Classifications

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  • 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
• • 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
  • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
  • C23C16/303—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
  • 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
  • C23C16/4488—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 in situ generation of reactive gas by chemical or electrochemical reaction
• • 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
  • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
  • C30B25/02—Epitaxial-layer growth
  • C30B25/10—Heating of the reaction chamber or the substrate
• • 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
  • H01L21/02367—Substrates
  • H01L21/0237—Materials
  • H01L21/02373—Group 14 semiconducting materials
  • H01L21/02381—Silicon, silicon germanium, germanium
• • 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
  • H01L21/02367—Substrates
  • H01L21/0237—Materials
  • H01L21/0242—Crystalline insulating materials
• • 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
• • 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
  • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

• the present invention relates to a hybrid deposition system.
• the invention further relates to a deposition system, which combines features of metal-organic chemical vapor deposition with hydride vapor-phase epitaxy.
• the present invention also relates to a method of forming semiconductor heterostructures, by two different deposition techniques, in a single reactor.
• HVPE Hydride vapor-phase epitaxy
• GaN Gallium nitride
• GaN is emerging as an important technological material.
• GaN is currently used in the manufacture of blue light emitting diodes, semiconductor lasers, and other opto-electronic devices. The background of the related art will be discussed with particular reference to the deposition of GaN.
• HVPE is a currently favored technique for GaN deposition, because it provides relatively rapid growth in a cost- effective manner.
• growth of GaN proceeds due to the high temperature, vapor-phase reaction between gallium chloride (GaCl) and ammonia (NH 3 ) .
• the ammonia is supplied from a standard gas source, while the GaCl is produced by passing HC1 over a heated liquid gallium supply.
• the two gases (ammonia and GaCl) are directed towards a heated substrate where they react to produce solid GaN on the substrate surface.
• HVPE allows for high growth rates of GaN
• HVPE is difficult to grow materials such as aluminum nitride (A1N) or alloys of A1N and GaN (AlGaN) by HVPE.
• AlGaN aluminum nitride
• the problem lies in providing an adequate supply of aluminum chloride.
• the latter substance is extremely stable, and tends to form a solid with low vapor pressure even at the elevated temperature of a HVPE reactor.
• the aluminum chloride that is formed tends to solidify and not to be carried towards the substrate.
• a technique for growing both A1N and GaN layers on the same sample is desirable for several applications.
• a buffer layer of A1N or AlGaN grown between an epitaxial GaN layer and a typical substrate such as sapphire improves the quality of the GaN epitaxial layer. This improved quality results from closer matching of lattice constant and thermal expansion coefficient between the buffer layer and the GaN.
• heterostructures including indium nitride (InN) and associated alloys (InGaN, InAlN, InAlGaN) in the same system.
• InN indium nitride
• InAlN InAlGaN
• HVPE high vacuum chemical vapor deposition
• dopants it is necessary to selectively incorporate dopants to provide conductive materials. Junctions of material incorporating different dopant types are key elements of almost all electronic devices, such as the diode, the transistor, and the semiconductor laser. However, some dopant materials are best utilized in organo-metallic form.
• HVPE HVPE-sensitive substrates
• certain substrates cannot be incorporated into an HVPE system until a certain amount of epitaxial material has been grown. For example, it may be desired to grow GaN or related materials on silicon (Si) substrates. Alternatively, it may be desired to use compound substrates (consisting of more than one type of material), or patterned substrates. If any of these substrates are subjected directly to HVPE growth, they may be destroyed. This is due to the presence in HVPE reactors of certain gases, such as HC1, which act as etchants on HVPE- sensitive substrates (e.g., Si).
• gases such as HC1 which act as etchants on HVPE- sensitive substrates (e.g., Si).
• the present invention provides a hybrid deposition system for the efficient growth of aluminum nitride, indium nitride, gallium nitride, metal alloy-nitrides and related materials.
• Methods of the invention allow the incorporation of complex dopants and complex dopant mixtures into epitaxial layers and provides for the production of a large variation of film thicknesses and growth rates.
• methods of the invention can accommodate many different substrate types .
• the invention combines features of metal-organic chemical vapor deposition (MOCVD) and HVPE into a single, highly versatile, hybrid deposition system.
• the present invention uses metal-organic sources and a HVPE reagent delivery chamber (e.g., liquid gallium supply), in a hybrid reactor.
• the system of the invention can be switched between operation in MOCVD mode and HVPE mode, or can be operated in combined MOCVD/HVPE mode. Such switching between modes is easily achieved by changing the nature of the source or reagent gases supplied to the reactor, and by any appropriate changes to the operating or growth temperature of the reactor.
• At least one metallo-organic and ammonia gas are supplied to the reactor.
• the metallo-organic supply is shut off, and a supply of a second reagent gas (e.g., GaCl) is provided by passing HC1 over liquid metal (Ga) .
• a second reagent gas e.g., GaCl
• the temperature of the reactor may be changed when switching between HVPE mode and MOCVD mode.
• AIN and thin InN layers can be conveniently grown (by MOCVD) in the same reactor as is used for the growth of thick GaN (by HVPE) .
• AIN, InN, GaN, and their alloys can be grown in the same reactor by MOCVD and HVPE, either consecutively or concurrently. Therefore, a diverse array of heterostructures of AIN, InN, GaN and their alloys can be grown quickly and inexpensively using systems and methods of the invention.
• a method for growing III-V nitride layers on a non-native substrate, using both HVPE and MOCVD growth techniques simultaneously.
• two different source gases such as GaCl and an aluminum- containing metallo-organic, are both supplied to the system together with ammonia.
• each source gas reacts with the ammonia gas at the location of the substrate, leading to deposition of AlGaN.
• InGaN or InAlGaN may be grown by an analogous method by supplying the appropriate source gases.
• dopants may be incorporated in layers of GaN or its alloys grown using the hybrid deposition system of the invention.
• a method for using HVPE-sensitive substrates for deposition of III-V compounds by HVPE.
• Substrates that would normally be destroyed by HVPE growth such as Si substrates or patterned substrates, are stable under MOCVD growth.
• a first, protective layer of a III-V compound is first grown on the substrate by MOCVD in the hybrid reactor.
• the hybrid reactor may then be switched to operate in HVPE mode, and at least one additional layer is formed by HVPE on the first layer.
• HVPE has the advantage of having a faster growth rate and is less expensive than MOCVD.
• One feature of the invention is that it provides a hybrid deposition system. Another feature of the invention is that it provides a deposition system that can be operated in two different modes. Another feature of the invention is that it provides a hybrid MOCVD/HVPE deposition system. Another feature of the invention is that it provides a deposition system including a reactor and a plurality of heating units for heating the reactor.
• Another advantage of the invention is that it provides a hybrid deposition system including a reactor that is moveable with respect to at least one heating unit.
• Yet another advantage of the current invention is that a high quality device structure can be produced by first producing a thin buffer layer by MOCVD, a thicker GaN layer by HVPE on the thin buffer layer and a third nitride layer on the thicker GaN layer by MOCVD.
• a hybrid deposition system including: a reactor; a reagent delivery chamber having a reagent delivery chamber inlet, the reagent delivery chamber coupled to the reactor; at least one heating unit for supplying heat to the reactor; and at least one metallo-organic source coupled to the reactor.
• a method of forming a semiconductor layer including the steps of: a) arranging a substrate within a reactor; b) heating the reactor to a first growth temperature; c) supplying a first reagent gas and an organo-metallic vapor to the reactor to provide, by MOCVD, a first III-V nitride layer on the substrate; d) after step c) , stopping the supply of organo-metallic vapor to the reactor; and e) while continuing to supply the first reagent gas to the reactor, supplying a second reagent gas to the reactor to provide at least one additional III-V nitride layer on the first III-V nitride layer.
• a method of forming a semiconductor layer comprising the steps of: a) arranging a substrate within a reactor; b) heating the reactor to a first growth temperature; c) supplying a first reagent gas to the reactor; d) supplying a metallo-organic vapor to the reactor to provide, by MOCVD, a first III-V nitride layer on the substrate; e) after step d) , while continuing to supply the first reagent gas and the metallo-organic vapor to the reactor, supplying a second reagent gas to the reactor to provide at least one additional III-V nitride layer on the first III-V nitride layer.
• Fig. 1 schematically represents a MOCVD system of the prior art
• Fig. 2 schematically represents a HVPE system of the prior art
• Fig. 3 schematically represent a hybrid deposition system, according to the invention
• Fig. 4 schematically represents multiple organo-metallic sources and a dopant source for use in conjunction with a deposition system, according to one embodiment of the invention
• Fig. 5A schematically represents a series of steps involved in a method of hybrid deposition, according to the invention
• Fig. 5B schematically represents a series of steps involved in a method of hybrid deposition, according to another embodiment of the invention
• Fig. 6A schematically represents a series of steps involved in a method of hybrid deposition, according to another embodiment of the invention.
• Fig. 6B schematically represents a series of steps involved in a method of hybrid deposition, according to another embodiment of the invention.
• Fig. 1 schematically represents a MOCVD system 6 according to the prior art .
• system 6 includes a reactor 8, at least part of which is surrounded by a heating unit 16.
• a substrate 14, arranged within reactor 8, is heated by means of heating unit 16.
• Ammonia is provided from a standard gas source 13.
• Vapor of a metallo-organic compound is supplied by passing a carrier gas 17, typically nitrogen or hydrogen, through a liquid supply of the metallo-organic compound contained within a bubbler 15.
• the temperature of the metallo-organic compound supply is precisely controlled, and the flow of carrier gas 17 is regulated to provide a stream of gas that contains a known amount of vapor of the metallo- organic compound.
• the ammonia and the vapor of the metallo- organic compound are introduced into chamber 8. Deposition of InN, AIN GaN or alloy nitrides of In, Al, and Ga, occurs on the surface of substrate 14 due to the high temperature vapor-phase reaction of the metallo-organic compound with the ammonia gas.
• the metallo-organic (or organo-metallic) compound in bubbler 15 is an aluminum- containing organo-metallic
• the organo-metallic compound in bubbler 15 is a gallium-containing organo-metallic
• Fig. 2 schematically represents a HVPE system 18 according to the prior art .
• system 18 includes a growth tube or reactor 21 having inlet 22, and outlet 19, and a reagent delivery chamber or reaction assembly 26.
• System 18 may be contained entirely within a heat source, e.g., a furnace 24.
• Epitaxial deposition on heated substrate 14 proceeds by the vapor-phase reaction of source or reagent gases, which are introduced into reactor 21.
• a reagent gas such as gallium chloride, indium chloride, or aluminum chloride, may be projected towards substrate 14 via reaction assembly 26; while ammonia may be introduced into growth tube 21 through reactor inlet 22.
• Reagent gas e.g.
• GaCl may be formed in reaction assembly 26 by passing HCl over liquid metal (e.g., gallium) at elevated temperatures. The direction of gas flow is indicated by the arrows.
• Reagent gases e.g., GaCl, InCl, AlCl
• Fig. 3 schematically represents a hybrid deposition system 30, according to one embodiment of the invention.
• System 30 includes a reactor chamber 32 having an inlet 34 and an outlet 36, and a reagent delivery chamber 38 coupled to reactor chamber 32.
• Reactor inlet 34 is coupled to a first reagent gas source 46, and to at least one metallo-organic source 52. The direction of gas flow is indicated by the arrows.
• First reagent gas source 46 supplies a first reagent gas to reactor 32.
• the first reagent gas is preferably ammonia.
• Metallo-organic source 52 contains a metallo-organic composition for supplying a metallo-organic vapor to reactor chamber 32.
• the metallo-organic composition is preferably an aluminum-, indium-, or gallium containing metallo-organic compound, or a mixture or alloy of at least two metallo-organic compounds having two different metals selected from Ga, In, and Al .
• metallo-organic compounds useful in the practice of the invention are: trimethylaluminum (TMA) , triethyl- aluminum (TEA) , trimethylindium (TMI) , triethylindium (TEI) , trimethylgallium (TMG) , and triethylgallium (TEG) .
• organo-metallic and metallo-organic may be used interchangeably.
• Metallo-organic source 52 may be in the form of a bubbler, the latter well known in the art.
• Reagent delivery chamber 38 is coupled to a precursor gas source 48 and to a carrier gas source 50.
• Precursor gas source 48 supplies precursor gas, preferably HCl, to reagent delivery chamber 38.
• Reagent delivery chamber 38 contains liquid metal such as Ga, In, Al, preferably Ga or In.
• a second reagent gas is generated within reagent delivery chamber 38 when HCl gas is passed over liquid metal within chamber 38. The second reagent gas passes from reagent delivery chamber 38 into reactor 32.
• Carrier gas source 50 supplies a carrier gas.
• Carrier gas source 50 is coupled both to reagent delivery chamber inlet 38a, and to metallo-organic source 52.
• Carrier gas from carrier gas source 50 serves to carry precursor gas from source 48 to inlet 38a of chamber 38.
• Carrier gas from carrier gas source 50 also supplies organo-metallic vapor from the metallo-organic composition contained within metallo-organic source 52.
• Flow of carrier gas from carrier gas source 50 to inlet 38a of reagent delivery chamber 38 is controlled by a first valve unit 54a.
• Flow of carrier gas from carrier gas source 50 to the metallo-organic source 52 is controlled by a second valve unit 54b.
• First and second valve units 54a, 54b allow the control of carrier gas flow from source 50 to the reagent delivery chamber 38 and to metallo-organic source 52.
• a third valve unit 54c controls flow of the precursor gas from source 48 to reagent delivery chamber 38.
• the deposition mode of system 30 can be determined and adjusted by means of first, second, and third valve units 54a-c.
• valve units 54a and 54c are closed, while valve unit 54b is opened.
• Carrier gas from source 50 carries metallo-organic vapor via source 52 to reactor 32, while source 46 supplies first reagent gas (ammonia) to reactor 32.
• the temperature of reactor 32 and of substrate 14 is adjusted, for MOCVD deposition of a particular III-V compound or alloy, by means of heating units 40, 42, 44. Deposition on substrate 14 then proceeds solely by MOCVD .
• the deposition mode of system 30 may be "switched” or changed from solely MOCVD mode to solely HVPE mode, without interrupting deposition or removing the substrate from reactor 32, as follows.
• Valve unit 54b is closed, while valve units 54a and 54c are opened.
• Valve units 54a and 54c may be opened first, and thereafter valve unit 54b closed.
• Metallo-organic vapor is no longer supplied to reactor 32. Instead, precursor gas is supplied from source 48 to chamber 38, the latter in turn supplies the second reagent gas (e.g., GaCl, InCl) to reactor 32; while source 46 continues to supply first reagent gas (ammonia) to reactor 32.
• second reagent gas e.g., GaCl, InCl
• the temperature of reactor 32 and of substrate 14 may be adjusted, for HVPE deposition of a particular III-V compound or alloy, by means of heating units 40, 42, 44. Deposition on substrate 14 then proceeds solely by HVPE.
• the precise timing of opening and closing of valve units 54a-c is, at least to some extent, a matter of design choice.
• the deposition mode of system 30 may also be switched from solely MOCVD or solely HVPE mode, to a combined MOCVD/HVPE mode.
• MOCVD/HVPE mode is characterized by simultaneous deposition by MOCVD and HVPE. Changes between each of these modes may be performed without interrupting deposition, or removing the substrate from reactor 32.
• each of valve units 54a, 54b, and 54c may be opened to an appropriate extent.
• ammonia is supplied to reactor 32 via source 46
• metallo-organic vapor is supplied to reactor 32 via source 52
• the second reagent gas is supplied to reactor 32 from chamber 38.
• Deposition then proceeds by both MOCVD and HVPE to form a hybrid MOCVD/HVPE layer on the substrate or sample.
• the relative contribution of each deposition technique may be determined by adjustments to valve units 54a-c.
• the temperature of reactor 32 may be adjusted by means of heating units 40, 42, 44. Alternatively, the temperature of reactor 32 may be adjusted by moving reactor 32 with respect to heating units 40, 42, 44.
• alloys having various compositions of III-V compounds may be readily deposited on substrate 14.
• a dopant source in the form of a bubbler, evaporative or sublimation source, or in the form of added gas component to the carrier gas stream, or in the form of a dilute pre-mixed mixture of dopant gas and carrier gas, may be introduced via the reactor inlet 34 during HVPE growth steps, in order to form doped III-V nitride layers.
• a III-V nitride layer such as GaN, may also be doped by including a dopant source along with the liquid metal supply within the reagent delivery chamber 38 or by providing a separate dopant delivery system in communication with the reactor chamber through a separate dopant inlet, which is not integrated with the metal reagent delivery chamber or the reactor chamber inlet as shown on Fig. 4.
• System 30 of the invention is useful inter alia, for deposition of an epitaxial layer (e.g., of GaN or an alloy thereof) on substrates that are normally destroyed by HVPE but are stable under MOCVD growth conditions.
• HVPE- sensitive substrates are silicon, and patterned substrates.
• a protective layer may first be formed in reactor 32 via MOCVD. Thereafter, the deposition mode of system 30 may be switched, either wholly or in part, to HVPE mode. This allows the faster and less costly HVPE mode to be used for epitaxial growth on a HVPE-sensitive substrate.
• system 30 may be switched from MOCVD mode to HVPE mode, and vice versa, without interruption of deposition or removal of the sample from reactor 32.
• System 30 may include a plurality of different heating units.
• system 30 may include a first heating unit 40, a second heating unit 42, and a third heating unit 44.
• First, second, and third heating units 40, 42, 44 may each be in the form of a furnace, one or more lamps, or a plurality of radio frequency or micro-wave heater induction coils.
• First, second, and third heating units 40, 42, 44 may be located at different positions, both laterally and longitudinally with respect to reactor 32. Then, by moving reactor 32 with respect to first, second, and third heating units 40, 42, 44 the temperature of the reactor may be adjusted according to the particular mode of deposition to be performed.
• Manipulation e.g., movement
• adjustment of heating units 40, 42, 44 allows for fine tuning of deposition within reactor 32.
• Longitudinal movement of reactor 32 is indicated in Fig. 3 by double-headed arrow 32' .
• one or more of first, second, and third heating units 40, 42, 44 may themselves be moved, independently of each other, with respect to reactor 32 in order to effect temperature changes within reactor 32.
• an internal heating unit 31 that is positioned within the reactor 32, may be used to control the temperature.
• the internal heating unit 31 is preferably positioned within the substrate platform 11 and controls the surface temperature of the substrate platform 11 and the attached substrate 14.
• Fig. 4 schematically represents part of a deposition system 30', according to another embodiment of the invention.
• System 30' is analogous to system 30 (Fig.3), except that the former includes a plurality of metallo-organic sources 52a, 52b, 52c. Although three such sources are shown in Fig. 4, other numbers are within the scope of the invention.
• Each metallo-organic source 52a, 52b, 52c is connected to carrier gas source 50 for supplying carrier gas to metallo-organic sources 52a, 52b, 52c.
• the supply of carrier gas to each of sources 52a, 52b, 52c is controlled by a valve, e.g., 54.
• Each metallo-organic source 52a, 52b, 52c is further coupled to reactor 32 for supplying metallo-organic vapor to reactor 32.
• Each metallo-organic source 52a, 52b, 52c may contain a different metallo-organic composition.
• sources 52a, 52b, 52c may contain a A1-, an In-, and a Ga-containing compound, respectively.
• sources 52a, 52b, 52c may contain an A1-, In-, or Ga-containing compound with or without various dopants.
• the reactor chamber 32 may be equipped with a separate inlet 85 for delivering a dopant source 83 to the reactor chamber 32 during deposition processes.
• the dopant source 83 is delivered to the reactor chamber 32 via a bubbler.
• a dopant carrier gas 81 is bubbled through a dopant reagent or source 83 with a flow rate that is controlled by a valve 84, in similar fashion to that which is described above for delivering metallo-organic sources to the reactor chamber 32.
• Suitable dopant reagents include organo-nitrogen, organo- arsenic and organo-phosphorus .
• each metallo-organic composition and dopant supplied to reactor 32 may be precisely controlled over time.
• layers of AlN, InN, GaN, and their alloys e.g., AlGaN, InAlN, InAlGaN
• MOCVD Metal Organic Chemical Vapor Deposition
• system 30' to operate in HVPE mode, MOCVD mode, or in joint HVPE/MOCVD mode, while providing a plurality of metallo-organic sources 52a-c, allows greater control over the composition and thickness of various III-V nitride layers to be formed according to the invention.
• systems 30 and 30' are highly versatile in their operation, and allow for the formation of a huge array of semiconductor layers and heterostructures using a single apparatus .
• Fig. 5A schematically represents a series of steps involved in a hybrid deposition method, according to the invention, in which step 50 involves performing HVPE in a reactor of a hybrid deposition system to provide a semiconductor layer or III-V compound on a substrate.
• hybrid deposition system is meant a system adapted for deposition by at least two distinct modes (e.g., MOCVD and HVPE), in which the two distinct modes may be performed either consecutively or simultaneously in the same reactor.
• the substrate or sample is not removed from the reactor while the mode of operation of the deposition system is changed.
• the sample may be a non-native substrate, such as silicon or sapphire.
• Step 52 involves performing MOCVD in the same reactor of the hybrid deposition system as used for step 50.
• Step 52 may be performed before, after, or at the same time as step 50, depending on the particular application of the sample, the nature of the material to be deposited by HVPE and MOCVD, the nature of the substrate, etc.
• Fig. 5B schematically represents a series of steps involved in a method of hybrid deposition, according to another embodiment of the invention, in which step 54 involves performing MOCVD on a substrate.
• the substrate is arranged within a reactor of a hybrid deposition system.
• the substrate may be a non-native substrate, such as silicon or sapphire, and may be a patterned substrate.
• a layer of a semiconductor, such as a III-V nitride may be deposited on the substrate to any desired thickness, but is preferably in the range 1.0 nanometer to 5.0 micron.
• a relatively thin protective layer of, for example, AIN may be deposited by MOCVD on a HVPE-sensitive substrate.
• Step 54 may be performed, for example, by supplying ammonia gas and vapor from an aluminum-containing organic compound to the reactor housing the substrate.
• Step 56 involves performing HVPE in the reactor of the hybrid deposition system while continuing MOCVD deposition.
• Step 56 may be performed, for example, by supplying a second reagent gas (e.g., GaCl or InCl) to the reactor housing the substrate, together with ammonia gas and vapor from a metallo-organic compound.
• Step 56 may be performed with no interruption of the deposition initiated in step 54.
• Fig. 6A schematically represents a series of steps involved in a method of hybrid deposition, according to another embodiment of the invention, in which step 60 involves arranging a substrate in a reactor of a hybrid deposition system.
• the hybrid deposition system may be any of the embodiments of a hybrid deposition system described hereinabove, or variants thereof as may be apparent to the skilled artisan.
• Step 62 involves heating the reactor.
• the reactor may be heated to any desired temperature by means of at least one heating unit. Heating units may be in the form of, e.g., one or more furnaces, at least one lamp, a plurality of rf heater coils, or an internal heating unit.
• the desired growth temperature may be determined by factors such as the mode of deposition, the materials to be deposited, the nature of the substrate, etc.
• Step 64 involves supplying, to the reactor, suitable reagents for performing MOCVD on the substrate. Reagents for MOCVD together with techniques suitable for supplying them to the reactor of a hybrid deposition system have been described hereinabove .
• Step 66 involves forming a first layer on the substrate by MOCVD.
• the first layer deposited on the substrate may be a III-V nitride, such as AlN, GaN, InN, or an alloy thereof.
• step 68 involves supplying HVPE reagents to the reactor of the hybrid deposition system, generally according to techniques and processes described hereinabove.
• the reactor temperature may be adjusted, as deemed appropriate for deposition of at least one additional layer (step 70) on the first layer.
• the temperature of the reactor may be adjusted by means of the at least one heating unit, or by, for example, changing the location of the reactor with respect to the at least one heating unit.
• Step 70 involves forming at least one additional layer on the first layer.
• the at least one additional layer may be formed by HVPE alone or by a combination of HVPE and MOCVD.
• the at least one additional layer may be a III-V nitride or an alloy of two or more III-V nitrides.
• the at least one additional layer includes GaN and/or an alloy of GaN.
• Fig. 6B schematically represents a series of steps involved in a method of hybrid deposition, according to another embodiment of the invention, in which step 60' is analogous to step 60 (Fig. 6A) .
• Step 62' involves heating the reactor to a first growth temperature, generally as described hereinabove for step 62 (Fig. 6A) .
• the first growth temperature of step 62 ' may be selected to fit deposition of a particular material, e.g., AlN, by a particular technique, such as MOCVD.
• Steps 64' and 66' are analogous to steps 64 and 66 (Fig. 6A) .
• Step 72 involves stopping the supply to the reactor of vapor from the metallo- organic reagent.
• Optional step 74 involves adjusting the reactor to a second growth temperature, as appropriate for deposition of a particular material, e.g., GaN, by HVPE (step 78) .
• the reactor may be adjusted to the second growth temperature generally as described for step 62 (Fig. 6A) .
• Step 76 involves supplying reagents for HVPE, e.g., ammonia and a chloride of Ga or In, generally as described hereinabove.
• Step 78 involves forming at least one additional layer, e.g., of a III-V nitride, on the first layer (step 66') .
• the at least one additional layer formed in step 78 may be formed solely by HVPE.

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