US20100086703A1 - Vapor Phase Epitaxy System - Google Patents

Vapor Phase Epitaxy System Download PDF

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US20100086703A1
US20100086703A1 US12/572,245 US57224509A US2010086703A1 US 20100086703 A1 US20100086703 A1 US 20100086703A1 US 57224509 A US57224509 A US 57224509A US 2010086703 A1 US2010086703 A1 US 2010086703A1
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precursor gas
electrode
gas
precursor
injecting
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Joshua Mangum
William E. Quinn
Eric Armour
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Veeco Compound Semiconductor Inc
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Veeco Compound Semiconductor Inc
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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
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/511—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 using electric discharges using microwave discharges
    • 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
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C23C16/45548—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction
    • C23C16/45551—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction for relative movement of the substrate and the gas injectors or half-reaction reactor compartments
    • 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
    • C23C16/48—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 by irradiation, e.g. photolysis, radiolysis, particle radiation
    • C23C16/483—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 by irradiation, e.g. photolysis, radiolysis, particle radiation using coherent light, UV to IR, e.g. lasers
    • 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
    • C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
    • 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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • 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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • 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

Definitions

  • Vapor phase epitaxy is a type of chemical vapor deposition (CVD) which involves directing one or more gases containing chemical species onto a surface of a substrate so that the reactive species react and form a film on the surface of the substrate.
  • VPE can be used to grow compound semiconductor material on a substrate.
  • the substrate is typically a crystalline material in the form of a disc, which is commonly referred to as a “wafer.”
  • Materials are typically grown by injecting at least a first and a second precursor gas into a process chamber containing the crystalline substrate.
  • MOVPE Metalorganic vapor phase epitaxy
  • MOCVD metalorganic chemical vapor deposition
  • OMCVD organometallic chemical vapor deposition
  • the gases are reacted with one another at the surface of a substrate, such as a sapphire, Si, GaAs, InP, InAs or GaP substrate, to form a III-V compound of the general formula In X Ga Y Al Z N A As B P C Sb D , where X+Y+Z equals approximately one, and A+B+C+D equals approximately one, and each of X, Y, Z, A, B, C, and D can be between zero and one.
  • bismuth may be used in place of some or all of the other Group III metals.
  • Compound semiconductors can also be formed by growing various layers of semiconductor materials on a substrate using a hydride or a halide precursor gas process.
  • Group III nitrides e.g., GaN, AN
  • HVPE halide vapor phase epitaxy
  • Group III nitrides e.g., GaN, AN
  • NH 3 ammonia gas
  • the metal chlorides are generated by passing hot HCl gas over the hot Group III metals. All reactions are done in a temperature controlled quartz furnace.
  • One feature of HVPE is that it can have a very high growth rate, up to 100 ⁇ m per hour for some state-of-the-art processes.
  • Another feature of HVPE is that it can be used to deposit relatively high quality films because films are grown in a carbon free environment and because the hot HCl gas provides a self-cleaning effect.
  • the substrate is maintained at an elevated temperature within a reaction chamber.
  • the precursor gases are typically mixed with inert carrier gases and are then directed into the reaction chamber.
  • the gases are at a relatively low temperature when they are introduced into the reaction chamber.
  • the gases reach the hot substrate, their temperature, and hence their available energy for reaction, increases.
  • Formation of the epitaxial layer occurs by final pyrolysis of the constituent chemicals at the substrate surface. Crystals are formed by a chemical reaction and not by physical deposition processes. Growth occurs in the gas phase at moderate pressures. Consequently VPE is a desirable growth technique for thermodynamically metastable alloys.
  • VPE is commonly used for manufacturing laser diodes, solar cells, and LEDs.
  • FIG. 1 illustrates a known vapor phase epitaxy system used to form compound semiconductors.
  • FIG. 2 illustrates a vapor phase epitaxy system according to the present teachings that includes at least one electrode positioned in a flow of a first precursor gas and being substantially isolated from a flow of a second precursor gas.
  • FIG. 3 illustrates a top-view of one embodiment of a disk-shaped gas injector according to the present teaching that includes a first region that is positioned in quadrants of the gas injector and a second region extending radially through the quadrants.
  • FIG. 4A illustrates a cross-section of one embodiment of a disk-shaped gas injector according to the present teaching that includes a plurality of first and second regions which alternates across the gas injector.
  • FIG. 4B illustrates an expanded view of the disk-shaped gas injector illustrating mechanical or chemical barriers that isolate the electrodes from the second precursor gas.
  • FIG. 5 illustrates a perspective top-view of a vapor phase epitaxy system according to the present teachings that includes a horizontal flow gas injector.
  • FIG. 6 illustrates a foil-shaped electrode positioned close to the surface of the platen for thermally activating a precursor gas in a vapor phase epitaxy system according to the present teaching.
  • available energy refers to the chemical potential of a reactant species that is used in a chemical reaction.
  • the chemical potential is a term commonly used in thermodynamics, physics, and chemistry to describe the energy of a system (particle, molecule, vibrational or electronic states, reaction equilibrium, etc.).
  • more specific substitutions for the term chemical potential may be used in various academic disciplines, including Gibbs free energy (thermodynamics) and Fermi level (solid state physics), etc.
  • references to the available energy should be understood as referring to the chemical potential of the specified material.
  • FIG. 1 illustrates a known VPE system 100 used to form compound semiconductors.
  • This system 100 includes a reaction chamber 101 having a spindle 102 mounted therein.
  • the spindle 102 is rotatable about an axis 104 by a rotary drive mechanism 106 .
  • the axis 104 extends in an upstream direction U and a downstream direction D as shown in FIG. 1 .
  • a platen 108 which in many systems is a disc-like substrate carrier, is mounted on the spindle 102 for rotation therewith.
  • the platen 108 and spindle 102 rotate at rotation rates that are in the range of about 100-2,000 revolutions per minute.
  • the platen 108 is adapted to hold a plurality of disc-like substrates 110 so that surfaces 112 of the substrates 110 are in a plane perpendicular to axis 104 and face in the upstream direction U.
  • a heater 114 such as a resistance heating element, is positioned within the reaction chamber 101 proximate to the platen 108 .
  • the heater 114 heats the substrate carrier to the desired processing temperature.
  • a gas injector 116 which is sometimes known in the art as a flow inlet element, is mounted upstream of the platen 108 and spindle 102 .
  • the gas injector 116 is connected to process gas sources 118 , 120 , and 122 .
  • the gas injector 116 directs streams of various process gases into the reaction chamber 101 .
  • a fluid coolant supply 117 is coupled to liquid cooling channels in the flow injector 116 to circulate the cooling fluid in order to control the temperature of the gas injector 116 .
  • streams of process gases from the process gas sources 118 , 120 , and 122 flow generally downstream toward the platen 108 and substrates 110 in a region of the reaction chamber 101 between the gas injector 116 and the platen 108 , that is referred to herein as the “flow region 124 .”
  • this downward flow does not result in substantial mixing between separate streams of downwardly flowing gas. It is typically desirable to design and operate the system 100 so that there is laminar flow in the flow region 124 .
  • the platen 108 is rotated rapidly about the axis 104 with the rotary drive 106 so that the surface of the platen 108 and the surfaces of the substrates 110 are moving rapidly.
  • the rapid motion of the platen 108 and substrates 110 entrains the gases into rotational motion about axis 104 . Consequently, the process gases flow radially away from axis 104 , thereby causing the process gases in the various streams to mix with one another within a boundary layer that is schematically indicated in boundary layer region 126 .
  • the boundary layer 126 is generally regarded as a region in which the gas flow is substantially parallel to the surfaces of the substrates 110 .
  • the thickness of the boundary layer 126 is on order of about 1 cm and the distance from the downstream face of gas injector 116 to the surfaces 112 of the substrates 110 is about 5-8 cm.
  • the flow region 124 occupies the major portion of the space between the gas injector 116 and the platen 108 .
  • the rotational motion of the platen 108 pumps the gases outwardly around the peripheral edges of the platen 108 , and hence the gases pass downstream to an exhaust system 130 .
  • the reaction chamber 101 is maintained under an absolute pressure from about 25-1,000 Ton.
  • Many processes operate at an absolute pressure of about 50-760 Torr.
  • the gas injector 116 is maintained at a relatively low temperature, which is typically about 60° C. or less, although higher temperatures are sometimes used.
  • the Group III halide is maintained at an elevated temperature to prevent condensation. This elevated temperature is below the temperature of the substrates 110 where deposition occurs.
  • the relatively low temperature is chosen to inhibit decomposition of reactants and/or to inhibit the formation of undesired reactions of the reactants in the gas injector 116 and in the flow region 124 .
  • the walls 101 ′ of reaction chamber 101 are cooled to about 25° C. in order to minimize the rate of any reactions of the process gases in the flow region 124 remote from the platen 108 .
  • the reaction energy is provided primarily by heat from the platen 108 and substrates 110 .
  • the reaction energy is the energy required to dissociate a Group V hydride, such as NH 3 , to form reactive intermediates, such as NH 2 and NH.
  • a Group V hydride such as NH 3
  • reactive intermediates such as NH 2 and NH.
  • increasing the temperature of the platen 108 and substrates 110 also tends to increase dissociation of the deposited compound semiconductors.
  • increasing the temperature of the platen 108 and substrates 110 can result in a loss of nitrogen from the semiconductor especially when growing Indium-rich compounds such as InGaN and InN.
  • VPE systems include one or more electrically active electrodes that are used to add additional energy to a process gas in order to increase the reaction rate or to modify the reaction chemistry.
  • electrically active electrodes such as wires and filaments in any shape, which are exposed to a process gas in the process chamber 101 .
  • the present teachings it is desirable to supply energy to one of the process gases without supplying significant energy to other process gases.
  • the Group V hydride precursor gases which for example, can be ammonia (NH3) without supplying significant energy to the Group III metal precursor gases.
  • the one or more electrically active electrodes can be physically isolated from a precursor gas that will react in the presence of the elevated temperatures. Physical isolation can be achieved by introducing the gases separately in different regions of the reactor and by using baffles and/or gas curtains as described herein.
  • gases can be introduced separately, but at the same distance from the substrates 110 in order to maintain laminar flow over the surfaces of the substrates 110 .
  • FIG. 2 illustrates a vapor phase epitaxy system 200 according to the present teachings that includes at least one electrode positioned in a flow of a first precursor gas and being substantially isolated from a flow of a second precursor gas.
  • the VPE system 200 is similar to the VPE system described in connection with FIG. 1 .
  • the VPE system 200 includes a process chamber 201 for containing process gasses.
  • the VPE system 200 includes a platen 202 , which is a disk-shaped substrate carrier that supports substrates 204 for vapor phase epitaxy.
  • the VPE system 200 includes a gas injector 206 comprising multiple regions that are separated by physical barriers and/or chemical barriers.
  • the VPE system 200 can include a first region 208 that is coupled to a first precursor gas source 210 and a second region 212 that is coupled to a second precursor gas source 214 .
  • Any type of precursor gas can be used in the VPE system according to the present teachings.
  • the gas injector 206 can include additional regions that are separated by physical barriers and/or chemical barriers that may or may not be coupled to additional precursor and/or inert gas sources 211 .
  • the first region 208 in the gas injector 206 is positioned in quadrants of a disk and a second region 212 extends radially through the quadrants.
  • the first and second regions 208 , 212 in the gas injector 206 include a plurality of first and second regions that alternate across at least a portion of the gas injector 206 .
  • the gas injector 206 comprises liquid cooling channels to control a temperature of the gas injector 206 .
  • a fluid coolant supply 216 is coupled to liquid cooling channels in the flow injector 206 to circulate the cooling fluid in order to control the temperature of the gas injector 206 .
  • the gas injector 206 is designed to flow the first and second precursor gases over the platen 202 that supports the substrates 204 with either a laminar flow or a non-laminar flow. Also, in various embodiments, the gas injector 206 flows the first and second precursor gases in various directions relative to the platen 202 that supports the substrates 204 . For example, in some VPE systems according to the present invention, the gas injector 206 flows at least one of the first and second precursor gases in a direction that is perpendicular to the surface of platen 202 that supports the substrates 204 .
  • the gas injector 206 flows at least one of the first and second precursor gases in a direction that is parallel to the platen 202 that supports the substrates 204 .
  • the gas injector 206 flows one of the first and second precursor gases in a direction that is substantially parallel to the platen 202 that supports the substrates 204 and the other of the first and second precursor gases through the gas injector 206 in a direction that is substantially perpendicular to the platen 202 that supports the substrates 204 .
  • Electrodes 218 , 219 are positioned in the first region 212 so that first precursor gas flows in contact with or in close proximity to the electrodes 218 , 219 .
  • the electrodes 218 , 219 are positioned so that they are substantially isolated from the flow of the second precursor gas.
  • the electrodes 218 , 219 can be oriented in numerous ways.
  • the electrodes 218 , 219 can be oriented in a plane of the gas injector 206 (e.g. electrode 218 ).
  • the electrodes 218 , 219 can also be oriented perpendicular to the plane of the gas injector 206 (e.g. electrode 219 ).
  • the electrodes 218 , 219 can be positioned anywhere between the gas injector 206 and the platen 202 that supports the substrates 204 including in close proximity to the gas injector 206 and in close proximity to the platen 202 that supports the substrates 204 .
  • the electrodes 218 , 219 can be formed of any type of electrode material. However, the electrodes 218 , 219 are typically formed of a material that is resistant to corrosion so that they do not introduce any contamination into the VPE system 200 . Also, in various embodiments, any type of electrode configuration can be used including any number of electrodes, which can include only one electrode. In addition, in various embodiments, the electrodes 218 , 219 can be formed in any shape.
  • the VPE system 200 shows two different types of electrodes, a linear (straight) electrode 218 and a non-linear electrode 219 , such as a coiled electrode or other structure that increases or maximizes the surface area of the electrode that is exposed to the first precursor gas. In many systems, the same type of electrode is used, but in some systems two or more different types of electrodes are used.
  • the electrodes 218 , 219 are electrically active. In the embodiment shown in FIG. 2 , the electrodes 218 , 219 are at a floating potential when not powered. An output of a power supply 220 is electrically connected to the electrodes 218 , 219 . The power supply 220 generates a current that heats the electrodes 218 , 219 so as to thermally activate at least some of the first precursor gas molecules flowing in contact with or proximate to the electrodes 218 , 219 .
  • the gas injector 206 includes one or more baffles 222 or other types of physical structure that physically separates the first region 208 from the second region 212 so as to isolate the electrodes 218 , 219 from the flow of the second precursor gas.
  • the one or more baffles 222 are formed of non-thermally conductive materials so that the thermal profile in the process chamber 201 does not significantly change from thermal radiation emitted by the baffles 222 .
  • the one or more baffles 222 are shaped to preserve laminar flow of at least one of the first and second precursor gases across the platen 202 that supports the substrates 204 .
  • the electrodes 218 , 219 are formed of a catalytic material.
  • a heater can be positioned in thermal communication with the catalytic material so as to increase a reaction rate of the catalytic material.
  • the electrodes 218 , 219 are formed of a catalytic material including at least one of rhenium, tungsten, niobium, tantalum, and molybdenum.
  • the electrodes 218 , 219 can be formed of refractory and/or transition metals.
  • a method of operating a vapor phase epitaxy system includes injecting a first precursor gas for vapor phase epitaxy in the first region 208 proximate to a platen 202 supporting substrates 204 and injecting a second precursor gas for vapor phase epitaxy in a second region 212 proximate to the platen 202 supporting substrates.
  • the first and second precursor gases are injected in a plurality of respective alternating first and second regions as described in connection with FIG. 4A .
  • the first precursor gas can be a hydride precursor gas, such as NH 3 and the second precursor gas can be an organometalic precursor gas, such as trimethyl gallium, that is used to grow GaN by VPE.
  • the first precursor gas can be a hydride precursor gas, such as NH 3 and the second precursor gas can be a metal halide precursor gas, such as gallium chloride, that is used to grow GaN by VPE.
  • three precursor gases are used.
  • the first precursor gas can be a hydride precursor gas, such as NH 3
  • the second precursor gas can be an organometalic precursor gas, such as trimethyl gallium.
  • the third precursor gas can be a halide precursor gas, such as HCl. With these three precursor gases, the halide precursor gas and the organometallic precursor gas react to form a metal halide.
  • the gas injector 206 can include a third region for injecting the third precursor gas. Alternatively, the third precursor gas can be injected in the either the first or the second regions 208 , 212 .
  • the first and second precursor gases can be injected at any angle including perpendicular and parallel to the platen 202 supporting substrates 204 .
  • the angle of injection for the second precursor gas can be the same as or different from the angle of injection of the first precursor gas.
  • First precursor gas molecules flow in contact with or in close proximity to the electrodes 218 , 219 .
  • the electrodes 218 , 219 are at least partially isolated from the flow of the injected second precursor gas.
  • the electrodes 218 , 219 are then electrically activated.
  • the electrodes 218 , 219 are isolated from a flow of the injected second precursor gas with physical baffles 222 .
  • the baffles 222 can be performed so as to preserves laminar flow over the platen 202 supporting substrates 204 as described in connection with FIG. 6 .
  • inert gases are injected in regions that isolate the electrodes 218 , 219 from a flow of the second precursor gas.
  • inert gas refers to a gas which does not substantially participate in the growth reactions. Inert gases are often mixed with the precursor gases. Such inert gases are referred to in the art as “carrier gases.”
  • carrier gases For example, when growing III-V semiconductor materials, gases, such as N2, H2, He or mixtures thereof, are commonly used as carrier gases for precursor gases.
  • the power supply 220 generates a current that flows through the electrodes 218 , 219 so that the electrodes 218 , 219 generates heat that thermally activates the first precursor gas molecules without activating a substantial amount of second precursor gas molecules.
  • the heated electrodes 218 , 219 transfer energy to the first precursor gas molecules by various mechanisms including thermionic emission of electrons and interaction of the electrons with the reactant species.
  • the electrons do not have sufficient energy to ionize the reactant species.
  • One example where the electrons do not have sufficient energy to ionize the reactant species is ionizing NH 3 . In methods that ionize NH 3 , the electrons interact with the reactant species so as to promote the species to a higher energy state.
  • the electrodes 218 , 219 are catalytic electrodes, which are formed of a catalytic material capable of catalyzing the first precursor gas if conditions are favorable.
  • the catalytic electrode can be heated with a separate heater to enhance the catalytic reaction.
  • such a catalytic electrode is useful to decompose NH 3 close to the gas injector 206 surface because it is far from the platen 202 supporting the substrate 204 and, therefore, may not have enough thermal energy for decomposition.
  • Using a catalytic electrode lowers the activation energy for decomposition and, therefore, increases the probability of NH 3 decomposition even in regions of the process chamber 201 that have relatively low temperatures (i.e.
  • the catalytic electrode allows the reaction to proceed or, if the reaction was inclined to occur, to proceed more rapidly by lowering the activation energy of the reaction or having the reaction proceed through a different reaction pathway.
  • the catalytic electrode is positioned proximate to the boundary layer region 126 ( FIG. 1 ) so that the first precursor gas mixes with the second precursor gas shortly after the first precursor gas interacts with the catalytic electrode.
  • VPE systems include a catalytic electrode that is not energized. This is a catalytic electrode that is not powered by a power supply and that uses only the catalytic material and ambient heat to enhance the catalytic reaction.
  • a catalytic electrode can be positioned anywhere in the process chamber 201 . In some of these VPE systems, the catalytic electrode is positioned proximate to the platen 202 . Catalytic electrodes positioned proximate to the platen 202 can reach effective catalytic activity through secondary heating from the platen 202 alone.
  • Slab-like streams of thermally activated first precursor gas molecules flow generally downstream toward the platen 202 and substrates 204 in a flow region 224 of the reaction chamber 201 between the gas injector 206 and the platen 202 .
  • the downward flow does not result in substantial mixing between separate streams of downwardly flowing gas. It is sometimes desirable to design and operate the system 200 so that there is laminar flow in the flow region 224 .
  • the platen 202 is rotated rapidly about the axis 104 with the rotary drive 106 so that the surface of the platen 202 and the surfaces of the substrates 204 are moving rapidly.
  • the rapid motion of the platen 202 and substrates 204 entrains the gases into rotational motion about axis 104 .
  • the process gases flow radially away from axis 104 , thereby causing the process gases in the various streams to mix with one another within a boundary layer that is schematically indicated in boundary layer region 126 .
  • the activated first precursor gas molecules and the second precursor gas molecules in the mixture within the boundary layer flow over the surface of the substrates 204 , thereby reacting to form a VPE film.
  • precursor gasses are introduced into the process chamber 201 at a relatively low temperature, and hence have low available energy, typically well below the energy required to induce rapid reaction of the reactants on the surface of the substrate 204 .
  • most of the heating, and hence most of the increase in available energy of the reactants occurs within the boundary layer region 126 .
  • substantially all of the heating depends upon the temperature of the substrate 204 and platen 202 .
  • substantial energy is supplied to at least one precursor gas other than energy applied by heat transfer from the substrate, platen, and chamber walls.
  • the location where the energy is applied can be controlled. For example, by applying the energy to the first precursor gas near the transition between the flow region 124 ( FIG. 1 ) and the boundary layer region 126 , the time between the moment when a given portion of a first precursor gas reaches a high available energy and the time when that portion encounters the substrate surface can be minimized.
  • Such control can help to minimize undesired side reactions.
  • ammonia having high available energy may spontaneously decompose into species such as NH 2 and NH, and then these species in turn may decompose to monatomic nitrogen, which very rapidly forms N 2 .
  • Nitrogen is essentially unavailable for reaction with a metal organic.
  • the desired reactions which deposit the semiconductor at the surface such as reaction of the excited NH 3 with the metal organic or reaction of NH 2 or NH species with the metal organic at the substrate surface can be enhanced, whereas the undesirable side reaction can be suppressed.
  • one feature of the present teachings is that by using the electrodes according to the present invention, the operator has the ability to control the available energy of at least one precursor gas independently of the temperature of the substrates 204 .
  • the available energy of at least one precursor gas in the boundary layer region 126 can be increased without increasing the temperature of the substrates 204 and the platen 202 .
  • the substrates 204 and the platen 202 can be maintained at a lower temperature while still maintaining an acceptable level of available energy.
  • FIG. 3 illustrates a top-view of one embodiment of a disk-shaped gas injector 300 according to the present teaching which includes a first region 302 that is positioned in quadrants of the gas injector 300 and a second region 304 extending radially through the quadrants.
  • the top-view shown in FIG. 3 is presented looking upstream toward the precursor gas inlets in the gas injector 300 .
  • the disk-shaped gas injector 300 includes mechanical or chemical barriers 305 that isolate the first and second regions 302 , 304 .
  • the mechanical or chemical barriers 305 can be physical structures, such as baffles and/or gas curtains that inject inert gases to isolate the first and second regions 302 , 304 .
  • FIG. 3 shows electrodes 306 , 308 in two quadrants for clarity.
  • electrodes 306 , 308 are positioned in each of the quadrants of the first region 302 .
  • each of the electrodes 306 , 308 is suspended with an insulating support structure so that the electrodes 306 , 308 are electrically floating and easily connected to the power supply 220 ( FIG. 2 ).
  • the electrodes can be linear (straight) electrodes or non-linear electrodes, such as coiled electrodes or other structures that increases or maximizes the surface area of the electrodes 306 , 308 that are exposed to the first precursor gas.
  • the same type of electrode is used throughout the first region 302 , but in some systems two or more different types of electrodes are used in different positions in the first region 302 .
  • the type of electrode near the second region 304 can be different from the type of electrode in the middle of the first region 302 .
  • FIG. 3 shows a first type of electrode 306 , which can be either linear or non-linear, positioned in the plane of the first precursor gas flow.
  • FIG. 3 shows a second type of electrode 308 positioned in the plane of the gas injector 300 .
  • FIG. 3 shows the second type of electrode 308 in a linear pattern.
  • the second type of electrode can also be formed in a non-linear pattern, such as a coil.
  • the electrodes 306 , 308 are positioned far enough from the second region 304 so that the chemical potential of the second precursor is not changed based on its proximity to the electrodes 306 , 308 . In other words, the electrodes 306 , 308 have essentially no interaction with the second precursor gas.
  • One feature of the VPE system of the present teachings is that the first and second precursor gases can be injected at the same distance from the substrate 204 ( FIG. 2 ). In other words, the second precursor gas does not have to be injected below the first precursor gas in the process chamber 201 to avoid activation. Injecting both the first and the second precursor gases at the same level in the process chamber 201 is important in many VPE processes because such injection can achieve laminar flow over large areas in vertical flow VPE process chambers. Laminar flow is desirable for many VPE processes because it improves uniformity.
  • Methods of operating VPE systems comprising the gas injector 300 of FIG. 3 include injecting the first precursor gas in the quadrants of the first region 302 so that first precursor gas molecules contact the electrodes 306 , 308 .
  • the electrodes 306 , 308 are powered with power supply 220 ( FIG. 2 ) so that they thermally activate the first precursor gas molecules.
  • the first precursor gas can be a hydride precursor gas precursor gas admixture with a carrier gas.
  • the second precursor gas is injected in the second region 304 adjacent to the electrodes 306 , 308 .
  • the second precursor gas can be an organometallic admixture with a carrier gas such as nitrogen.
  • Process conditions are chosen so that the second precursor gas does not flow close enough to the electrodes 306 , 308 to be thermally activated by heat generated by the electrodes.
  • the activated first precursor gas molecules and the second precursor gas molecules then flow over the surface of the substrates 204 ( FIG. 2 ), thereby reacting to form a VPE film.
  • FIG. 4A illustrates a cross-section of one embodiment of a disk-shaped gas injector 400 according to the present teaching that includes a plurality of first and second regions 402 , 404 which alternates across the gas injector 400 .
  • the top-view shown in FIG. 4A is presented looking upstream toward the precursor gas inlets in the gas injector 400 .
  • the plurality of first regions 402 includes gas inlets for injecting hydride or halide precursor gases with a carrier gas.
  • the plurality of second regions 404 includes gas inlets for injecting organometallic gases with a carrier gas.
  • the area of the first regions 402 is larger than the area of the second regions 404 .
  • the flow rates of the first and second precursor gases and of the carrier gases during operation can be adjusted for the particular dimensions of the first and the second regions 402 , 404 so that the desired volumes and concentrations of precursor gases flow across the substrates 204 ( FIG. 2 ) being processed.
  • the gas injector 400 includes a plurality of electrodes 406 , 408 positioned in the plurality of first regions 402 .
  • the plurality of electrodes 406 , 408 are positioned in the first region 402 or as far from the flow of the second precursor gas as possible so as to minimize the activation of second precursor gas molecules with the electrodes 406 , 408 .
  • FIG. 4A illustrates electrodes 406 , 408 in two different orientations. Electrodes are only shown in a few sections of the plurality of first regions 402 for clarity. In many VPE systems according to the present teachings, electrodes 406 , 408 are positioned in each of the plurality of the first regions 402 .
  • each of the electrodes 406 , 408 is suspended with an insulating support structure so that the electrodes 406 , 408 are electrically floating and easily connected to the power supply 220 ( FIG. 2 ).
  • the electrodes 406 , 408 can be linear (straight) electrodes or non-linear electrodes, such as coiled electrodes or other structures that increases or maximizes the surface area of the electrodes 406 , 408 that are exposed to the first precursor gas.
  • FIG. 4A shows a first type of electrode 406 , which can be either linear or non-linear, positioned in the plane of the first precursor gas flow.
  • FIG. 4A shows a second type of electrode 408 positioned in the plane of the gas injector 400 .
  • FIG. 4A shows the second type of electrode 408 as a non-linear electrode that can also be coiled.
  • the second type of electrode 408 can also be a linear electrode.
  • FIG. 4B illustrates an expanded view of the disk-shaped gas injector 400 illustrating mechanical or chemical barriers 405 that isolate the electrodes 406 ( FIG. 4A ), 408 from the second precursor gas.
  • the mechanical or chemical barriers 405 isolate the electrodes 406 , 408 in first region 402 from the precursor gas flowing in the second region 404 .
  • the barriers 405 can be a physical structure, such as baffle.
  • the barriers 405 can be a gas curtains that inject inert gases between the first and second regions 402 , 404 as described herein.
  • Methods of operating VPE systems comprising the gas injector 400 of FIGS. 4A and 4B include injecting the first precursor gas in the plurality of first regions 402 so that first precursor gas molecules contact the electrodes 406 , 408 .
  • the electrodes 406 , 408 are powered with the power supply 220 ( FIG. 2 ) so that they thermally activate the first precursor gas molecules.
  • the first precursor gas can be a hydride precursor gas admixture with a carrier gas that is thermally activated when it flows in contact with the electrodes 406 , 408 .
  • the second precursor gas is injected in the plurality of second regions 404 .
  • the second precursor gas can be an organometallic admixture with a carrier gas.
  • Process conditions are chosen so that the second precursor gas does not flow close enough to the electrodes 406 , 408 to be thermally activated by heat generated by the electrodes 406 , 408 .
  • the activated first precursor gas molecules and the second precursor gas molecules then flow over the surface of the substrates 204 ( FIG. 2 ), thereby reacting to form a VPE film.
  • FIG. 5 illustrates a perspective top-view of a VPE system 500 according to the present teachings that includes a horizontal flow gas injector 502 .
  • the VPE system 500 is similar to the VPE system 200 that was described in connection with FIG. 2 .
  • the VPE system 500 includes circular gas injectors 504 , 506 , and 508 that inject precursor gases and inert gases in the plane of the platen 510 (i.e. horizontal flow into the process chamber).
  • the first circular gas injector 504 is coupled to a first precursor gas source 512 .
  • the second circular gas injector 506 is coupled to an inert gas source 514 .
  • the third circular gas injector 508 is coupled to a second precursor gas source 516 .
  • the first and third circular gas injectors 504 , 508 are also coupled to a carrier gas source.
  • the first circular gas injector 504 injects the first precursor gas in a first horizontal region 518 .
  • the third circular gas injector 508 injects the second precursor gas in a second horizontal region 520 .
  • a circular electrode 522 is positioned in the first horizontal region 518 so that first precursor gas molecules flow in contact with or proximate to the circular electrode 522 .
  • a physical or chemical barrier can be positioned between the first and the second horizontal regions 518 , 520 in order to isolate the circular electrode 522 from the flow of the second precursor gas molecules.
  • a baffle is positioned above the circular electrode 522 to substantially prevent the first precursor gas molecules from being thermally activated by the electrode 522 as they flow to the platen 510 .
  • a gas curtain is used to separate the first and the second horizontal regions 518 and 520 .
  • the second circular gas injector 506 injects inert gas between the first and the second horizontal regions 518 , 520 in a pattern that substantially prevents the second precursor gas molecules from being activated by the circular electrode 522 .
  • Methods of operating the VPE system 500 of FIG. 5 include injecting the first precursor gas with the first circular gas injectors 504 and injecting the second precursor gas with the third circular gas injectors 508 .
  • An inert gas is injected between the first and the second horizontal regions 518 , 520 with the second circular gas injectors 506 to form a chemical barrier that prevents the second precursor gas molecules from being activated by the circular electrode 522 .
  • the circular electrode 522 is powered by a power supply 220 ( FIG. 2 )
  • the circular electrode 522 thermally activates first precursor gas molecules injected by the first circular gas injector 504 that flow in contact with or in close proximity to the circular electrode 522 .
  • the activated first precursor gas molecules and the second precursor gas molecules then flow over the surface of the substrates 524 , thereby reacting to form a VPE film.
  • FIG. 6 illustrates a foil-shaped electrode 600 positioned close to the surface of the platen 602 for thermally activating a precursor gas in a VPE system according to the present teaching.
  • the electrode 600 is positioned close to the surface of the platen 602 and substrate 604 being processed.
  • the electrode 600 shown in FIG. 6 is shaped as an airfoil in order to provide a laminar or near laminar flow of precursor gases across the surface of the substrate 604 .
  • the electrode 600 can be shaped to provide a relatively large surface area for the catalytic reaction.

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US20100087050A1 (en) 2010-04-08
WO2010040011A3 (fr) 2010-07-01
TWI411700B (zh) 2013-10-11
EP2347028A1 (fr) 2011-07-27
SG194408A1 (en) 2013-11-29
CN102239277A (zh) 2011-11-09
CN102239277B (zh) 2013-10-23
JP5587325B2 (ja) 2014-09-10
US8815709B2 (en) 2014-08-26
JP2012504866A (ja) 2012-02-23
EP2332167A4 (fr) 2012-06-20
TW201022488A (en) 2010-06-16
WO2010040011A2 (fr) 2010-04-08
JP2012504873A (ja) 2012-02-23
WO2010039252A1 (fr) 2010-04-08
CN102171795A (zh) 2011-08-31
KR20110079831A (ko) 2011-07-08
US20110174213A1 (en) 2011-07-21
TW201026887A (en) 2010-07-16
EP2332167A2 (fr) 2011-06-15
TWI429791B (zh) 2014-03-11
US20140318453A1 (en) 2014-10-30

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