WO2019167715A1 - Procédé de production de film mince au nitrure de gallium - Google Patents

Procédé de production de film mince au nitrure de gallium Download PDF

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WO2019167715A1
WO2019167715A1 PCT/JP2019/006012 JP2019006012W WO2019167715A1 WO 2019167715 A1 WO2019167715 A1 WO 2019167715A1 JP 2019006012 W JP2019006012 W JP 2019006012W WO 2019167715 A1 WO2019167715 A1 WO 2019167715A1
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gas
thin film
gallium nitride
partial pressure
nitride thin
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PCT/JP2019/006012
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English (en)
Japanese (ja)
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雅紀 白井
拓司 山本
悟 高澤
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株式会社アルバック
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Priority to CN201980002104.7A priority Critical patent/CN110574144B/zh
Priority to KR1020197031371A priority patent/KR102211304B1/ko
Priority to JP2019537199A priority patent/JP6722361B2/ja
Publication of WO2019167715A1 publication Critical patent/WO2019167715A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02458—Nitrides
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/564—Means for minimising impurities in the coating chamber such as dust, moisture, residual gases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02494—Structure
    • H01L21/02496—Layer structure
    • H01L21/02505—Layer structure consisting of more than two layers
    • H01L21/02507—Alternating layers, e.g. superlattice

Definitions

  • the present invention relates to a method for producing a gallium nitride thin film, and more particularly to a method for producing a gallium nitride thin film having good crystal orientation.
  • gallium nitride thin films are used in LEDs, semiconductors for wireless communication, etc., and in order to improve the characteristics of electronic devices using gallium nitride thin films, methods for obtaining thin films with good crystallinity have been researched and developed. Yes.
  • Patent Document 1 describes a technique for growing a gallium nitride thin film by a reactive sputtering method
  • Patent Document 2 describes a method for producing a gallium nitride thin film using radicals
  • Patent Document 3 describes a reactive sputtering method using an ion beam, which is considered to have improved crystallinity, but a technique for further improving the crystallinity is required.
  • FIG. 7 is a graph showing the relationship between the nitrogen gas partial pressure and the nitrogen content of the thin film formed when sputtering a metal gallium target to form a gallium nitride thin film.
  • the radical reaction is dominant, the thin film formed is a gallium thin film, and the reactive sputtering reaction is dominant at the nitrogen gas partial pressure in the region B.
  • the thin film formed is a gallium nitride thin film, but it is oriented. Inferior.
  • An object of the present invention is to obtain a gallium nitride thin film with good crystallinity.
  • the present invention is an invention for forming a gallium nitride thin film excellent in orientation by performing reactive sputtering while irradiating nitrogen gas radicals in the region C of FIG.
  • the present invention is produced by sputtering a metal gallium target with a plasma of a mixed gas containing nitrogen gas and sputtering gas while irradiating a substrate disposed in a vacuum chamber from a discharge port of a radical gun portion with nitrogen radicals.
  • the sputtered particles reach the substrate to form a gallium nitride thin film.
  • the present invention provides a method for producing a gallium nitride thin film in which the target is disposed in a deposition-proof plate container so as to face the substrate, and the sputtering gas and the nitrogen gas are introduced into the deposition-proof plate container. It is.
  • the present invention is the method of manufacturing a gallium nitride thin film in which a filter for removing nitrogen gas ions is disposed at the outlet.
  • the value of the raw material gas partial pressure which is the partial pressure value of the nitrogen gas introduced into the radical gun part, inside the vacuum chamber is a partial pressure value of the nitrogen gas contained in the mixed gas.
  • the value of the raw material gas partial pressure which is the partial pressure value of the nitrogen gas introduced into the radical gun portion inside the vacuum chamber is And nitriding to make the range of 38% or more and 50% or less of the total value of the reaction gas partial pressure, which is the partial pressure of nitrogen gas contained in the mixed gas, and the raw material gas partial pressure
  • gallium nitride crystal When growing a gallium nitride crystal, nitridation is promoted on both the target side and the substrate side, so that a gallium nitride thin film with good crystallinity can be obtained.
  • Film forming apparatus used in the present invention Diagram for explaining the positional relationship between the substrate and the gallium nitride thin film Graph showing the relationship between nitrogen gas pressure and full width at half maximum Graph showing the relationship between nitrogen gas pressure and growth rate Example of LED using gallium nitride thin film manufactured by the present invention
  • Other examples of film forming apparatus used in the present invention Graph showing the relationship between nitrogen partial pressure and nitrogen content in the thin film formed
  • reference numeral 2 is a film forming apparatus used in the present invention, and has a vacuum chamber 10. Inside the vacuum chamber 10, there are a substrate placement unit 20, a reactive sputtering unit 30, and a radical gun unit 40.
  • the substrate placement unit 20 includes a substrate holder 21 on which the substrate 22 is placed, and a heater 23 that heats the substrate 22 placed on the substrate holder 21.
  • the substrate holder 21 is provided on the ceiling of the vacuum chamber 10, and the heater 23 is fixed to the ceiling so as to be positioned between the back surface of the substrate 22 disposed on the substrate holder 21 and the ceiling.
  • the reactive sputtering unit 30 and the radical gun unit 40 are disposed below the substrate holder 21, and the surface of the substrate 22 disposed on the substrate holder 21 faces the reactive sputtering unit 30 and the radical gun unit 40. So that it is directed downwards.
  • the substrate holder 21 may be provided not on the ceiling but on the wall surface or bottom surface of the vacuum chamber 10, and the reactive sputtering unit 30 and the radical gun unit 40 may be provided at positions facing the substrate holder 21.
  • the reactive sputtering unit 30 has a deposition plate container 31, and a sputtering electrode 32 is disposed inside the deposition plate container 31.
  • the sputter electrode 32 has a container shape, and a target 33 made of metallic gallium is disposed in the container which is the sputter electrode 32.
  • the deposition preventing plate container 31 has a discharge port 37, and the opening 34 of the sputter electrode 32 and the discharge port 37 of the deposition preventing plate container 31 are communicated with each other.
  • the target 33 is disposed so as to face the substrate 22 disposed on the substrate holder 21 through the opening 34 and the discharge port 37.
  • a sputtering power source 35 and a heating power source 28 are disposed outside the vacuum chamber 10.
  • the sputter electrode 32 is connected to the sputter power source 35, and the vacuum chamber 10 is connected to the ground potential.
  • the sputter power source 35 operates, the sputter voltage is applied to the sputter electrode 32, and when the heating power source 28 operates, the heater 23 is energized. Fever.
  • a gas supply device 15 is disposed outside the vacuum chamber 10.
  • the gas supply device 15 includes a sputtering gas source 26 that supplies a sputtering gas, a reaction gas source 27 that supplies a reaction gas, and a mixer 36 that is connected to the sputtering gas source 26 and the reaction gas source 27. .
  • the mixer 36 is connected to the deposition plate container 31, and the sputtering gas and the reactive gas are respectively supplied from the sputtering gas source 26 and the reactive gas source 27 to the mixer 36 at a desired flow rate.
  • the gas and the reaction gas are mixed by the mixer 36, converted into a mixed gas, and supplied to the inside of the deposition preventing plate container 31.
  • a rare gas such as argon is used as the sputtering gas, and the reaction gas is a gas containing nitrogen atoms.
  • N 2 gas nitrogen gas
  • NH 3 gas, N 2 H 4 gas, NO 2 gas, NO gas N 2 O gas or the like can be used.
  • nitrogen gas is used.
  • a vacuum evacuation device 19 is connected to the vacuum chamber 10.
  • the vacuum evacuation device 19 When the vacuum evacuation device 19 is operated, the inside of the vacuum chamber 10 is evacuated to form a vacuum atmosphere.
  • the sputtering power source 35 is activated while the mixed gas is being introduced from the mixer 36 of the gas supply device 15 into the inside of the deposition-prevention plate container 31, and the sputtering electrode 32 is supplied with an alternating current.
  • a sputtering voltage is applied, a mixed gas plasma including an argon gas plasma and a nitrogen gas plasma is formed on the surface of the target 33, and the surface of the target 33 is sputtered by the argon gas plasma.
  • the metal gallium on the surface of the target 33 is nitrided by nitrogen gas plasma, and the gallium nitride on the surface of the target 33 is sputtered.
  • Sputtered particles 38 which are gallium nitride particles jumping out from the surface of the target 33, pass through the opening 34 and the discharge port 37, are released into the vacuum chamber 10, and reach the substrate 22 disposed on the substrate holder 21.
  • the AC sputtering voltage is a high frequency voltage of 13.56 MHz.
  • the radical gun unit 40 includes a reaction tube 44 and an activation device 43 provided in the reaction tube 44.
  • the vacuum vessel 10 is provided with an apparatus container 42, and the reaction cylinder 44 is disposed inside the apparatus container 42.
  • a raw material gas supply source 45 and a reaction power source 46 are disposed outside the vacuum chamber 10.
  • a source gas is disposed in the source gas supply source 45 and supplies the source gas into the reaction tube 44.
  • the source gas is nitrogen gas.
  • the source gas is activated inside the reaction tube 44, and source gas ions (nitrogen ions) and source gas radicals (nitrogen radicals 48). ) And are generated.
  • the activation device 43 is a coil wound around the reaction tube 44.
  • reference numeral 24 denotes a shutter, which is rotated by a rotating shaft 25, and the substrate 22 is exposed or covered by opening and closing the shutter 24. Here, the shutter 24 is opened and the substrate 22 is exposed.
  • the reaction cylinder 44 has a discharge port 49.
  • a known filter device 47 that does not allow ions to pass through is disposed at the discharge port 49, and nitrogen radicals 48 that are radicals of the source gas generated inside the reaction tube 44 pass through the filter device 47, but the source gas Ions cannot pass through the filter device 47, and ions of the source gas are prevented from leaking out of the reaction tube 44 from the discharge port 49.
  • the ions of the source gas are not released from the radical gun unit 40, but the nitrogen radicals 48, which are radicals of the source gas, are released and reach the surface of the substrate 22 disposed on the substrate holder 21.
  • the heater 23 is energized by a heating power source 28, and the substrate 22 is heated by the heater 23 that has generated heat to raise the temperature to 600 ° C. or higher. However, if the temperature of the substrate 22 is 300 ° C. or higher, it may be lower than 900 ° C.
  • the gallium in the sputtered particles 38 that are deficient in nitrogen reacts with the nitrogen radicals 48 to form a gallium nitride crystal with an increased proportion of nitrogen. A gallium nitride thin film is grown.
  • Reference numeral 6 in FIG. 2 denotes a gallium nitride thin film formed to a predetermined film thickness
  • the substrate 22 is an n-type nitride grown on the sapphire substrate 4 by HVPE (hydride vapor phase epitaxy).
  • a gallium thin film 5 is disposed, and a gallium nitride thin film 6 grown by the film deposition apparatus 2 of the present invention is disposed in contact with the surface of the n-type gallium nitride thin film 5.
  • the reaction gas contains an impurity compound that determines the p-type or n-type of the gallium nitride thin film 6 to be formed.
  • an impurity compound that determines the p-type or n-type of the gallium nitride thin film 6 to be formed.
  • the gallium nitride thin film grows on the surface of the substrate 22.
  • magnesium is doped therein, a p-type gallium nitride thin film is formed.
  • the gallium nitride thin film 6 was formed on the surface of the substrate 22 where the n-type gallium nitride thin film 5 formed by the HVPE method was exposed by changing the content of the reaction gas in the mixed gas.
  • Table 1 below shows the conditions under which the thin film was formed.
  • the pressure of sputtering gas composed of argon (sputtering gas partial pressure) is maintained at a constant value of 0.130 Pa, and the pressure (raw material gas) in the vacuum chamber 10 of nitrogen gas, which is the raw material gas introduced into the radical gun unit 40. (Partial pressure) is also maintained at a constant value of 0.030 Pa, and in this state, the pressure (reactive gas partial pressure) in the vacuum chamber 10 of nitrogen gas, which is a reactive gas mixed with the sputtering gas, is changed. Yes.
  • “Nitrogen ratio 1” in Table 1 is the ratio of the raw material gas partial pressure RG (constant value 0.03 Pa) to the total value of the raw material gas partial pressure RG (Pa) and the reaction gas partial pressure RE (Pa).
  • “Nitrogen ratio 2” is the sum of the raw material gas partial pressure RG (Pa) and the reactive gas partial pressure RE (Pa), the raw material gas partial pressure RG (Pa), the reactive gas partial pressure RE (Pa), and the sputtering rig. This is the ratio to the total value with the gas partial pressure SP (Pa).
  • the source gas partial pressure RG (Pa) and the reaction gas partial pressure RE (Pa) are the partial pressures in the vacuum chamber 10 when the pressure of the atmosphere in which the substrate 22 is disposed in the vacuum chamber 10 is the total pressure. Pressure value.
  • Nitrogen ratio 1 RG / (RG + RE)
  • Nitrogen ratio 2 (RG + RE) / (RG + RE + SP)
  • Table 1 shows the changed reaction gas partial pressure RE (Pa) value and the nitrogen ratio 1 and nitrogen ratio 2 corresponding to the reaction gas partial pressure RE (Pa) value as the film formation conditions. Yes.
  • the obtained gallium nitride thin film 6 was subjected to X-ray diffraction analysis (here, X-ray rocking curve method). From the relationship between ⁇ and X-ray diffraction intensity, the full width at half maximum of the peak indicating (10-10) orientation ( Second: arcsec). The results are shown in the following Table 1 and the graph of FIG.
  • the film thickness of the obtained gallium nitride thin film 6 was measured, and the growth rate (nm / min) of the gallium nitride thin film 6 was calculated from the measurement result and the film formation time.
  • the results are shown in the following Table 1 and the graph of FIG.
  • Table 1 shows that when the gallium nitride thin film is formed by radical irradiation, the nitrogen ratio 1 is preferably in the range of 40% to 63%.
  • the column with “-” is the result of the film formation conditions in which gallium nitride could not be confirmed, but metal was observed visually under the condition of the reaction gas partial pressure of 0.035 Pa, but X-ray From this, it is considered that a gallium nitride thin film is formed under the metal layer on the surface.
  • the partial pressure value of nitrogen gas introduced into the vacuum chamber 10 from the radical gun unit 40 (the source gas partial pressure in Table 1) and the nitrogen gas introduced into the vacuum chamber 10 as a reactive sputtering reaction gas (10-10) plane XRC full width at half maximum (XRC: X-ray rocking curve method), (0002) plane XRC full width at half maximum, and growth rate.
  • the partial pressure value of the sputtering gas is 0.13 Pa for each condition.
  • Argon gas was used as the sputtering gas.
  • “ ⁇ ” indicates a measurement result with a narrow half-value width
  • “ ⁇ ”, “ ⁇ ”, and “ ⁇ ” indicate that the half-value width increases in this order.
  • a thin film formed under the conditions described in “X” is a defective product that cannot be used, but a thin film formed under the conditions described in “ ⁇ ” and a thin film formed under the conditions described in “ ⁇ ” And the thin film formed under the conditions where “ ⁇ ” is described are of usable quality.
  • Table 4 “ ⁇ ” indicates a measurement result with a high film formation rate, and “ ⁇ ”, “ ⁇ ”, and “ ⁇ ” indicate the values of the film formation rate decreasing in this order.
  • the film formation rate under the conditions described with “x” is small and it takes a long time to form a thin film, it is not suitable for actual use, but the conditions with “ ⁇ ” and the conditions with “ ⁇ ” are The film formation speed with the condition “ ⁇ ” is a condition that can be actually used.
  • FIG 5 shows a light emitting device (LED) 50 using the gallium nitride thin film 6 formed according to the present invention.
  • LED light emitting device
  • the light emitting element 50 is composed of gallium nitride thin films 52 to 55, 6, and 57 to 59 formed by epitaxial growth on the sapphire substrate 51. Specifically, the light emitting element 50 is in contact with the surface of the sapphire substrate 51.
  • the n-GaN thin film 52 having a thickness of 2 ⁇ m and the light emitting layer (MQW) 53 having a thickness of 70 nm grown on the n-GaN thin film 52 are formed. It is formed in contact with the thin film 52.
  • a p-type base thin film 54 having a thickness of 20 nm is grown in contact with the light emitting layer 53, and a p-type layer thin film 55 having a thickness of 100 nm is grown on the surface of the p-type base thin film 54.
  • the light emitting layer 53 is a gallium nitride thin film having a multiple quantum well (MQW) structure.
  • the impurity of the p-type base thin film 54 is aluminum.
  • an n + -type gallium nitride thin film 57 having a thickness of 2 nm containing silicon is grown on the surface of the p + -type gallium nitride thin film 6, an n + -type gallium nitride thin film 57 having a thickness of 2 nm containing silicon is grown.
  • the surface of the gallium nitride thin film 57 has a thickness of 400 nm.
  • the n-type gallium nitride thin film 58 is grown.
  • a contact thin film 59 having a thickness of 20 nm containing a high concentration of n-type impurities is grown, and the anode electrode 61 is formed in contact with the contact thin film 59. .
  • the anode electrode 61 and the cathode electrode 62 are metal thin films in which a titanium thin film, an aluminum thin film, a titanium thin film, and a gold thin film are laminated in this order, and the contact resistance is reduced. When a current is passed between them, the light emitting layer 53 emits light with high efficiency.
  • the p + -type gallium nitride thin film 6 with a thickness of 4 nm positioned on the p-type layer thin film 55 with a thickness of 100 nm is formed according to the present invention, but each gallium nitride thin film positioned on the light emitting layer 53 is In particular, the n + -type gallium nitride thin film 57 having a thickness of 2 nm, the n-type gallium nitride thin film 58 having a thickness of 400 nm, and a thickness of 20 nm containing a high concentration of n-type impurities.
  • Application of the present invention to the contact thin film 59 is conceivable.
  • an impurity compound gas is contained in the reactive gas to form an n-type or p-type gallium nitride thin film.
  • an n-type or p-type gallium nitride thin film is formed using a target containing impurities. Can be formed.
  • Reference numeral 2 'in FIG. 6 is a film forming apparatus that can be used in the manufacturing method in this case, and the film forming apparatus 2' has a reactive sputtering unit 30a and an auxiliary sputtering unit 30b.
  • the reactive sputtering unit 30a of the film forming apparatus 2 ′ of FIG. 6 has the same structure as the reactive sputtering unit 30 of the film forming apparatus 2 of FIG. 1, and the reactive sputtering unit 30 of the film forming apparatus 2 of FIG.
  • the same reference numerals as those in FIG. 1 denote the members of the reactive sputtering unit 30 of the film forming apparatus 2 in FIG. Further, among the other members of the film forming apparatus 2 ′, the same members as those of the film forming apparatus 2 of FIG.
  • the auxiliary sputtering unit 30b has an auxiliary deposition plate container 31b, and an auxiliary sputtering electrode 32b is disposed inside the auxiliary deposition plate container 31b.
  • An impurity target 33b made of an impurity that determines the p-type or n-type of the semiconductor is disposed on the auxiliary sputter electrode 32b.
  • the auxiliary deposition preventing plate container 31b has an auxiliary discharge port 37b, and the impurity target 33b is disposed so as to face the substrate 22 disposed on the substrate holder 21 through the auxiliary discharge port 37b.
  • An auxiliary sputtering power source 35 b is disposed outside the vacuum chamber 10.
  • the auxiliary sputtering electrode 32b is connected to the auxiliary sputtering power source 35b, and the vacuum chamber 10 is connected to the ground potential.
  • a sputtering voltage is applied to the auxiliary sputtering electrode 32b.
  • An auxiliary gas supply device 15b is arranged outside the vacuum chamber 10.
  • the auxiliary gas supply device 15b is provided with an auxiliary sputtering gas source 26b for supplying an auxiliary sputtering gas that is a rare gas such as argon.
  • the target 33 a of the reactive sputtering unit 30 a of the film forming apparatus 2 ′ is reactively sputtered by the same operation as that of the film forming apparatus 2 of FIG. 1, and nitrogen radicals 48 are released from the radical gun unit 40 and are nitrided on the surface of the substrate 22.
  • the impurity target 33b of the auxiliary sputter unit 30b is sputtered with an auxiliary sputtering gas, and the generated auxiliary sputtering particles 38b reach the surface of the substrate 22; thus, nitridation formed on the surface of the substrate 22
  • the gallium thin film contains the impurities of the auxiliary sputtered particles 38b, and a p-type or n-type gallium nitride thin film can be formed.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Led Devices (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne la formation d'un film mince sur la surface d'un substrat 22 par une exécution de la pulvérisation réactive sur une cible de nitrure de gallium 33 tout en introduisant un gaz de pulvérisation et un gaz d'azote tous deux pour une utilisation dans la formation d'un film mince au nitrure de gallium ayant une bonne cristallinité et en libérant en même temps un radical azoté 48 d'une section de pistolet à radicaux 40 vers le substrat 22. La nitrogénation peut être obtenue à la fois du côté cible 33 et du côté substrat 22 et, par conséquent, un film mince au nitrure de gallium ayant une bonne cristallinité peut être formé.
PCT/JP2019/006012 2018-03-01 2019-02-19 Procédé de production de film mince au nitrure de gallium WO2019167715A1 (fr)

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CN201980002104.7A CN110574144B (zh) 2018-03-01 2019-02-19 氮化镓薄膜的制造方法
KR1020197031371A KR102211304B1 (ko) 2018-03-01 2019-02-19 질화갈륨 박막의 제조 방법
JP2019537199A JP6722361B2 (ja) 2018-03-01 2019-02-19 窒化ガリウム薄膜の製造方法

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WO2022176422A1 (fr) * 2021-02-19 2022-08-25 株式会社ジャパンディスプレイ Procédé de production d'un film de nitrure de gallium
WO2022215670A1 (fr) * 2021-04-05 2022-10-13 東ソー株式会社 Structure de film multicouche et son procédé de production
WO2023218840A1 (fr) * 2022-05-10 2023-11-16 株式会社ジャパンディスプレイ Dispositif de formation de film et procédé de formation de film pour film de nitrure de gallium
WO2024024268A1 (fr) * 2022-07-25 2024-02-01 株式会社ジャパンディスプレイ Dispositif de formation de film
WO2024024267A1 (fr) * 2022-07-25 2024-02-01 株式会社ジャパンディスプレイ Dispositif de formation de film et procédé de formation de film de nitrure de gallium

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EP4130331A4 (fr) * 2020-03-30 2023-08-16 Tosoh Corporation Film stratifié, structure comprenant un film stratifié, élément semi-conducteur, dispositif électronique et procédé de production de film stratifié

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022176422A1 (fr) * 2021-02-19 2022-08-25 株式会社ジャパンディスプレイ Procédé de production d'un film de nitrure de gallium
WO2022215670A1 (fr) * 2021-04-05 2022-10-13 東ソー株式会社 Structure de film multicouche et son procédé de production
WO2023218840A1 (fr) * 2022-05-10 2023-11-16 株式会社ジャパンディスプレイ Dispositif de formation de film et procédé de formation de film pour film de nitrure de gallium
WO2024024268A1 (fr) * 2022-07-25 2024-02-01 株式会社ジャパンディスプレイ Dispositif de formation de film
WO2024024267A1 (fr) * 2022-07-25 2024-02-01 株式会社ジャパンディスプレイ Dispositif de formation de film et procédé de formation de film de nitrure de gallium

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CN110574144B (zh) 2023-05-12
KR20190131541A (ko) 2019-11-26
JPWO2019167715A1 (ja) 2020-04-16
KR102211304B1 (ko) 2021-02-03
JP6722361B2 (ja) 2020-07-15
TWI720431B (zh) 2021-03-01
TW201938829A (zh) 2019-10-01

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