°C to 150°C) to vaporize the reducing agent as necessary.
  • the reducing agent supply unit 140 supplies a reducing agent gas into the processing vessel 110 via a valve 141, a flow rate adjustment means 142, and pipes 121 and 143.
  • the reducing agent gas may be diluted with an inert gas.
  • the inert gas supply unit 150 supplies inert gas into the processing vessel 110 via a valve 151, a flow rate control means 152, and pipes 121 and 153.
  • the inert gas supply unit 150 also supplies the inert gas into the reducing agent supply unit 140 via a valve 161, a flow rate adjustment means 162, and a pipe 163. Similarly, the inert gas supply unit 150 also supplies the inert gas into the molybdenum precursor supply unit 130 via a valve 171, a flow rate adjustment means 172, and a pipe 173.
  • a pipe 121 is connected to one side wall of the processing vessel 110, and a molybdenum precursor gas, a reducing agent gas, and an inert gas are supplied into the processing vessel 110 via the pipe 121.
  • a pressure gauge 122 is provided on the pipe 121. The supply amounts of the molybdenum precursor gas, the reducing agent gas, and the inert gas into the processing vessel 110 are controlled by controlling the valves 131, 141, and 151 using the flow rate adjustment means 132, 142, and 152 based on the pressure measured by the pressure gauge 122, etc.
  • a pipe 124 is connected to the other side wall of the processing vessel 110.
  • the pipe 124 is connected to a vacuum pump 126 via a valve 125, and exhaust is performed through a pipe 127 connected to the vacuum pump 126.
  • a pressure gauge 123 is provided on the pipe 124. The pressure inside the processing vessel 110 is controlled by controlling the valve 125 based on the pressure measured by the pressure gauge 123, etc.
  • the deposition apparatus 100 has a control unit (not shown) that controls each component, specifically, the valve, power supply, heater, pump, etc.
  • This control unit has a process controller equipped with a microprocessor (computer), a user interface, and a storage unit (all not shown).
  • the process controller is configured to electrically connect and control each component of the deposition apparatus 100.
  • the user interface is connected to the process controller and includes a keyboard through which an operator inputs commands to manage each component of the deposition apparatus 100, and a display that visualizes and displays the operating status of each component of the deposition apparatus.
  • the storage unit is also connected to the process controller, and stores a control program for realizing various processes performed by the deposition apparatus 100 under the control of the process controller, a control program for causing each component of the deposition apparatus 100 to perform a predetermined process according to the processing conditions, i.e., a processing recipe, various databases, etc.
  • the processing recipe is stored in a storage medium (not shown) in the storage unit.
  • the storage medium may be a fixed one such as a hard disk, or a portable one such as a CD-ROM, DVD, or flash memory. Additionally, recipes may be transmitted from other devices, for example via electrical communication lines, as appropriate.
  • a specific processing recipe is retrieved from the memory unit in response to an instruction from the user interface, etc., and executed by the process controller, whereby the desired processing is performed in the film forming apparatus 100 under the control of the process controller.
  • the method for producing a substrate having a metal molybdenum film of the present disclosure includes a deposition process of supplying a gas containing a molybdenum precursor and a gas containing a reducing agent to a substrate to deposit a metal molybdenum film on the substrate. More specifically, the method includes a deposition process of supplying a gas containing gaseous MoOF4 and a gas containing a gaseous reducing agent to a substrate to deposit a metal molybdenum film on the substrate.
  • the substrate is as described above.
  • the film formation process may be performed using, for example, the film formation apparatus 100.
  • the objects to be processed (wafers) 112, 113, and 114 are carried into the processing vessel 110, and placed on the mounting portion 111 in the processing vessel 110 which has been heated to a predetermined temperature by the heating means 160. After the pressure is reduced to a predetermined vacuum level, a metal molybdenum film is formed (vapor phase film formation) by the CVD method or the ALD method as described below.
  • an inert gas as a purge gas is supplied from the inert gas supply unit 150 into the processing vessel 110 by opening and closing a valve to increase the pressure and stabilize the temperatures of the objects to be processed (wafers) 112, 113, and 114 on the mounting unit 111.
  • the inert gas is supplied from the inert gas supply unit 150 into the processing vessel 110, and further, the molybdenum precursor gas is supplied from the molybdenum precursor supply unit 130 and the reducing agent gas is supplied from the reducing agent supply unit 140 into the processing vessel 110.
  • the product of the reaction between the molybdenum precursor gas and the reducing agent gas is deposited on the surfaces of the workpieces (wafers) 112, 113, and 114, forming a metal molybdenum film.
  • valves 131 and 141 are closed to stop the supply of the molybdenum precursor gas and the reducing agent gas, and only an inert gas is supplied as a purge gas into the processing vessel 110 to purge the processing vessel 110. This completes deposition by the CVD method.
  • the thickness of the metal molybdenum film at this time can be controlled by the deposition time.
  • ALD Deposition by atomic layer deposition
  • the molybdenum precursor gas is further supplied from the molybdenum precursor supply unit 130 into the processing vessel 110 for a short period of time to adsorb the molybdenum precursor onto the surfaces of the workpieces (wafers) 112, 113, and 114 to be processed (molybdenum precursor gas supply step), and then the valve 131 is closed to stop the supply of the molybdenum precursor gas, and the excess molybdenum precursor gas in the processing vessel 110 is purged with the inert gas supplied from the inert gas supply unit 150 into the processing vessel 110 (purge step).
  • reducing agent gas is supplied from the reducing agent supply unit 140 into the processing vessel 110 for a short period of time to react with the molybdenum precursor adsorbed on the workpieces (wafers) 112, 113, and 114 (reducing agent gas supply step), and then the valve 141 is closed to stop the supply of reducing agent gas, and the excess inert gas in the processing vessel 110 is purged with the inert gas supplied from the inert gas supply unit 150 into the processing vessel 110 (purge step).
  • a thin molybdenum unit film is formed by one cycle of the molybdenum precursor gas supply step, purge step, reducing agent gas supply step, and purge step. These steps are then repeated multiple times to form a metal molybdenum film of the desired thickness. The thickness of the metal molybdenum film at this time can be controlled by the number of times the cycle is repeated.
  • gaseous MoOF4 is used as the molybdenum precursor.
  • other molybdenum precursors such as MoOCl4 , MoOBr4 , MoOI4 , molybdenum halides, molybdenum oxyhalides, and molybdenum carbonyls may be used as the molybdenum precursor.
  • the content of MoOF4 in 100% by mass of the molybdenum precursor is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass.
  • the substrate manufacturing method of the present disclosure preferably includes a MoOF 4 gas preparation step of heating and/or reducing pressure the solid MoOF 4 to prepare the gaseous MoOF 4 , and a film formation step of supplying a gas containing the gaseous MoOF 4 obtained by the MoOF 4 gas preparation step and a gas containing a gaseous reducing agent to the substrate to form a metal molybdenum film on the substrate.
  • the temperature may be preferably set to 50°C to 150°C, more preferably 90°C to 120°C.
  • reducing agents include hydrogen, monomethylsilane, dimethylsilane, trimethylsilane, monofluorosilane, difluorosilane, trifluorosilane, silane, borane, germane, ammonia, phosphine, and disilane. These may be used alone or in combination of two or more.
  • At least one selected from the group consisting of hydrogen, monomethylsilane, dimethylsilane, trimethylsilane, monofluorosilane, difluorosilane, trifluorosilane, disilane, and silane is preferable, at least one selected from the group consisting of hydrogen, monomethylsilane, dimethylsilane, trimethylsilane, monofluorosilane, difluorosilane, and trifluorosilane is more preferable, at least one selected from the group consisting of hydrogen, monomethylsilane, dimethylsilane, and trimethylsilane is particularly preferable, and hydrogen is the most preferable.
  • a hydrosilane-based reducing agent with low activity such as monomethylsilane, dimethylsilane, trimethylsilane, monofluorosilane, difluorosilane, or trifluorosilane, or hydrogen as a reducing agent, it is possible to form a metallic molybdenum film with a reduced content of silicon atoms in the metallic molybdenum film.
  • the gas containing a molybdenum precursor and the gas containing a reducing agent may further contain an inert gas.
  • the concept of supplying a gas containing MoOF4 and a gas containing a reducing agent includes the case where the MoOF4 gas and the reducing agent gas are separately supplied as in the ALD method described above.
  • the inert gas is not particularly limited as long as it is a gas that is not involved in the reaction between the molybdenum precursor and the reducing agent, and examples thereof include nitrogen, argon, helium, and other gases. These may be used alone or in combination of two or more. Of these, nitrogen gas is preferred.
  • the gas pressure (the pressure of the gas in contact with the substrate, the pressure of the gas in the processing vessel) is preferably 0.1 Pa to 10 kPa, more preferably 0.1 Pa to 5 kPa.
  • the temperature of the substrate is preferably 25° C. to 800° C., more preferably 300° C. to 600° C., even more preferably 350° C. to 550° C., particularly preferably 350° C. to 500° C., and most preferably 400° C. to 500° C. This tends to more suitably obtain the effects of the present disclosure. Furthermore, since the film formation reaction proceeds more easily at higher temperatures, it is preferable to set the temperature of the substrate higher than the temperature of the wall of the processing vessel in order to cause the film formation reaction to proceed preferentially on the substrate.
  • the amount of inert gas supplied to the substrate is not particularly limited. This is because the inert gas is continued to be supplied until the state in the processing vessel becomes stable, for example.
  • the amount of MoOF 4 (MoOF 4 gas) and the reducing agent (reducing agent gas) supplied to the substrate is not particularly limited as long as the reaction between the two is possible on the substrate.
  • the volume ratio of MoOF 4 (MoOF 4 gas) and the reducing agent (reducing agent gas) is preferably 1:10 to 1:10000, more preferably 1:100 to 1:1000.
  • the total content of MoOF4 ( MoOF4 gas), reducing agent (reducing agent gas), and inert gas in the total amount of gas supplied to the substrate (100% by volume) is preferably 60% by volume or more, more preferably 80% by volume or more, even more preferably 90% by volume or more, particularly preferably 95% by volume or more, and may be 100% by volume.
  • the molybdenum precursor gas ( MoOF4 gas) and the reducing agent gas may be gases containing 100% by volume of each, or may be gases diluted with an inert gas, etc.
  • the molybdenum precursor ( MoOF4 gas) and reducing agent concentrations in the gas are not particularly limited, but the higher the concentration, the more quickly a metal molybdenum film can be formed.
  • the time for the film formation process can be set appropriately depending on the amount of metal molybdenum film to be formed.
  • the cross section of the substrate after film formation was observed with a scanning electron microscope (SEM), and the interface between the base material and the metal molybdenum film was observed at 50,000x magnification to calculate the ten-point average roughness of the interface.
  • the ten-point average roughness was calculated by adding the average of the absolute values of the elevations of the highest to fifth peaks from the mean line of the interface and the average of the absolute values of the elevations of the lowest to fifth valleys within a reference length of approximately 1.9 ⁇ m.
  • the thickness of the metal molybdenum film was measured from a cross-sectional image taken with a scanning electron microscope (SEM). The content of each atom in the metal molybdenum film was measured by secondary ion mass spectrometry (SIMS). The electrical conductivity of the metallic molybdenum film was measured by a four-terminal method at 25° C. The measured electrical conductivity included that of TiN on the substrate surface, so the electrical conductivity of the metallic molybdenum film was calculated by subtracting the TiN content.
  • a metal molybdenum film was formed on a wafer substrate using the film formation apparatus shown in Figure 1.
  • the specific steps are as follows.
  • the wafer substrate was placed in the processing chamber and heated under N 2 gas flow at the same flow rate (50 to 100 mL/min) as in the film formation test, and the substrate temperature was adjusted to the film formation temperature shown in Tables 1 to 3.
  • the temperature was set to 105° C. in order to convert the solid MoOF 4 into gas.
  • MoOF4 gas and reducing agent gas were supplied to the processing vessel while N2 gas was also circulated to the molybdenum precursor supply unit 130, and MoOF4 gas/reducing agent gas/ N2 gas were circulated in the processing vessel for the film formation time shown in Tables 1 to 3, and film formation was performed under the following conditions.
  • Gas pressure in the processing vessel deposition pressure shown in Tables 1 to 3
  • the temperature inside the processing vessel was lowered to room temperature under the flow of N2 gas.
  • a hot-wall type film formation chamber made of Ni was used as the processing vessel.
  • the wafer substrate used had a base material of Si, SiO2 , TiN, TaN, Ti, Co, Ru or Ta on the top surface (the surface on which the metal molybdenum film was formed).
  • the MoOF4 gas was changed to MoO2Cl2 gas , and the experiment was carried out under the conditions described in Table 2.
  • the MoOF4 gas was changed to MoOCl4 gas, and the experiment was carried out under the conditions described in Table 2.
  • the MoOF4 gas was changed to MoF6 gas, and the experiment was carried out under the conditions described in Table 2.
  • Comparative Example 5 the MoOF4 gas was changed to Mo(CO) 6 gas, and the experiment was carried out under the conditions described in Table 2.
  • Example 11 was carried out under the conditions described in Table 3.
  • the deposition using MoOF4 was able to deposit a metal molybdenum film on all of the underlayer materials used in the test while suppressing damage to the underlayer.
  • the ten-point average roughness of the underlayer material after deposition was 2 nm or less.
  • no oxygen atoms, fluorine atoms, or chlorine atoms were detected in the metal molybdenum film, indicating that a high-purity film was deposited.
  • Film forming apparatus 110 Processing container 111 Placement section 112, 113, 114 Processing object (wafer) 122, 123 Pressure gauge 126 Vacuum pump 130 Molybdenum precursor supply section 140 Reducing agent supply section 150 Inert gas supply section 160 Heating means 125, 131, 141, 151, 161, 171 Valves 132, 142, 152, 162, 172 Flow rate adjustment means 121, 124, 127, 133, 143, 153, 163, 173 Pipes

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