WO2014126203A1 - SOURCE D'ALIMENTATION EN MATIÈRE DE DÉPART POUR ÉPITAXIE DE FILM DE ZnO, FILM DE ZnO, DISPOSITIF ET PROCÉDÉ DE FABRICATION DE FILM DE ZnO, ET ÉLÉMENT ÉLECTROLUMINESCENT CONTENANT DU FILM DE ZnO - Google Patents

SOURCE D'ALIMENTATION EN MATIÈRE DE DÉPART POUR ÉPITAXIE DE FILM DE ZnO, FILM DE ZnO, DISPOSITIF ET PROCÉDÉ DE FABRICATION DE FILM DE ZnO, ET ÉLÉMENT ÉLECTROLUMINESCENT CONTENANT DU FILM DE ZnO Download PDF

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WO2014126203A1
WO2014126203A1 PCT/JP2014/053486 JP2014053486W WO2014126203A1 WO 2014126203 A1 WO2014126203 A1 WO 2014126203A1 JP 2014053486 W JP2014053486 W JP 2014053486W WO 2014126203 A1 WO2014126203 A1 WO 2014126203A1
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zno
raw material
containing film
reaction vessel
supply source
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PCT/JP2014/053486
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English (en)
Japanese (ja)
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松潤 康
熊谷　義直
纐纈　明伯
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東京エレクトロン株式会社
国立大学法人東京農工大学
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Publication of WO2014126203A1 publication Critical patent/WO2014126203A1/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
    • H01L21/02612—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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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    • 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
    • C23C16/4481—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 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
    • C23C16/45563—Gas nozzles
    • C23C16/45578—Elongated nozzles, tubes with holes
    • 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
    • C23C16/458—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 supporting substrates in the reaction chamber
    • C23C16/4582—Rigid and flat substrates, e.g. plates or discs
    • C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
    • C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
    • 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
    • C23C16/46—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 heating the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • 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
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • 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
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table

Definitions

  • Embodiments of the present invention relate to a raw material supply source for ZnO-containing film growth, a ZnO-containing film manufacturing apparatus, a manufacturing method, and a light-emitting element including the ZnO-containing film.
  • ZnO zinc oxide
  • GaN gallium nitride
  • Patent Document 1 describes a semiconductor element in which a p-type MgZnO layer is formed on an n-type ZnO substrate using a molecular beam epitaxy method. This p-type MgZnO layer is formed using zinc (Zn) and oxygen gas (O 2 ) as main raw materials, and nitrogen gas (N 2 ) is used as a p-type dopant raw material.
  • Patent Document 2 a reaction gas composed of zinc chloride (ZnCl 2 ) and water (H 2 O) is introduced into a reaction container in which a substrate is accommodated under normal pressure, and ammonia (NH 3 ) is introduced. It is described that a ZnO-containing film to which nitrogen is added is grown on a substrate by introducing it into a reaction vessel as a p-type impurity source gas.
  • Patent Document 1 the molecular beam epitaxy method described in Patent Document 1 needs to grow a ZnO-containing film while maintaining an ultrahigh vacuum state, and is not suitable for mass production of a semiconductor film.
  • a raw material supply source for growing a ZnO-containing film supplies a raw material for growing a ZnO-containing film into a reaction vessel that houses a substrate on which the ZnO-containing film is to be formed.
  • a raw material supply source that communicates with the inside of the reaction vessel and contains a solid raw material containing Zn, a heating part that heats the raw material storage part, and the inside of the raw material storage part to be at normal pressure
  • a carrier gas supply source for supplying a carrier gas not containing chlorine and hydrogen into the raw material container
  • a reaction gas supply source for supplying a reaction gas containing nitric oxide into the reaction vessel so that the inside of the reaction vessel has a normal pressure
  • a control device wherein the control device is configured to control the heating unit to a temperature at which Zn is vaporized in the raw material storage unit when supplying the carrier gas into the raw material storage unit.
  • Zn is vaporized under normal pressure in the raw material container by heating the inside of the raw material container.
  • the vaporized Zn is transported by a carrier gas not containing chlorine and hydrogen supplied into the raw material container, and supplied as a raw material gas into the reaction vessel.
  • a reaction gas containing nitric oxide is supplied into the reaction vessel so that the reaction vessel has a normal pressure, and the reaction gas and the raw material gas react to form a ZnO-containing film on the substrate.
  • the source gas does not contain chlorine and etching of the ZnO-containing film does not occur, the ZnO-containing film can be grown at a low temperature.
  • the doping amount of nitrogen as an acceptor has a property that depends on the growth temperature, and the doping concentration of nitrogen becomes high at a low temperature of 700 ° C. or lower.
  • the source gas does not contain hydrogen, generation of crystal defects due to etching with hydrogen gas is prevented. Therefore, according to this raw material supply source, a raw material gas for growing a ZnO-containing film capable of producing a ZnO semiconductor film having high crystallinity and having high doping concentration of nitrogen added under normal pressure. Can be supplied.
  • An apparatus for producing a ZnO film according to an aspect of the present invention includes an installation table on which a substrate on which a ZnO film is to be formed is disposed, a reaction container that houses the installation table, a solid container that contains Zn and communicates with the inside of the reaction container.
  • a carrier gas that supplies a carrier gas that does not contain chlorine and hydrogen into the raw material container so that the inside of the raw material container is at a normal pressure, a raw material container that contains the raw material, a heating unit that heats the installation base and the raw material container
  • the heating unit is controlled so that the inside of the raw material storage unit is set to a first temperature at which Zn is vaporized, and the installation base is set to a second temperature equal to or higher than the first temperature. .
  • Zn is vaporized under normal pressure in the raw material container by heating the raw material container.
  • the vaporized Zn is transported by a carrier gas not containing chlorine and hydrogen supplied into the raw material container, and supplied as a raw material gas into the reaction vessel.
  • a reaction gas containing nitric oxide is supplied into the reaction vessel so that the reaction vessel has a normal pressure, and the reaction gas and the raw material gas react to form a ZnO-containing film on the substrate.
  • the source gas does not contain chlorine and etching of the ZnO-containing film does not occur, the ZnO-containing film can be grown at a low temperature.
  • the doping amount of nitrogen as an acceptor has a property that depends on the growth temperature, and the doping concentration of nitrogen becomes high at a low temperature of 700 ° C. or lower.
  • the source gas does not contain hydrogen, generation of crystal defects due to etching with hydrogen gas is prevented. For this reason, according to this manufacturing apparatus, it is possible to produce a ZnO semiconductor film having high crystallinity and having high doping concentration of nitrogen added under normal pressure.
  • the reaction gas may not contain oxygen.
  • the partial pressure of the nitric oxide gas that contributes to doping of the ZnO-containing film can be increased in the reaction vessel, a ZnO semiconductor film to which nitrogen having a higher doping concentration is added can be manufactured. it can.
  • the first temperature may be 300 ° C. to 400 ° C.
  • the second temperature may be 400 ° C. to 600 ° C.
  • a method for producing a ZnO film according to an aspect of the present invention includes a mounting base on which a substrate on which a ZnO-containing film is to be formed is disposed, a reaction container that houses the mounting base, and inside the reaction container, and contains Zn.
  • a ZnO-containing film using a manufacturing apparatus comprising a gas supply source, a reaction gas supply source for supplying a reaction gas containing nitric oxide into the reaction vessel, and a control device so that the inside of the reaction vessel has a normal pressure
  • a ZnO semiconductor film having a high crystallinity and having a high doping concentration of nitrogen added under normal pressure can be produced.
  • the substrate may be a ZnO substrate, and in the installation step, the substrate may be installed such that a ZnO-containing film grows on the + C surface of the substrate.
  • a ZnO semiconductor film to which nitrogen having a higher doping concentration is added can be manufactured.
  • a light-emitting element includes a ZnO-containing film manufactured under normal pressure, and the ZnO-containing film has a nitrogen doping concentration of 1 ⁇ 10 20 atm / cm 3 or more. It is characterized by.
  • the price of the light emitting element can be reduced by using ZnO as a material.
  • a ZnO semiconductor film to which nitrogen having a high doping concentration is added can be manufactured under normal pressure.
  • FIG. 2 is a cross-sectional view taken along line II-II in FIG. It is a flowchart which shows the manufacturing method of the ZnO containing film
  • (A) is a graph which shows the relationship between the growth temperature of the produced ZnO film
  • FIG. 1 is a cross-sectional view schematically showing a ZnO-containing film manufacturing apparatus 1 according to an embodiment, and shows a cross section of the manufacturing apparatus 1.
  • 2 is a cross-sectional view taken along line II-II of the manufacturing apparatus 1 shown in FIG.
  • the manufacturing apparatus 1 includes a raw material container 10, a reaction vessel 20, a carrier gas supply source 16, a reaction gas supply source 32, and an inert gas supply source.
  • the manufacturing apparatus 1 is an apparatus that forms a ZnO-containing film to which nitrogen is added on a substrate 2 under normal pressure.
  • “normal pressure” means a pressure excluding an ultra-high vacuum state, and specifically means a range of 0.7 atm to 1.3 atm.
  • the raw material container 10, the carrier gas supply source 16, the reactive gas supply source 32, and the inert gas supply source 34 function as a raw material supply source MS.
  • the reaction vessel 20 is a means for accommodating the substrate 2 on which the ZnO-containing film is to be formed, and defines a reaction space S1 as its internal space.
  • the reaction vessel 20 includes a side wall 22a, an upper wall 22b, and a bottom wall 22c.
  • the side wall 22a has a substantially cylindrical shape extending in the vertical direction along the axis Z.
  • the upper wall 22b is provided on the upper end side of the side wall 22a.
  • An exhaust pipe 30 having an exhaust hole 30a is attached to the upper wall 22b.
  • the exhaust pipe 30 is connected to the exhaust device 36.
  • the exhaust device 36 is controlled by a control device 40 described later, controls the flow rate of the exhausted gas, and adjusts the pressure in the reaction vessel 20.
  • the exhaust device 36 has a vacuum pump such as a dry pump.
  • the inside of the reaction vessel 20 and the raw material container 10 are maintained at normal pressure by the exhaust device 36.
  • the bottom wall 22 c is provided on the lower end side of the side wall 22 a and supports a structure accommodated in the reaction vessel 20.
  • a cylindrical reaction tube 24 whose upper end is closed is provided inside the reaction vessel 20.
  • the reaction tube 24 is made of a heat resistant material such as quartz (SiO 2 ) or silicon carbide (SiC).
  • a plurality of openings 24 a are formed on the side surface of the reaction tube 24.
  • An installation table 26 is provided in the hollow portion in the reaction tube 24.
  • the installation table 26 includes a support portion 26a and a plurality of mounting tables 26b.
  • the mounting table 26b has a disk shape and can hold a plurality of substrates 2 horizontally on the upper surface thereof. In one example, as shown in FIG. 2, seven substrates 2 can be placed on the upper surface of one placement table 26b.
  • a plurality of mounting tables 26b are spaced apart at predetermined intervals along the axis Z, and a plurality of mounting tables 26b are supported by a long support portion 26a.
  • a rotation mechanism 28 is provided on the base end side of the support portion 26a.
  • the rotation mechanism 28 is configured to be capable of rotating a plurality of mounting tables 26b with the support portion 26a as a rotation axis.
  • the reaction vessel 20 further includes a heater (heating unit) H1 for heating the inside of the reaction vessel 20.
  • a plurality of heaters H ⁇ b> 1 are provided along the inner periphery of the side wall 22 a of the reaction vessel 20.
  • the heater H1 is a heating means that uses principles such as resistance heating, lamp heating, and high-frequency heating. As an example, a heating furnace using resistance heating can be employed.
  • the heater H ⁇ b> 1 is connected to the heater power supply 38, generates heat by the electric power supplied from the heater power supply 38, and heats the inside of the reaction vessel 20, that is, the installation table 26.
  • the heater power supply 38 is controlled by a control device 40 to be described later, controls the power supplied to the heater H1, and adjusts the amount of heat generated by the heater H1.
  • the raw material storage unit 10 includes a storage container 12.
  • the storage container 12 defines a storage space S2 as its internal space.
  • the raw material accommodating part 10 accommodates the stage 14 and the solid raw material M arrange
  • the solid material M contains Zn that is a material for the ZnO-containing film.
  • the raw material storage unit 10 further includes a heater (heating unit) H2 for heating the inside of the raw material storage unit 10.
  • the heater H2 is a heating means that uses principles such as resistance heating, lamp heating, and high-frequency heating. As an example, a heating furnace using resistance heating may be employed.
  • the heater H ⁇ b> 2 is connected to the heater power supply 15, generates heat by the electric power supplied from the heater power supply 15, and can heat the stage 14.
  • the heater power supply 15 is controlled by the control device 40, controls the power supplied to the heater H2, and adjusts the amount of heat generated by the heater H2.
  • a part of Zn contained in the solid material M is gasified by heating the inside of the material container 10 using the heater H2.
  • the carrier gas supply source 16 supplies the carrier gas into the raw material container 10 so that the inside of the raw material container 10 has a normal pressure.
  • the carrier gas supply source 16 communicates with the inside of the raw material container 10 through a conduit P1.
  • the carrier gas supply source 16 supplies a carrier gas from a gas source stored therein.
  • the conduit P1 introduces the carrier gas supplied from the carrier gas supply source 16 into the storage container 12.
  • the carrier gas supply source 16 is connected to the control device 40, controls the gas flow rate supplied to the conduit P ⁇ b> 1, and adjusts the flow rate of the carrier gas supplied into the raw material storage unit 10.
  • the carrier gas supplied from the carrier gas supply source 16 is an inert gas that does not contain chlorine (Cl) and hydrogen (H).
  • nitrogen gas (N 2 ) can be used as the carrier gas.
  • not containing chlorine and hydrogen is a concept including not only containing no chlorine and hydrogen but also containing a negligible amount of chlorine and hydrogen in the production of a ZnO film.
  • not including chlorine and hydrogen indicates that the content ratios of chlorine and hydrogen in the carrier gas are each 1% or less (molar concentration).
  • the raw material container 10 communicates with the inside of the reaction vessel 20 through a conduit P2.
  • One end of the conduit P ⁇ b> 2 is connected to the raw material container 10, the other end of the conduit P ⁇ b> 2 penetrates the reaction vessel 20, and an axis line extends between the side wall 22 a of the reaction vessel 20 and the side wall of the reaction tube 24. It extends along the Z direction.
  • a plurality of gas supply holes h ⁇ b> 2 for supplying a source gas containing Zn transported from the source container 10 into the reaction container 20 is formed in a portion of the conduit P ⁇ b> 2 located in the reaction container 20.
  • the reaction gas supply source 32 supplies the reaction gas into the reaction container 20 so that the inside of the reaction container 20 becomes normal pressure.
  • the reaction gas supplied from the reaction gas supply source 32 is a gas containing nitric oxide (NO).
  • the reaction gas may further contain nitrogen gas. Further, the reaction gas may not contain at least any of chlorine, hydrogen, and oxygen. In particular, since the reaction gas does not contain oxygen, the partial pressure of nitrogen that contributes as an acceptor of the ZnO-containing film can be increased.
  • the reactive gas supply source 32 communicates with the inside of the reaction vessel 20 through a conduit P3.
  • the conduit P3 passes through the upper surfaces of the reaction vessel 20 and the reaction tube 24, and extends along the axis Z direction into the space between the side wall of the reaction tube 24 and the installation base 26.
  • a plurality of gas supply holes h3 for supplying a reaction gas containing nitrogen monoxide conveyed from the reaction gas supply source 32 into the reaction vessel 20 is formed in a portion of the conduit P3 located in the reaction tube 24.
  • the inert gas supply source 34 supplies an inert gas into the reaction vessel 20 so that the inside of the reaction vessel 20 becomes a normal pressure.
  • the inert gas supplied from the inert gas supply source 34 is, for example, nitrogen gas.
  • the inert gas supply source 34 communicates with the inside of the reaction vessel 20 through a conduit P4.
  • the conduit P4 passes through the reaction vessel 20 and the reaction tube 24, and extends in the space between the side wall of the reaction tube 24 and the installation base 26 along the axis Z direction.
  • a plurality of gas supply holes h4 for supplying the inert gas conveyed from the inert gas supply source 34 into the reaction vessel 20 are formed in a portion of the conduit P4 located in the reaction tube 24.
  • the raw material gas supplied from the raw material container 10 As described above, the raw material gas supplied from the raw material container 10, the reactive gas supplied from the reactive gas supply source 32, and the inert gas supplied from the inert gas supply source 34 pass through different paths. It will be introduced into the reaction vessel 20.
  • the inert gas supply source 34 is not an essential configuration.
  • the manufacturing apparatus 1 may include a control device 40 that controls each part of the manufacturing apparatus 1.
  • the control device 40 controls the flow rate of the carrier gas using the carrier gas supply source 16, controls the flow rate of the reactive gas using the reactive gas supply source 32, controls the flow rate of the inert gas using the inert gas supply source 34, and controls the flow of the inert gas. Control of the rotation speed of the mounting table 26b, temperature control of the raw material container 10 by the heater power supply 15, temperature control of the reaction vessel 20 by the heater power supply 38, and the like are performed.
  • the control device 40 may be a programmable computer device, for example.
  • the carrier gas supplied from the carrier gas supply source 16 is introduced into the raw material container 10 via the conduit P1.
  • the carrier gas introduced into the raw material storage unit 10 transports Zn vaporized in the raw material storage unit 10 and flows into the reaction vessel 20 through the conduit P2 as a raw material gas containing Zn.
  • the source gas containing Zn ejected from the gas supply hole h ⁇ b> 2 of the conduit P ⁇ b> 2 passes through the opening 24 a and flows in the direction of the substrate 2 arranged inside the reaction tube 24.
  • reaction gas and the inert gas supplied from each of the reaction gas supply source 32 and the inert gas supply source 34 react directly through the gas supply hole h3 of the conduit P3 and the gas supply hole h4 of the conduit P4, respectively. It flows into the tube 24.
  • Zn contained in the source gas reacts with NO contained in the reaction gas, and a ZnO-containing film 2A grows on the substrate 2 disposed on the mounting table 26b.
  • This ZnO-containing film 2A is a p-type ZnO-containing semiconductor film in which nitrogen is doped at a high concentration as an acceptor.
  • the source gas, the reaction gas, and the inert gas in the reaction tube 24 that contributed to the growth of the ZnO-containing film 2A are provided on the side facing the opening 24a into which the source gas flows by the suction action of the exhaust device 36. It passes through the part 24 a and flows out of the reaction tube 24. Then, the source gas, the reaction gas, and the inert gas flow out of the reaction vessel 20 through the exhaust pipe 30.
  • FIG. 3 illustrates a method for manufacturing the ZnO-containing film 2A according to an embodiment using the manufacturing apparatus 1 described above.
  • the substrate 2 is carried into the reaction vessel 20, and then installed on the mounting table 26b of the installation table 26 (installation process).
  • the substrate 2 is a 1 cm square ZnO substrate manufactured by a hydrothermal synthesis method.
  • the substrate 2 may be placed so that the + C plane of the ZnO crystal structure of the substrate 2 is the upper surface. That is, the substrate 2 may be installed so that the ZnO-containing film 2A is formed on the + C plane of the substrate 2. This is because, as will be described later, by forming the ZnO-containing film 2A on the + C surface of the substrate 2, a higher concentration of nitrogen is added to the ZnO-containing film 2A.
  • step S2 the heater H1 and the heater H2 are controlled, and the inside of the raw material container 10 and the reaction vessel 20 are heated (film formation preparation step).
  • step S ⁇ b> 2 the control device 40 controls the heater power supply 15 to bring the inside of the raw material container 10 to a temperature at which Zn is vaporized (first temperature), and controls the heater power supply 38 to set the installation table 26. The temperature is higher than the temperature at which Zn vaporizes (second temperature).
  • the control device 40 controls the heater power supply 15 and sets the inside of the raw material container 10 to 300 ° C. to 400 ° C., controls the heater power supply 38, and sets the installation table to 400 ° C. to 600 ° C. Can be brought to ° C.
  • the control device 40 may control the rotation mechanism 28 and rotate the mounting table 26b on which the substrate 2 is mounted.
  • control device 40 controls the carrier gas supply source 16, the reactive gas supply source 32, and the inert gas supply source 34 while maintaining the heating, and the source gas, the reactive gas, and the reactive gas supply source 34, respectively.
  • An inert gas is supplied into the reaction vessel 20 (film formation step).
  • the control device 40 controls the exhaust device 36 and maintains the inside of the reaction vessel 20 and the raw material container 10 at normal pressure. In this way, the ZnO-containing film 2A is formed on the substrate 2.
  • the Zn contained in the solid raw material M in the raw material container 10 is heated under normal pressure by heating the raw material container 10 under normal pressure. Is vaporized.
  • the vaporized Zn is transported by a carrier gas not containing chlorine and hydrogen supplied into the raw material container 10 and supplied as a raw material gas into the reaction vessel.
  • a reaction gas containing nitrogen monoxide is supplied into the reaction vessel 20 so that the inside of the reaction vessel becomes normal pressure, and the reaction gas reacts with the raw material gas to form the ZnO-containing film 2A. .
  • the ZnO-containing film 2A can be grown at a relatively low temperature of 400 ° C. to 600 ° C.
  • the amount of doping (doping) of the acceptor nitrogen has a property that depends on the growth temperature, and the doping concentration of nitrogen becomes high at a low temperature of 700 ° C. or lower.
  • the inventors have found that the combination of Zn and nitric oxide is highly reactive. Therefore, according to the manufacturing apparatus 1 and the manufacturing method, the ZnO semiconductor film 2A to which nitrogen having a high doping concentration is added can be manufactured under normal pressure.
  • the source gas does not contain hydrogen, generation of crystal defects due to etching with hydrogen gas is prevented. Therefore, according to the manufacturing apparatus 1 and the manufacturing method, the ZnO semiconductor film 2A having excellent crystallinity can be manufactured.
  • the partial pressure of the nitric oxide gas that contributes to the doping of the ZnO-containing film 2A can be increased in the reaction vessel 20 by preventing the reaction gas from containing oxygen, nitrogen having a higher doping concentration can be obtained.
  • a ZnO semiconductor film to which is added can be manufactured.
  • control device 40 controls the heater power supply 15 and controls the inside of the raw material container 10 to 300 ° C. to 400 ° C. Further, by controlling the heater power supply 38 and controlling the installation base at 400 ° C. to 600 ° C., Zn can be vaporized appropriately and the ZnO-containing film 2A can be grown appropriately.
  • a sample of the ZnO-containing film 2A was manufactured using the manufacturing apparatus 1 shown in FIG. 1, and various characteristics were evaluated. Sample manufacturing conditions are as follows.
  • FIG. 4 is a graph showing the relationship between the depth ( ⁇ m) of a sample prepared under the above manufacturing conditions and the nitrogen doping concentration (atm / cm 3 ).
  • the ZnO-containing film 2A was produced by crystal growth on each of the + C plane and the ⁇ C plane of the substrate 2.
  • the growth temperature of the ZnO-containing film 2A that is, the temperature of the installation table 26 was set to 400 ° C. This measurement was performed using a secondary ion mass spectrometer (SIMS).
  • the ZnO-containing film 2A is crystal-grown up to a depth of 0 to 0.7 ⁇ m, and the substrate 2 is a base after the depth of 0.7 ⁇ m.
  • the ZnO-containing film 2A grown on the + C plane of the substrate 2 is doped with nitrogen exceeding 1 ⁇ 10 21 atm / cm 3 at a depth of 0.7 ⁇ m or less. It was confirmed that a ZnO film having a high doping concentration was formed.
  • the nitrogen doping concentration is 1 ⁇ . It was confirmed that it was 10 20 atm / cm 3 or more.
  • FIG. 5A is a graph showing the relationship between the growth temperature of the sample produced under the above manufacturing conditions and the ⁇ FWHM value obtained by X-ray diffraction measurement.
  • the ZnO-containing film 2A was produced by crystal growth on the + C plane of the substrate 2.
  • the ⁇ FWHM value is a difference value of the FWHM value of the substrate 2 with respect to the FWHM value of the sample.
  • the ⁇ FWHM value was measured for the tilt component (X-ray rocking curve half-value width of (0002) plane) and twist component (X-ray rocking curve half-value width of (10-11) plane).
  • the ⁇ FWHM value when the growth temperature is changed from 400 ° C. to 600 ° C. is ⁇ 10 to 10 arcsec. From this value, it was confirmed that the FWHM value of the sample hardly changed even when compared with the FWHM value of the substrate 2, and a very high quality crystal was obtained.
  • FIG. 5B is a graph showing the relationship between the growth temperature of the sample prepared under the above manufacturing conditions and the ⁇ lattice constant of the a axis and c axis obtained by X-ray diffraction measurement.
  • the ZnO-containing film 2A was produced by crystal growth on the + C plane of the substrate 2.
  • the ⁇ lattice constant is a difference value of the lattice constant of the substrate 2 with respect to the lattice constant of the sample.
  • the ⁇ lattice constants of the a axis and the c axis when the growth temperature is changed from 400 ° C. to 600 ° C. are ⁇ 0.0007 to 0.0001 ⁇ . From this value, it was confirmed that the lattice constant of the sample hardly changed even when compared with the lattice constant of the substrate 2, and a very high quality crystal was obtained.
  • FIG. 6 shows the PL spectra of samples 1 to 3 made with different growth temperatures.
  • the horizontal axis in FIG. 6 represents the light energy, and the vertical axis represents the PL intensity.
  • 6A shows the PL spectrum of Sample 1 with a growth temperature of 400 ° C.
  • FIG. 6B shows the PL spectrum of Sample 2 with a growth temperature of 500 ° C.
  • FIG. 6C shows the growth temperature. It is a PL spectrum of the sample 3 which made 600 degreeC.
  • Other manufacturing conditions except for the growth temperatures of Samples 1 to 3 are the same as the above-described sample manufacturing conditions.
  • the ZnO-containing films 2A of Samples 1 to 3 were produced by crystal growth on the + C plane of the substrate 2.
  • the peak of PL emission of Sample 2 and Sample 3 was observed at 3.2 eV to 3.5 eV.
  • sample 1 no PL emission peak was observed at 3.2 eV to 3.5 eV. Note that the peak observed in the vicinity of 3.8 eV is due to the laser for PL emission, and not due to the prepared sample.
  • FIG. 7 shows the film thickness of the ZnO-containing film 2A of samples prepared at different growth temperatures. As shown in FIG. 7, in the range where the growth temperature is lower than 500 ° C., the thickness of the ZnO-containing film 2A increases as the temperature approaches 500 ° C., and in the range where the growth temperature is higher than 500 ° C., the thickness is higher than 500 ° C.
  • the film thickness of the ZnO-containing film 2A decreases as the height increases. However, it was confirmed that in the range of 400 ° C. to 600 ° C., the change in the growth rate of the ZnO-containing film 2A is small and the influence due to the change in the growth temperature is small.
  • the ZnO-containing film 2A doped with nitrogen of 1 ⁇ 10 20 atm / cm 3 or more can be grown on the substrate 2 under normal pressure. .
  • the light emitting element 42 includes a ZnO-containing film 2A grown on the ZnO substrate 2 at room temperature.
  • the substrate 2 serving as a base is an n-type semiconductor containing ZnO as a main component.
  • the ZnO-containing film 2A is a p-type semiconductor to which nitrogen having a doping concentration of 1 ⁇ 10 20 atm / cm 3 or more is added, and forms a pn junction at the interface with the substrate 2.
  • An electrode E1 is formed on the ZnO-containing film 2A.
  • An electrode E2 is formed on the entire lower surface of the substrate 2.
  • the electrodes E1 and E2 can be formed by using, for example, Ti / Au as a material and using a vapor deposition method.
  • the light emitting element 42 emits light by connecting the electrode E2 to the ground and changing the voltage applied to the electrode E1. According to the light emitting element 42, the price of the light emitting element can be reduced by using ZnO as a semiconductor material.
  • steps S2 to S3 in FIG. 3 may be performed in an arbitrary order or may be performed simultaneously.
  • the raw material container 10 is provided outside the reaction vessel 20.
  • the raw material container 10 can be accommodated in the reaction vessel 20.
  • the raw material container 10 and the reaction vessel 20 do not necessarily need to be at normal pressure using the exhaust device 36.
  • the raw material container 10 and the reaction vessel 20 may be maintained at normal pressure by taking outside air from the exhaust pipe 30 provided in the reaction vessel 20 without providing the exhaust device 36.

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Abstract

L'invention concerne une source d'alimentation en matière de départ (MS), qui est conçue pour réaliser l'épitaxie d'un film de ZnO, et qui prend une matière de départ destinée à l'épitaxie d'un film de ZnO et la débite à l'intérieur d'un réacteur (20) contenant un substrat (2) sur lequel il est prévu de réaliser le film de ZnO. Cette source d'alimentation en matière de départ comporte une réserve de matière de départ (10), un réchauffeur (H2), une source d'alimentation en gaz vecteur (16), une source d'alimentation en gaz de réaction (32), et un dispositif de commande (40). La réserve de matière de départ (10), qui débouche à l'intérieur du réacteur (20), contient une matière de départ solide contenant du zinc (M). Le réchauffeur (H2) sert à réchauffer la réserve de matière de départ (10). La source d'alimentation en gaz vecteur (16) sert à débiter un gaz vecteur exempt de chlore ou d'hydrogène à l'intérieur de la réserve de matière de départ (10) de façon à y amener la pression intérieure à un niveau standard. La source d'alimentation en gaz de réaction (32) sert à débiter un gaz de réaction contenant du monoxyde de carbone à l'intérieur du réacteur (20) de façon à y amener la pression intérieure à un niveau standard. Quand le gaz vecteur est débité dans la réserve de matière de départ (10), le dispositif de commande régule le réchauffeur (H2) de façon à amener l'intérieur de la réserve de matière de départ (10) à une température à laquelle le zinc se vaporise.
PCT/JP2014/053486 2013-02-14 2014-02-14 SOURCE D'ALIMENTATION EN MATIÈRE DE DÉPART POUR ÉPITAXIE DE FILM DE ZnO, FILM DE ZnO, DISPOSITIF ET PROCÉDÉ DE FABRICATION DE FILM DE ZnO, ET ÉLÉMENT ÉLECTROLUMINESCENT CONTENANT DU FILM DE ZnO WO2014126203A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270799A (ja) * 2000-03-27 2001-10-02 Toyo Ink Mfg Co Ltd 酸化亜鉛薄膜およびその製造方法
JP2010157574A (ja) * 2008-12-26 2010-07-15 Tokyo Univ Of Agriculture & Technology 酸化亜鉛系半導体、酸化亜鉛系半導体の製造方法および製造装置
JP2011501877A (ja) * 2007-09-26 2011-01-13 イーストマン コダック カンパニー ドープ型酸化亜鉛の形成方法
JP2011096884A (ja) * 2009-10-30 2011-05-12 Stanley Electric Co Ltd ＺｎＯ系化合物半導体の製造方法及び半導体発光素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270799A (ja) * 2000-03-27 2001-10-02 Toyo Ink Mfg Co Ltd 酸化亜鉛薄膜およびその製造方法
JP2011501877A (ja) * 2007-09-26 2011-01-13 イーストマン コダック カンパニー ドープ型酸化亜鉛の形成方法
JP2010157574A (ja) * 2008-12-26 2010-07-15 Tokyo Univ Of Agriculture & Technology 酸化亜鉛系半導体、酸化亜鉛系半導体の製造方法および製造装置
JP2011096884A (ja) * 2009-10-30 2011-05-12 Stanley Electric Co Ltd ＺｎＯ系化合物半導体の製造方法及び半導体発光素子

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