CN103221586B - The method forming block III-nitride material on metal nitride growth templates layer and the structure formed by described method - Google Patents

The method forming block III-nitride material on metal nitride growth templates layer and the structure formed by described method Download PDF

Info

Publication number
CN103221586B
CN103221586B CN201180056320.3A CN201180056320A CN103221586B CN 103221586 B CN103221586 B CN 103221586B CN 201180056320 A CN201180056320 A CN 201180056320A CN 103221586 B CN103221586 B CN 103221586B
Authority
CN
China
Prior art keywords
template layer
gas
nitride
metal
metal nitride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201180056320.3A
Other languages
Chinese (zh)
Other versions
CN103221586A (en
Inventor
尚塔尔·艾尔纳
罗纳德·托马斯·伯特伦
埃德·林多
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Soitec SA
Original Assignee
Soitec SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Soitec SA filed Critical Soitec SA
Publication of CN103221586A publication Critical patent/CN103221586A/en
Application granted granted Critical
Publication of CN103221586B publication Critical patent/CN103221586B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02458—Nitrides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C30B25/22—Sandwich processes
    • 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
    • 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
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The present invention relates to utilize metal terchoride precursor to deposit block III-nitride semiconductor material on the metal nitride template layer of growing substrate in HPVE method.The deposition of block III-nitride semiconductor material can be carried out in the case of forming template layer not utilizing mocvd method dystopy.In some embodiments, before utilizing HVPE method to deposit block III-nitride semiconductor material on template layer, non-mocvd method dystopy is utilized to form nucleation template layer.In other embodiment, before utilizing HVPE method to deposit block III-nitride semiconductor material on template layer, mocvd method is utilized to be formed in situ nucleation template layer.In other embodiments, before utilizing HVPE method to deposit block III-nitride semiconductor material on template layer, HVPE method is utilized to be formed in situ nucleation template layer.

Description

The method forming block III-nitride material on metal nitride growth templates layer And the structure formed by described method
Technical field
Embodiments of the present invention are generally directed to the method for substrate deposit III-nitride material, and by institute State the structure that method is formed.More specifically, embodiments of the present invention relate to comprising growth templates layer that (it contains Have metal nitride materials) the method for substrate deposit III-nitride material, and the knot formed by described method Structure body.
Background technology
Chemical gaseous phase deposition (CVD) is for the chemical method at substrate deposit solid material, and is commonly used to manufacture Semiconductor device.In chemical vapour deposition technique, one or more reagent gas of substrate contact, described reagent gas is sent out Raw reaction and/or decomposition are so that solid material deposits on the surface of matrix.
The CVD of a kind of particular type is referred to as vapour phase epitaxy method (VPE) in the art.In VPE method, base Body contacts one or more reagent vapor in the reaction chamber, and described reagent vapor reacts and/or decomposes, so that Obtain solid material epitaxial deposition on the surface of matrix.VPE method is generally used for deposition of Group III-V race semi-conducting material. When a kind of reagent vapor in VPE method comprises halide vapor, the method is referred to alternatively as halide gas phase extension (HVPE) method.
It is known in the art that and utilize wherein metallorganic (MO) precursor material to be decomposed to form III in the reaction chamber The VPE method of nitride semi-conductor material is formed such as III-nitride semiconductor material such as gallium nitride (GaN).Described Method is commonly referred to gas phase epitaxy of metal organic compound (MOVPE) method, and is also referred to as metal organic-matter chemical gas Deposition (MOCVD) method mutually.Described MOVPE method is usually carried out: use several continuous print pre-deposition process, Then the block III-nitride semiconductor material needed for deposition.These continuous print pre-deposition processes comprise the steps that growth The high temperature hydrogen baking of matrix (such as sapphire substrates), the nitridation of growing substrate, on growing substrate with lower temperature shape Become the annealing at higher temperature of the nucleating layer of III-nitride material, nucleating layer, the coalescence of nucleating layer, and finally exist The block III-nitride material layer of growth on nucleating layer.
HVPE method is additionally operable to be formed such as III-nitride semiconductor material such as gallium nitride (GaN).In the process, The monochlor(in)ate gallium (GaCl) carried out in reative cell under about 500 DEG C～about 1,000 DEG C of high temperature and ammonia (NH3Gas between) Phase reaction can cause GaN epitaxial growth on matrix.NH3Can be by the NH of standard3Source of the gas is supplied.At some In method, make hydrogen chloride (HCl) gas (can be supplied by the HCl gas source of standard) by the liquid gallium (Ga) being heated Top is to be formed in situ GaCl in reative cell, thus provides GaCl steam.Liquid gallium can be heated to about 750 DEG C～ The temperature of about 850 DEG C.Can be by GaCl and NH3Guide by hot basal body (such as wafers of semiconductor material) surface (such as This surface).January 30 calendar year 2001 authorizes the U.S. Patent No. 6,179,913 of Solomon etc. and discloses use Gas injection system in described system and method.
Pre-with the above-mentioned several continuous print for forming the MOVPE method of block III-nitride semiconductor material relevant Deposition process is likely difficult to carry out in HVPE deposition reactor.
Summary of the invention
Thering is provided this section summary of the invention is the concept in order to introduce multiple reduced form, and these concepts will be below by this The detailed description of some bright illustrative embodiments is further described.This section summary of the invention is not intended to determine The key feature of theme required for protection or essential feature, be not in order to for limiting theme required for protection Scope.
As it has been described above, be used for forming the nucleating layer of III-nitride material on growing substrate (then on this nucleating layer The block III-nitride semiconductor material of deposition) several continuous print pre-deposition processes be likely difficult in HVPE deposition anti- Answer in device and carry out.As a result, the most sharp for depositing the known HVPE method of block III-nitride semiconductor material With comprising by mocvd method dystopy deposition (that is, the independent deposition process carried out in single chamber) on matrix The growing substrate of nucleating layer of metal nitride materials.Then the independent HVPE process carried out in single chamber In on growing substrate deposition needed for block III-nitride material.
In some embodiments, present invention resides in the block III-nitride semiconductor material of deposition on growing substrate Method.Matrix forms metal nitride nucleation template layer thus forms growing substrate, and utilize halide gas phase Extension (HVPE) method deposits block III-nitride semiconductor material on this growing substrate.Growing substrate deposits The process of block III-nitride semiconductor material can include making in metal terchoride and metal tetrachloride at least One is decomposed thus is formed metal chloride Group III precursor steam, and makes metal chloride Group III precursor steam and V Race's precursor vapor reaction to form block III-nitride semiconductor material on growing substrate.
The most in some embodiments, present invention resides in do not utilize mocvd method dystopy formed nucleation template layer In the case of, utilize the method that HPVE method deposits block III-nitride material on growing substrate.
In some embodiments, present invention resides in the block III-nitride semiconductor material of deposition on growing substrate Method.Nonmetal organic chemical vapor deposition (MOCVD) method is utilized to form gold on matrix in the first chamber Belong to nitride nucleation template layer thus form growing substrate, and in the second chamber, utilize halide gas phase extension (HVPE) Method deposits block III-nitride semiconductor material on this growing substrate.The block III nitrogen of deposition on growing substrate The process of compound semi-conducting material can include making at least one in metal terchoride and metal tetrachloride and NH3 Flow to the second chamber.
On growing substrate in other embodiments of the method for the block III-nitride semiconductor material of deposition, in chamber Room utilize metal-organic chemical vapor deposition equipment (MOCVD) method form metal nitride nucleation template layer on matrix Thus form growing substrate, and utilize halide gas phase extension (HVPE) method in the same chamber on this growing substrate The block III-nitride semiconductor material of deposition.Halide gas phase extension (HVPE) method is utilized to deposit on growing substrate The process of block III-nitride semiconductor material can include making in metal terchoride and metal tetrachloride at least One and NH3Flow to same chamber.
On growing substrate in other embodiments of the method for the block III-nitride semiconductor material of deposition, in chamber Room utilizes halide gas phase extension (HVPE) method form metal nitride nucleation template layer on matrix thus form life Long matrix, and utilize halide gas phase extension (HVPE) method to deposit block III on this growing substrate in the same chamber Hi-nitride semiconductor material.Halide gas phase extension (HVPE) method is utilized to deposit block III nitrogen on growing substrate The process of compound semi-conducting material can include making at least one in metal terchoride and metal tetrachloride and NH3 Flow to same chamber.
Other embodiments of the present invention include structure, and this structure comprises what use method disclosed herein was formed Block III-nitride semiconductor material.
Accompanying drawing explanation
By with reference to hereafter detailed description to the exemplary embodiment of the invention shown in accompanying drawing, can be more fully Understand the present invention, in accompanying drawing:
Fig. 1 is the simplification sectional view of the matrix of the embodiment that can be used for the inventive method；
Fig. 2 is the simplification sectional view of growing substrate, this growing substrate can be used for the inventive method embodiment and can Formed by the substrate deposit nucleation template layer at Fig. 1；
Fig. 3 is the simplification sectional view of the structure comprising block III-nitride semiconductor material, this bulk III nitrogen Compound semi-conducting material deposits on the nucleation template layer of the growing substrate of Fig. 2 according to the embodiment of the inventive method And obtain；
Fig. 4 A is showing the exemplary embodiment party of the HVPE depositing system of the embodiment that can be used for the inventive method The schematic cross-section of formula, this HVPE depositing system includes reative cell and at least one gas syringe；
Fig. 4 B is the schematic cross-section that the reative cell shown in Fig. 4 A intercepts along transversal 4B-4B shown in it；
Fig. 5 show schematically show the embodiment of the transconversion into heat gas syringe of the depositing system that can be used for Fig. 4 A；
Fig. 6 show schematically show the another exemplary embodiment party of the gas syringe of the depositing system that can be used for Fig. 4 A Formula；
Fig. 7 is the amplification partial sectional view of a part for the gas syringe of Fig. 6；With
Fig. 8 is the schematic diagram representing the deposition process that make use of the HVPE depositing system shown in Fig. 4 A and 4B, institute State deposition process to can be used on growing substrate, depositing block III nitride semiconductor material according to embodiment of the present invention Material.
Detailed description of the invention
Diagram given herein is not intended to become any concrete assembly, device or the actual view of system, and is only For describing the idealization manifestation mode of embodiment of the present invention.
A large amount of list of references is cited herein, and no matter the most how it characterizes, drawn list of references all it is not considered that It is the prior art relevant to the invention of this paper claim theme.
As used herein, term " III-V race semi-conducting material " represents and includes at least main by periodic table of elements IIIA One or more elements of one or more elements (B, Al, Ga, In and Ti) of race and periodic table of elements VA race (N, P, As, Sb and Bi) any semi-conducting material of constituting.Such as, III-V race semi-conducting material includes but not limited to GaN, GaP, GaAs, InN, InP, InAs, AlN, AlP, AlAs, InGaN, InGaP, InGaNP etc..
As used herein, term " III-nitride semiconductor material " represents and includes at least main by the periodic table of elements One or more elements (B, Al, Ga, In and Ti) of Group IIIA and nitrogen are constituted any III-V race quasiconductor material Material.Such as, III-nitride semiconductor material include GaN, InN, AlN, InGaN, GaAlN, GaAlN, InAlN etc..
As used herein, term " metal nitride " represents metal and nitrogen compound.Metal nitride materials include but It is not limited to aluminium nitride (AlN), gallium nitride (GaN), aluminium gallium nitride alloy (AlxGa1-xN), titanium nitride (TiN), hafnium nitride (Hf), Chromium nitride (CrN), tungsten nitride (WN) and tantalum nitride (TaN).
As used herein, term " chemical gaseous phase deposition " and " CVD " are synonyms, and represent and comprise following any Method: described method in the reaction chamber by solid materials deposition at matrix, wherein substrate contact one or more Reagent gas, described reagent gas reacts and/or decomposes so that solid material deposits on the surface of matrix.
As used herein, term " vapour phase epitaxy " and " VPE " are synonyms, and represent and comprise following any CVD Method: wherein one or more reagent vapor of substrate contact, described reagent vapor react and/or decompose so that Solid material is epitaxial deposition on the surface of matrix.
As used herein, term " halide gas phase extension " and " HVPE " are synonyms, and represent and comprise following Any VPE method: at least one reagent vapor used by described VPE method comprises halide vapor.
As used herein, term " metallorganic " represents and comprises any following compound: described compound contain to Few a kind of metallic element and the organic chemistry material (chemical species) comprising at least one carbons part.Metal is organic Thing is commonly referred to " organo-metallic compound " in the art, and these terms are synonym in the present invention.Metal Organic substance includes but not limited to trimethyl gallium (TMG), triethyl-gallium (TEG), trimethyl aluminium (TMA), triethyl aluminum (TEA), four (diethylamino) titanium (TDEAT) and four (dimethylamino) titanium (TDMAT).
As used herein, term " gas phase epitaxy of metal organic compound " and " MOVPE " are synonyms, and represent and wrap Containing following any VPE method: at least one reagent vapor used in described VPE method comprises metallorganic steam.
As used herein, term " nonmetal organic chemical vapor deposition method " and " non-mocvd method " are synonyms, And representing and comprising any is not the deposition process of mocvd method.
As used herein, term " nonmetal organics gaseous phase extended method " and " non-MOVPE method " they are synonyms, and Representing and comprising any is not the deposition process of MOVPE.
As used herein, term " gas " includes gas (neither have independent shapes and the most do not have the fluid of volume) and steam (liquid comprising diffusion or the gas of the solid matter wherein suspended), term " gas " and " steam " are herein as same Justice word uses.
Fig. 1～3 illustrates the block III nitride semiconductor of deposition on growing substrate according to the embodiment of the present invention The process of material.See Fig. 1, it is provided that matrix 10.Matrix 10 can be the disking body of general plane, and can With generally circular, rectangle etc..Matrix 10 can comprise " little chip (die) " or " wafer " alleged in this area. Matrix 10 can be at least substantially made up of homogeneous material 12.Material 12 such as can comprise such as oxide (e.g., dioxy SiClx (SiO2) or aluminium oxide (Al2O3, such as sapphire, it is α-Al2O3) etc. pottery or nitride (e.g., silicon nitride (Si3N4) Or boron nitride (BN)).As other example, material 12 can comprise semi-conducting material, such as silicon (Si), germanium (Ge), III-V race semi-conducting material etc..In some embodiments, the material 12 of matrix 10 can at least substantially by The monocrystalline of material 12 is constituted.It addition, in this embodiment, monocrystalline can have selected crystalline orientation, with The first type surface 14 making material 12 expose comprises the selected crystal face of the monocrystalline of material 12.As limiting examples, can To be chosen as including sapphire substrates by matrix 10.This sapphire substrates is commercially available.
See Fig. 2, (such as, deposition) metal nitride nucleation template layer can be formed on the first type surface 14 exposed 18, thus form growing substrate 20.According to the embodiment of the inventive method, metal nitride nucleation template layer 18 Can be formed on matrix by the multitude of different ways being further detailed below.As limiting examples, Ke Yi On the first type surface 14 exposed deposit metal nitride nucleation template layer 18, and make template layer 18 have about 2 nanometers (2nm)～ The average thickness T of about 5 microns (5 μm)1。
Utilize metal nitride nucleation template layer 18 so that block III-V race semi-conducting material energy on matrix 10 Enough depositions are to desired average total thickness, and the defect in the block III-V race semi-conducting material that simultaneously will be deposited is close Degree is maintained at expectation concentration.Due to the block III-V race half that the material 12 of matrix 10 is to be deposited with on matrix 10 Difference (this difference is commonly referred to " lattice misfit " in the art) between the lattice structure of conductor material, if by block Shape III-V race semi-conducting material is deposited directly on the first type surface 14 that matrix 10 exposes, then block III-V race The crystal structure of semi-conducting material may be containing of a relatively high, unacceptable such as defect densities such as dislocations.Therefore, exist The composition of the metal nitride nucleation template layer 18 provided between matrix 10 and block III-V race semi-conducting material and / or micro structure can be chosen and make metal nitride nucleation template layer 18 and matrix 10 and block III to be deposited on it Between-V race semi-conducting material, relative to the lattice misfit between matrix 10 and block III-V race semi-conducting material For, it is respectively provided with relatively low lattice misfit.In other words, nucleation template layer can be used for alleviating matrix 10 and its on to sink Lattice misfit between long-pending block III-V race semi-conducting material, thus described nucleation template layer 18 is in this area Also referred to as " buffering " layer.Additionally, nucleation template layer can be used as Seed Layer and makes block III-V race semi-conducting material exist Nucleating growth on it, thus described nucleation template layer 18 is also referred to as " seed " layer in this area.
See Fig. 3, formed after growing substrate 20, utilize HVPE method can make block III-V race quasiconductor Material 22 nucleation depositing on the first type surface 19 that metal nitride nucleation template layer 18 exposes.Although Fig. 3's Simplify visible metal nitride nucleation template layer 18 in figure and discrete between block III-V race semi-conducting material 22 Border (discrete boundary), it should be noted that metal nitride nucleation template layer 18 and block III-V race half Conductor material 22 can have the composition being at least substantially identical in some embodiments, thus is likely difficult to maybe can not make Any divergent boundary between metal nitride nucleation template layer 18 and block III-V race semi-conducting material 22 is visual Change, or otherwise determine metal nitride nucleation template layer 18 and block III-V race semi-conducting material 22 Between any divergent boundary.
As limiting examples, block III-V race semi-conducting material 22 can be made to deposit on growing substrate 20 To average total thickness T2Be at least about 5 microns (5 μm), at least about 7 microns (7 μm), at least about 10 microns (10 μm), At least about 20 microns (20 μm) or at least about 30 microns (30 μm).The metal nitrogen manufactured according to embodiment of the present invention The existence of compound nucleation template layer 18 can make block III-V race semi-conducting material 22 can deposit to above-mentioned averagely Gross thickness T2, the block III-V at first type surface 23 that simultaneously block III-V race semi-conducting material 22 exposed Dislocation density in race's semi-conducting material 22 keeps being about 5 × 108Concentration below/square centimeter.
Fig. 4 A and 4B is the HVPE depositing system showing the embodiment that can be used for the inventive method as herein described The rough schematic view of the embodiment of 100.As limiting examples, depositing system 100 can include following arbitrary The U.S. Patent Application Publication No. of JIUYUE in 2009 announcement on the 10th under one's name such as the depositing system described in document: Arena etc. No. US2009/0223442A1；The U.S. Provisional Patent Application that Arena etc. submit on March 3rd, 2009 No. 61/157,112；The U.S. Patent Application No. 12/894,724 submitted for 30th with Bertran2010 JIUYUE.Figure Depositing system 100 shown in 4A and 4B includes that reative cell 102 and one or more gas syringe (hereafter will enter One step describes in detail).
Below in the description to depositing system 100, more specifically, at the reative cell 102 to depositing system 100 Description in, term " longitudinally " and " laterally " for expression from the perspective view of Fig. 4 A and 4B relative to reative cell 102 For direction, be longitudinally wherein the vertical direction of Fig. 4 A perspective view and the direction in extending into the plane of Fig. 4 B, Laterally or lateral (lateral direction) is from the horizontal-extending direction of the perspective view of Fig. 4 A or 4B.The most also referred to as Extend the direction of " across reactor ".
Depositing system 100 includes reative cell 102, matrix body support structure 104 (such as, pedestal), and matrix support is tied The structure of structure body 104 can support that (matrix 106 initially can comprise shown in Fig. 1 one or more workpiece substrate 106 Growing substrate 20 shown in matrix 10 or Fig. 2), described matrix 106 needs in depositing system 100 deposition or with Alternate manner provides material.As limiting examples, reative cell 102 can have the height, about of about 2 inches The width of 12 inches and the length of about 20 inches, the structure of matrix body support structure 104 can support one 8 inches The workpiece substrate 106 of workpiece substrate 106, three 4 inches of workpiece substrate 106,6 inches or eight 2 The workpiece substrate 106 of inch.Depositing system 100 also comprises heating element heater 108 (Fig. 4 B), and it can be used for selectivity and adds Heat deposition system 100 thus in deposition process, the mean temperature in reative cell 102 is controlled under desired high temperature. Heating element heater 108 can comprise such as, resistive heating elements or radiative heating elements.
As shown in Figure 4 B, matrix body support structure 104 may be mounted on axle 110, and axle 110 can be with driving Device 112 connects (such as, direct organization connects, magnetic force connection etc.), driving means 112 for example, motor, its structure Make drivable shaft 110 to rotate, thus drive the matrix body support structure 104 in reative cell 102 to rotate.
In some embodiments, reative cell 102, matrix body support structure 104, axle 110 and reative cell 102 In any other assembly in one or more can be at least substantially made up of refractory ceramic material, such as pottery oxygen Compound (such as silicon dioxide (quartzy), aluminium oxide, zirconium oxide etc.), carbide (such as carborundum, boron carbide etc.) or nitride (such as silicon nitride, boron nitride etc.).
Depositing system 100 also includes air flow system, and it is used for injecting one or more gas in reative cell 102 and will Gas is discharged from reative cell 102.See Fig. 4 A, depositing system 100 can include respectively from each source of the gas 128A, 128B, 128C carries 3 gases inflow catheter 114A, 114B, 114C of gas.Optionally, it may include valve, One or more device 117A, 117B, 117C in back pressure regulator, mass flow controllers can be respectively used to select Property control to be flowed by the gas of gas inflow catheter 114A, 114B, 114C.
In some embodiments, at least one in source of the gas 128A, 128B can include such as U.S. Patent Application Publication No. US2009/0223442A1 described metal terchoride (such as GaCl3、InCl3Or AlCl3) external source. GaCl3、InCl3And AlCl3Can be presented in dimer, the most respectively Ga2Cl6、In2Cl6And Al2Cl6。 Therefore, at least one comprised dimer in source of the gas 128A, 128B, such as Ga2Cl6、In2Cl6Or Al2Cl6。 As limiting examples, one or more in source of the gas 128A, 128B provide GaCl3The mass flow conduct of steam Group IIIA precursor component.Source of the gas 128C can comprise such as ammonia (NH3) etc. the external source of VA race precursor.
One or more for GaCl in source of the gas 128A, 128B3Source or comprise GaCl3In the embodiment in source, Described GaCl3Source is included in liquid GaCl that at least 120 DEG C of (such as, about 130 DEG C) temperature preserve3Storage tank, and can Comprise enhancing liquid GaCl3The physical location (physical means) of evaporation rate.Described physical location can include, Such as, it is configured to stir liquid GaCl3Device, be configured to spray liquid GaCl3Device, be configured to Carrier gas is made to flow fast through liquid GaCl3Top device, be configured to make carrier gas pass through liquid GaCl3The device of bubbling, It is configured to make liquid GaCl3The device (such as piezo-electric device) etc. of ultrasonic disperse.As limiting examples, carrier gas For example, He, N2、H2, Ar or its mixture (such as, N2And H2Mixture), it is possible to by liquid GaCl3 Bubbling, simultaneously by liquid GaCl3Remain the temperature of at least 120 DEG C, so that source gas can comprise one or more Carrier gas.
In certain embodiments of the present invention, can control to be passed through one or more gas syringe 150A, 150B In GaCl3The flow of steam.Such as, in carrier gas by liquid GaCl3In the embodiment of bubbling, from source of the gas The GaCl of 128A, 128B, 128C3Flow depends on one or more factors, such as, include GaCl3Temperature, GaCl3Top pressure and pass through GaCl3The carrier gas of bubbling.Although in principle can be by appointing in these parameters What parameter controls GaCl3Mass flow, but in some embodiments, can change by utilizing mass flow controller Variable load flow of air controls GaCl3Mass flow.
In some embodiments, can control between source of the gas 128A, 128B and gas syringe 150A, 150B The temperature of gas inflow catheter 114A, 114B processed.Gas inflow catheter 114A, 114B and relevant quality stream The temperature of sensor and controller etc. can from first temperature in the exit of each source of the gas 128A, 128B (such as, about More than 120 DEG C) the second temperature (such as, less than about 160 DEG C) of gradually rising to gas syringe 150A, 150B, Thus prevent gas (such as, the GaCl in gas inflow catheter 114A and 114B etc.3Steam) condense.Optionally, Gas inflow catheter 114A, 114B's between each source of the gas 128A, 128B and gas syringe 150A, 150B Length can be about less than 3 feet, less than about 2 feet or less than about 1 foot.The pressure of source gas can utilize one Plant or multiple control pressurer system controls.
Two gases inflow catheter 114A, 114B can extend to two be described in more detail below the most alternatively In gas syringe 150A, 150B corresponding one.
In other embodiment, depositing system 100 can include less than 2 (i.e. 1) gas inflow catheters and Corresponding gas syringe, or depositing system 100 can comprise more than 2, and the individual gas such as (such as 3,4,5) flows into Conduit and corresponding gas syringe.
In the embodiment of Fig. 4 A and 4B, gas syringe 150A, 150B are positioned at reative cell 102 on the whole Outside.But, in other embodiments, gas syringe 150A, 150B can be arranged on reative cell on the whole In 102, or gas syringe 150A, 150B can at least partly extend through reative cell 102 at least partially.
Depositing system 100 can also comprise 3 offer reative cells 102 outwardly and inwardly between fluid communication gas Port 116A, 116B, 116C.Each gas ports 116A, 116B, 116C may pass through reative cell 102 wall, One or more each gas dispersing catheter 118A, 118B, 118C in reative cell 102 in top or the end and corresponding Gas syringe 150A, 150B between provide fluid communication.
Gas dispersing catheter 118A, 118B, 118C in reative cell 102 can be used for being carried by gas to closing space In desired position.The position of gas dispersing catheter 118A, 118B, 118C and structure can make gas along relative to The preferential direction of the workpiece substrate 106 of matrix body support structure 104 carrying is injected into the inside of reative cell 102.Gas The gas that dispersing catheter 118A, 118B, 118C carry, such as precursor gases and carrier gas can be along reative cells 102 Longitudinal direction (vertical direction of Fig. 4 A perspective view) flowing, and can be towards workpiece substrate 106 along reative cell 102 The direction of longitudinal extension injects from which, and described direction is exposed at least substantially parallel to workpiece substrate 106 top First type surface orients.Gas dispersing catheter 118A, 118B, 118C can be supported and protect by fixture to utilize conduit to support Hold appropriate location in reative cell 102.
The concrete of gas dispersing catheter 118A, 118B, 118C arranges and constructs to be only to can be used for embodiment of the present invention Numerous layouts and structure in one, in other embodiments of reative cell 102, gas dispersing catheter is at reative cell Different structures and layout can be had in 102.
Gas dispersing catheter 118A, 118B, 118C can carry out actively heating and/or passively heating.Such as, raw Thermal element (not shown) can be placed in gas dispersing catheter 118A, 118B, 118C at least some of near.? In some embodiments, gas dispersing catheter 118A, 118B, 118C are heated by heating element heater 108 (Fig. 4 B).Can Choosing, passive heat-transfer structure (such as, comprising the structure of the character material similar to black matrix) may be located at reaction Gas dispersing catheter 118A, 118B, 118C in room 102 at least some of the most near or around (proximate to), To improve the heat transmission to gas dispersing catheter 118A, 118B, 118C.
Such as, U.S. Patent Application Publication No. US as disclosed in 27 days Augusts in 2009 under one's name such as Arena As No. 2009/0214785A1 discloses, passive heat-transfer structure (such as, can be comprised character similar to black matrix The structure of material) be arranged in reative cell 102.For example, it is possible to by heat transfer plate 124 (with void in Fig. 4 A and 4B Line represents) it is placed in reative cell 102, so that heat transfer plate 124 at matrix body support structure 104 and is propped up by matrix Hold and extend across reative cell 102 on the workpiece substrate 106 that structure 104 is supported.By absorbing from heating element heater (example Such as heating element heater 108) radiation and the heat re-radiation that absorbed is given place's process gases, heat transfer plate 124 can help to make The process gas transconversion into heat of heat transfer plate 124 surrounding flowing.
This passive heat-transfer structure can improve heat in the transmission within reative cell 102, and can improve reative cell The uniformity of temperature and seriality in 102.Passive heat-transfer structure can comprise have high emissivity value (close to 1) and Also it is resistant in depositing system 100 material (black matrix material) of the high temperature corrosion environment that may meet with.This material Such as aluminium nitride (AlN), carborundum (SiC) and boron carbide (B can be included4C), its emissivity value is respectively 0.98,0.92 With 0.92.
The precursor gases of gaseous by-product, carrier gas and any excess can be arranged from reative cell 102 by chamber outlet 126 Go out.
As it has been described above, in gas syringe 150A, 150B of the depositing system 100 of Fig. 4 A and 4B one or Multiple can be the gas syringe described in further detail below with reference to Fig. 5～7, or include below with reference to Fig. 5～ 7 gas syringes described in further detail.
In some embodiments, gas syringe 150A, 150B can include Arena etc. 2010 9 under one's name The gas syringe disclosed in international publication the WO2010/101715A1st disclosed in the moon 10.Such as, Fig. 5 Being the perspective view of transconversion into heat gas syringe 160, transconversion into heat gas syringe 160 can be used for the gas injection shown in Fig. 4 A In device 150A and/or 150B.As shown in Figure 6, gas syringe 160 includes that conduit 162, conduit 162 include Inlet portion 164, spiral pars intermedia 166 and export department 168.Source gas (such as GaCl3), carrier gas (such as H2、N2 Deng) or the mixture of source gas and carrier gas can supply to inlet portion 164.One or more gases are from inlet portion 164 Flow through spiral pars intermedia 166, flow out from export department 168 and flow into reative cell 102 (Fig. 4 A).As the most further Illustrate, can at least the spiral pars intermedia 166 of conduit 162 be heated.By making conduit 162 coiled, lead The length of the physical space occupied by pipe 162 is significantly less than the physical length of the stream by conduit 162.In other words, The length of conduit 162 can be longer than the beeline between inlet portion 164 and export department 168.Conduit 162 can have it Its structure.Such as, conduit 162 can have serpentine coil structure, it include by the tune extended with 180 ° of angles with The multiple almost parallel straight section that end-to-end mode links together.
Conduit 162 can be configured to flow through with desired time quantum (that is, the time of staying) heating the gas of conduit 162, This time quantum can be the sectional area of the stream in conduit 162, by the flow velocity of the source gas of conduit 162 and conduit The function of the total length of 162.As hereinafter described in more detail, conduit 162 can be shaped and be configured to make its position Around one or more actively or passively heating element heater.
As it is shown in figure 5, shell 170 at least accommodates the spiral pars intermedia 166 of conduit 162.Shell 170 is all right As the other gas conduit for gases such as purge gass.Such as, as it is shown in figure 5, shell 170 can comprise shell enters Mouth 172 and shell outlet 174.Purge gas can be made to flow to shell outlet 174 from shell entrance 172 by shell 170.Blow Scavenging can be heated through transconversion into heat gas syringe 160 when by shell 170.
When conduit 162 and shell 170 may be embodied in use, its pyrometric scale stood is revealed stable and inert resistance to Fire material.Such as, conduit 162 and shell 170 can be formed by quartz and be at least substantially made up of quartz.
Utilize the one or more surroundings (near such as) in the spiral pars intermedia 166 being positioned at shell 170 and conduit 172 Active thermogenesis element transconversion into heat gas syringe 160 can be heated.Active heat element includes radiation-emitting unit Part, such as heating lamp, inductive heating element, electrical heating elements such as resistive heating elements etc..Transconversion into heat gas syringe 160 can also comprise passive heating element heater, itself do not produce heat, are but used for reallocating, reflect or otherwise Affect the internal heat transfer with surrounding of transconversion into heat gas syringe 160.Such as, as it is shown in figure 5, transconversion into heat gas syringe 160 can comprise active heat element 180, and active heat element 180 can include at least partially surrounding shell 170 outside Resistance-type heating tongs shell heater.Therefore, the gas flowing through conduit 162 and/or shell 170 can be through actively adding Thermal element 180 heats.As it is shown in figure 5, optional actively or passively heating element heater can be configured in shell 170 182.As it is shown in figure 5, heating element heater 182 can have in the middle of elongated cylindrical shape, and the spiral of serpentine pipe 162 Portion 166 can become spiral around heating element heater 182.As limiting examples, heating element heater 182 can include containing The rod of black matrix material, the heat that described black matrix material produces for active heat element 180 of reallocating.Heating element heater The existence of 182 can improve active heat element 180 to the gas in the spiral pars intermedia 166 of serpentine pipe 162 and shell The efficiency of heating surface of the gas in 170.
By the source gas of in source of the gas 128A, 128B one supply to transconversion into heat gas syringe 160 comprise as GaCl3Deng metal terchoride and hydrogen bearing gas H2Embodiment in, described metal terchoride and hydrogen decomposable asymmetric choice net shape Becoming such as metal monochloride steam and the HCl steams such as GaCl, described steam can be by the export department 168 of conduit 162 Discharge and arrive reative cell 102.
In other embodiment, gas syringe 150A, 150B can include U.S. Patent Application No. 12/894,724 Gas syringe disclosed in number.Such as, gas syringe 150A, 150B can comprise be configured to accommodate liquid metal Or other element or the storage tank of organic metal material, described liquid metal or other elements such as liquid gallium (Ga), liquid State aluminum (Al) or liquid indium (In), described organic metal material such as trimethyl gallium (TMG), triethyl-gallium (TEG), three Aluminium methyl (TMA), triethyl aluminum (TEA), four (diethylamino) titanium (TDEAT) and four (dimethylamino) titanium (TDMAT).In other embodiments, storage tank may be structured to accommodate for (or the decomposition of source gas of source gas Or product) solid reagent that reacts.Such as, storage tank may be structured to accommodate solid-state volume (solid volume) One or more materials, such as solid silicon (Si) or solid magnesium (Mg).
Fig. 6 is the perspective view of gas syringe 200, and gas syringe 200 can be used for the gas injection shown in Fig. 4 A Device 150A and/or 150B.As shown in Figure 6, gas syringe 200 includes that entrance 202, outlet 204, transconversion into heat are led Pipe 206 and container 210.Container 210 is configured to accommodate liquid reagent therein.Such as, container 210 can be put Put liquid metal such as liquid gallium, liquid indium, liquid aluminium etc., or Liquid organometallic material.Source gas is (such as GaCl3)、 Carrier gas is (such as H2、N2Deng) or the mixture of source gas and carrier gas can supply to entrance 202.One or more gases described Transconversion into heat conduit 206 can be flowed into from entrance 202.Transconversion into heat conduit 206 may be structured to desired time quantum (when i.e. stopping Between) heating flows through the gas of transconversion into heat conduit 206, this time quantum can be the stream in transconversion into heat conduit 206 sectional area, By the flow velocity of the source gas of transconversion into heat conduit 206 and the function of the total length of transconversion into heat conduit 206.As explained in greater detail below Description, can shape transconversion into heat conduit 206 and be configured to be located at one or more actively or passively heating element heaters Around.
It addition, transconversion into heat conduit 206 can include one or more tune or back bending (turn), therefore transconversion into heat conduit 206 institute The length of the physical space occupied is significantly less than the physical length of the stream by transconversion into heat conduit 206.In other words, transconversion into heat The length of conduit 206 can be longer than the beeline between entrance 202 and liquid container 210.In some embodiments, The length of transconversion into heat conduit 206 can be at least about 2 times of the beeline between entrance 202 and liquid container 210, It is at least about 3 times of beeline between entrance 202 and liquid container 210, or entrance 202 and liquid hold At least about 4 times of beeline between device 210.Such as, as shown in Figure 6, transconversion into heat conduit 206 can have snakelike Coil configuration, it include by the tune extended by 180 ° of angles with link together in the way of end-to-end multiple substantially Parallel straight section.
Transconversion into heat conduit 206 can comprise at least substantially by the refractory material pipe that such as quartz is constituted.
In some embodiments, the source gas at least partly decomposed during gas can be included in transconversion into heat conduit 206.Such as, GaCl is comprised at gas3Source gas and containing H2Carrier gas embodiment in, source gas decomposable asymmetric choice net formed gaseous state GaCl and hydrogen chloride (HCl).
Gas flows into container 210 from transconversion into heat conduit 206.Fig. 7 is the amplification partial sectional view of container 210.Such as Fig. 7 Shown in, container 210 includes diapire 212, roof 214 and at least one sidewall 216.Embodiment party at Fig. 6 and 7 In formula, storage tank is substantially cylindrical, and therefore diapire 212 and roof 214 are circular and the most substantially planar shape, And sidewall 216 is at least essentially cylindric (such as, tubulose).In the embodiment that the present invention is other, storage tank can It is configured to substituting geometric construction.Diapire 212, roof 214 and at least one sidewall 216 define sky jointly Heart body, defines inside it for accommodating such as the storage tank of the liquid reagents such as liquid gallium or organic metal material.
The inner space of hollow body 210 can partly load liquid reagent.Such as, container 210 can load liquid reagent The level shown in dotted line 220 to Fig. 7, so that the liquid reagent space present above in container 210 or space 222.From the space 222 that transconversion into heat conduit 206 effluent air can inject above the liquid reagent in container 210. As limiting examples, can be flowed into pipe 224 by diapire 212 from transconversion into heat conduit 206 effluent air.One In a little embodiments, pipe 224 can comprise transconversion into heat conduit 206 and extend into the necessary part in container 210.Pipe 224 May pass through the liquid reagent arranged in liquid container to extend in the space 222 above liquid reagent.Pipe 224 can comprise The turn of bilge of 90 °, so that the end of pipe 224 extends in liquid reagent upper horizontal.
As it is shown in fig. 7, can be at pipe 224 towards the cylindrical shape being arranged through pipe 224 on the side on liquid reagent surface The aperture of sidewall, so that the gas flowing through pipe 224 leaves pipe 224 by this aperture 226.Leave aperture 226 Gas can be derived along the direction on directional liquid reagent surface from this aperture, thus promote one or more gas componants with Reaction between liquid reagent.Such as, comprise by carrier gas (such as H at source gas2) GaCl that carries3And source gas Comprise gaseous state GaCl and the embodiment of chloride (such as, hydrogen chloride (HCl)) through decomposition in transconversion into heat conduit 206 In, the liquid reagent in liquid container can comprise liquid gallium, and this liquid gallium can be with the chlorination of generation in transconversion into heat conduit 206 Gas (such as HCl) reaction forms extra gaseous state GaCl.In container 210 in space 222 above liquid reagent Gas can pass through outlet port 228 flow container.Such as, outlet port 228 can be located at the horizontal extension of pipe 224 In the vessel top wall 214 of top.Outlet port 228 can lead to delivery channel 230, and the end of delivery channel 230 can Define the outlet 204 of gas syringe 200.
In other embodiment, the liquid reagent container 210 can be injected from transconversion into heat conduit 206 effluent air In, so that this gas by liquid reagent upwards bubbling and enters the space 222 above liquid reagent.
Each parts of container 210 can be made up of refractory material such as quartz at least substantially.
GaCl is the desired precursor gases for forming GaN.Therefore, by will be by GaCl3And H2(using Comprise GaCl3And H2Source gas system in) thermal decomposition produce excess chlorine compound such as hydrogen chloride gas (HCl) It is converted into extra GaCl, owing to the muriatic amount of reative cell 102 can be lowered into, thus can avoid The chloride of the amount adverse effect to the GaN material of deposition.Described adverse effect can include such as being introduced by chlorine atom In gallium nitride crystal lattice and make deposited GaN film rupture or delamination.Introduce excess chlorination hydrogen in the reaction chamber (HCl) may result in the GaN that hydrogen chloride acts in reative cell as etchant, thus reduce GaN growth speed or very To stoping GaN growth.It addition, form extra GaCl, Ke Yigai by making excess chlorine compound and liquid gallium react The efficiency of kind depositing system 100.
The HVPE depositing system 100 described above with reference to Fig. 4 A and 4B can be used for according to describing with reference to Fig. 3 above Embodiment of the present invention on growing substrate 20, deposit block III-nitride semiconductor material 22.Fig. 8 is aobvious Show that the schematic diagram of the limiting examples of HVPE sedimentation, described HVPE sedimentation may utilize Fig. 4 A's and 4B Depositing system 100 and be used for the block III-nitride semiconductor material 22 of deposition on growing substrate 20.Fig. 8 institute The sedimentation shown is only used as example to be provided, it is also possible to use other HVPE sedimentations to deposit block on growing substrate 20 Shape III-nitride semiconductor material 22 (Fig. 3).
Seeing Fig. 8, exemplary deposition method is by drawing the function curve as time t of temperature T in reative cell 102 Represent.As it can be seen, sedimentation included for ten (10) individual stages, these 10 stages are labeled as S1～S10 successively.Heavy In whole 10 stage S1～S10 of area method, the non-restrictive illustrative procedure parameter in each stage is given in Table 1 below.
As shown in Fig. 8 and Biao 1, workpiece substrate 106 is loaded on matrix body support structure 104 by stage S1 Loading stage.After being loaded on matrix body support structure 104 by workpiece substrate 106, reative cell 102 is at air Pressure is heated to temperature T of 350 DEG C1, make containing N with the flow velocity of 10 standard liter/min (slm) simultaneously2Purging air-flow Cross reative cell 102.
As shown in Figure 8, stabilisation stage S2 is at t1Time start and continue 30 seconds.In stabilisation stage S2, reaction Room 102 is heated to temperature T of 400 DEG C under the pressure of 200 torr2, make purge gas flow through reative cell 102 simultaneously.Blow Scavenging comprises the N that flow velocity is 15slm2It is the H of 2slm with flow velocity2。
The alternating temperature stage, S3 was at t2Time start and continue 4.5 minutes.At alternating temperature stage S3, reative cell 102 is with substantially Constant Cooling rate is by temperature T2Stablize and temperature T of laser heating to 1025 DEG C3.In alternating temperature stage S3, The pressure of reative cell 102 remains 200 torr.In alternating temperature stage S3, comprise NH3Group V source gas with 1slm Flow velocity flow through reative cell 102, and comprise the N that flow velocity is 23slm2It is the H of 16slm with flow velocity2Purge gas By reative cell 102.
The stabilisation stage, S4 was at t3Time start and continue 30 seconds.In stabilisation stage S4, reative cell 102 keeps Temperature T of 1025 DEG C3Pressure with 200 torr.In stabilisation stage S4, comprise NH3Group V source gas with The flow velocity of 18slm flows through reative cell 102, and comprises the N that flow velocity is 23slm2It is the H of 5slm with flow velocity2's Purge air through reative cell 102.
1st depositional phase S5 is at t4Time start and continue 5.0 minutes.In depositional phase S5, reative cell 102 is protected Hold temperature T of 1025 DEG C3Pressure with 200 torr.In depositional phase S5, comprise GaCl3III source gas Flow through reative cell with the flow velocity of 51 standard cubic centimeters per minute (sccm), and carrier gas comprises the N that flow velocity is 2.5slm2 It is the H of 0.8slm with flow velocity2.Comprise NH3Group V source gas flow through reative cell 102 with the flow velocity of 18slm.Bag It is the N of 23slm containing flow velocity2It is the H of 5slm with flow velocity2Purge gas also flow through reative cell 102.
2nd depositional phase S6 is at t5Time start and continue 20.0 minutes.Reative cell 102 is at the 2nd depositional phase S6 Temperature T3 of middle holding 1025 DEG C and the pressure of 200 torr.III source gas GaCl3Flow velocity at depositional phase S6 In increase to 80sccm, this GaCl3By comprising the N that flow velocity is 2.5slm2It is the H of 1.2slm with flow velocity2Load Gas carries.Comprise NH3Group V source gas flow through reative cell 102 with the flow velocity of 18slm.In the 2nd depositional phase S6 comprises the N that flow velocity is 23slm2It is the H of 5slm with flow velocity2Purge gas also flow through reative cell 102.
In at least one stage in the 1st depositional phase S5 and the 2nd depositional phase S6, block group III-nitride Semi-conducting material 22 can in HVPE method with at least about 10 microns (10 μm)/hour, the most about 20 micro- Rice (20 μm)/hour speed be deposited on growing substrate 20.This sedimentation rate can be significantly greater than with MOCVD The sedimentation rate that the block III-nitride semiconductor material of method deposition is reached.
Annealing stage S7 is at t6Time start and continue 20.0 minutes.In annealing stage S7, reative cell 102 keeps Temperature T of 1025 DEG C3Pressure with 200 torr.In annealing stage S7, comprise NH3Group V source gas with 14slm Flow velocity flow through reative cell 102, and comprise the N that flow velocity is 23slm2It is the H of 5slm with flow velocity2Purge gas Also by reative cell 102.
The alternating temperature stage, S8 was at t7Time start and continue 4.5 minutes.In alternating temperature stage S8, reative cell 102 is with substantially Upper constant Cooling rate is by temperature T3Stablize and temperature T of continuous coo1ing to 400 DEG C2.In alternating temperature stage S8, The pressure of reative cell 102 remains 200 torr.In alternating temperature stage S8, comprise NH3Group V source gas with 14slm Flow velocity flow through reative cell 102, and comprise the N that flow velocity is 23slm2It is the H of 12slm with flow velocity2Purge gas By reative cell 102.
Purge stages S9 is at t8Time start and continue 5.0 minutes.In purge stages S9, reative cell 102 keeps Temperature T of 400 DEG C2, the pressure in simultaneous reactions room 102 is by the 200 near atmospheric pressure of torr.In purge stages S9, Comprise N2Purge gas with the flow velocity of 16slm by reative cell 102.
At t9Time, unloading phase S10 starts and continues to workpiece substrate 106 to unload from reative cell 102.? In unloading phase S10, reative cell 102 is cooled to temperature T of 350 DEG C1And keep this temperature T1, and pressure guarantor Hold atmospheric pressure, make to comprise N simultaneously2Purge gas with the flow velocity of 10slm by reative cell 102.
Refer again to Fig. 1～3, as it has been described above, according to the embodiment of the inventive method, block group III-nitride half Conductor material 22 may utilize HPVE method (the most above-described HPVE method) and deposits on growing substrate 20, and not Mocvd method dystopy on matrix 10 must be utilized to be formed (such as, utilize another depositing system and/or react at another In room) metal nitride nucleation template layer 18.
In some embodiments, non-mocvd method is utilized to form metal on matrix 100 in the first reative cell Nitride nucleation template layer 18 (Fig. 2), thus form growing substrate 20, and anti-be different from the first reative cell second Answer and room utilizes HVPE method (the most above-described HVPE method) deposit block III nitridation on growing substrate 20 Thing semi-conducting material 22.Such as, metal nitride nucleation template layer 18 (Fig. 2) can comprise aluminium nitride (AlN) and nitridation At least one in titanium (TiN), and plasma-enhanced physical deposition methods (PEPVD) or plasma can be utilized Enhanced chemical sedimentation (PECVD) is formed on matrix 100.
As limiting examples, metal nitride nucleation template layer 18 can comprise aluminium nitride (AlN) and can profit 2004 Authorizes the plasma-enhanced thing disclosed in the U.S. Patent No. 6,784,085 of Cuomo et al. on August 31, Physical vapor deposition (PEPVD) system and method manufactures.Such as, matrix 100 and III metallic target can be loaded into In sputtering settling chamber (separating with the reative cell 102 of HVPE depositing system 100).Utilize the background gas being suitable for (such as Argon) energetic plasma enhancing environment can be produced in sputtering settling chamber.Separately nitrogen containing source gas can be passed through this Chamber.As supplementing, or alternatively, can serve as reactant source for producing the gas of plasma Gas, background gas can provide nitrogen substance (nitrogen species) in this case.The sputtering of III metallic target produces III source metal steam.III source metal steam is combined with nitrogenous gas, and this nitrogenous gas may be characterized as comprising as double One or more things such as the nitrogen of Nitrogen Atom, Nitrogen Atom, Nitrogen ion and partial ionization and nitrogen-containing compound (such as ammonia) Matter.As a result, generation is comprised the reactant vapor material of the composition of III metal and nitrogen by reative cell, and is deposited on On the first type surface 14 that matrix 10 exposes (on and over).The reactant vapor electrodeposition substance of deposition former state is at matrix 100 The metal nitride nucleation template layer 18 of upper generation Fig. 2.In some embodiments, the nitride metal of former state is deposited Thing nucleation template layer 18 can carry out one or many heat treatment and improve the metal nitride nucleation template layer of deposition former state The crystalline quality of 18.Such as, the metal nitride materials of deposition former state can be polycrystalline and/or amorphous, and can Carry out one or many heat treatment to strengthen the degree of crystallinity of metal nitride nucleation template layer 18.At some embodiments In, described one or many heat treatment can comprise rapid thermal annealing (RTA) method.Described one or many heat treatment is permissible One or more in heating furnace, rapid thermal annealing room and CVD reactor such as carried out.As non- Limitative examples, described one or many heat treatment can include the metal nitride nucleation template layer 18 making deposition former state Stand greater than about 600 DEG C, greater than about 800 DEG C or one or more temperature of greater than about 1000 DEG C.For processing deposition The one or many heat treatment of the metal nitride nucleation template layer 18 of former state can enter in controlled atmosphere OK.Such as, one or more during described atmosphere can comprise ammonia, nitrogen, hydrogen and argon.
It is alternatively possible to utilize known doping method that metal nitride nucleation template layer 18 is adulterated one or more Dopant element.For example, it is possible under controlled conditions the gas containing adulterant is imported reative cell.
As another limiting examples, metal nitride nucleation template layer 18 can comprise titanium nitride (TiN), and utilize On March 11st, 1997 authorizes the plasma enhancing disclosed in the U.S. Patent No. 5,610,106 of Foster et al. Type chemical gaseous phase deposition (PECVD) system and method manufactures.Such as, matrix 10 can be loaded into chemical gaseous phase deposition In room (being separated with the reative cell 102 of HVPE depositing system 100).Generation radio frequency can be set in a cvd chamber (RF) spray head (showerhead)/electrode, it is possible to by spray head/electrode by reactant gas towards matrix 10 Pump in described chamber.Reactant gas includes titanium tetrachloride (TiCl4), ammonia (NH3) and diluent.Diluent can wrap One or more in hydrogen, helium, argon and nitrogen.
Matrix 10 can be with spray head/electrode at a distance of about 0.25 inch～3 inches, so that active ion bombards matrix 10.When reactant gas is by spray head/electrode, the spray head/electrode producing RF is utilized to be produced by reactant gas Raw plasma.The reactive ion bombardment matrix 10 of plasma.
Pressure in CVD chamber can keep about 0.5 torr～about 20 torr (such as, about 5 torr).Base in deposition process Body 10 can keep the temperature of about 400 DEG C～about 500 DEG C (such as, about 450 DEG C).By heating it in deposition process The body support structure of upper placement matrix 10 carrys out heated substrate 10.It addition, place matrix 10 on it in deposition process Body support structure can with more than about 100 revs/min (rpm) rotate.
In CVD chamber, the concentration of reactant gas can pass through flow speed control.Generally, can be with about 1sccm～about 40sccm The flow velocity of (such as, about 10sccm) introduces titanium tetrachloride.TiCl4Dividing potential drop should be of a sufficiently low to form TiN.If TiCl4 Dividing potential drop is too high, then may will not form TiN.When stagnation pressure is 5 torr, TiCl4Dividing potential drop be smaller than 0.02 torr (example As, about 0.01 torr～about 0.001 torr).Under lower pressure (the most about 0.0001 torr), reaction rate may be too low, And phase step type covers (step coverage) and can not be accepted.When stagnation pressure increases above 5 torr, TiCl4Dividing potential drop can phase Should increase.Generally, NH3With TiCl4Mol ratio can be about 2:1 (NH3:TiCl4)～about 100:1 (NH3:TiCl4) (such as, about 10:1).
According to the described embodiment of the method forming metal nitride nucleation template layer 18, average thickness can be formed T1It is about 25 nanometers (25nm) below or about 10 nanometers (10nm) metal nitride nucleation template layer 18 below, And average thickness T can be deposited on metal nitride nucleation template layer 182It is at least about 2 microns (2 μm), extremely Block III-nitride semiconductor material 22 more than few about 5 microns (5 μm) or about 10 microns (10 μm).
PEPVD sedimentation disclosed in U.S. Patent No. 6,784,085 is utilized to form AlN on sapphire substrates Core template layer, utilizes metal terchoride source gas at AlN subsequently in HVPE sedimentation discussed herein above The block GaN of deposition on nucleation template layer, thus produce sample.In the first sample, AlN nucleation template layer exposes First type surface 19 (Fig. 2) tangent (offcut) with the A face of AlN crystal structure with 0.5 °, and AlN nucleation template layer There is the average thickness of about 10 nanometers (10nm).In the second sample, the first type surface 19 that AlN nucleation template layer exposes (Fig. 2) tangent with the M face of AlN crystal structure with 0.25 °, and AlN nucleation template layer has about 25 nanometers (25nm) Average thickness.
The crystalline quality of the block GaN material of gained utilizes X-ray diffraction (XRD) to analyze and measures, and finds that it is tied Brilliant quality is essentially identical to the crystalline quality of the block GaN utilizing conventional MOCVD technique to be formed reported.Separately Outward, after block GaN material being deposited on the AlN nucleation template layer of growing substrate, measure block GaN The surface roughness of the first type surface 23 that material exposes.Observe, be deposited on the first sample (tangent with 0.5 ° of A face 10nm AlN nucleation template layer) on the first type surface ratio that exposes of block GaN material be deposited on the second sample (with M face 0.25 ° of tangent 25nm AlN nucleation template layer) on the first type surface that exposes of block GaN material more smooth.Concrete and Speech, the first sample shows root-mean-square (RMS) surface roughness of about 9.72nm, and the second sample shows about 10.58nm rms surface roughness.
Refer again to Fig. 1～3, in other embodiment, utilize in reative cell 102 (Fig. 4 A and 4B) Mocvd method is formed in situ metal nitride nucleation template layer 18 (Fig. 2), same reative cell 102 on matrix 100 In HVPE method, on this template layer 18, block III-nitride semiconductor material 22 is deposited for subsequently.Such as, Metal nitride nucleation template layer 18 (Fig. 2) can comprise gallium nitride (GaN), aluminium nitride (AlN), aluminium gallium nitride alloy (AlxGa1-xN) at least one and in titanium nitride (TiN).
Therefore, in some embodiments, the depositing system 100 described with reference to Fig. 4 A and 4B before this can be carried out Each of in mocvd method and HVPE method, and be configured to can carry out in mocvd method and HVPE method Each of.Seeing Fig. 4 A, as limiting examples, one in source of the gas 128A, 128B can comprise organic The source of metal precursor, described organic metal precursors such as trimethyl gallium (TMG), triethyl-gallium (TEG), trimethyl aluminium (TMA), triethyl aluminum (TEA), four (diethylamino) titanium (TDEAT) and four (dimethylamino) titanium (TDMAT) In one or more.In said embodiment, it may not be necessary to utilize the transconversion into heat being connected with the source of Organometallic precursor Gas syringe 150A, 150C, but Organometallic precursor is carried to reative cell by available carrier gas.Such as, Carrier gas can by the storage tank bubbling of Liquid organometallic precursor that is heated thus form organic metal vapors, this is organic subsequently Metal vapors can flow in reative cell 102.Organic metal steam 102 can decompose in reative cell 102, thus Workpiece substrate 106 (such as, the matrix 100 shown in Fig. 1) upper deposition metal nitride nucleation template layer 18.Can use Mocvd method forms metal nitride nucleation template layer 18 at reative cell 102 situ, and same reative cell 102 is used In utilizing depositing system as herein described to deposit block III-nitride semiconductor material in HVPE method, described Mocvd method is such as in U.S. Patent Application Publication No. disclosed in Choi under one's name 23 days July in 2009 No. 2009/0184398A1 has been disclosed.
In said embodiment, average thickness T can be formed1It is about half nanometer (0.5nm)～about 2 microns (2 μm) Metal nitride nucleation template layer 18, and form average thickness T2Be at least about 2 microns (2 μm), at least about 5 Micron (5 μm), at least about 7 microns (7 μm), at least about 10 microns (10 μm), at least about 20 microns (20 μm) Or the block III-nitride semiconductor material 22 of at least about 30 microns (30 μm).It addition, at some embodiments In, the first type surface 23 that the block III-nitride semiconductor material 22 of deposition is exposed can have about 2 nanometers (2.0nm) The rms surface roughness of (such as, about 0.112nm) below.
Refer again to Fig. 1～3, in other embodiment, in reative cell 102 (Fig. 4 A and 4B), utilize HVPE Method is formed in situ metal nitride nucleation template layer 18 (Fig. 2) on matrix 100, and same reative cell 102 is for subsequently On template layer 18, block III-nitride semiconductor material 22 is deposited in HVPE method as herein described.Such as, Metal nitride nucleation template layer 18 (Fig. 2) can comprise at least one in aluminium nitride (AlN) and titanium nitride (TiN), and And the available U.S. Patent No. 6,221,174 authorizing April 24 calendar year 2001 such as Chen etc. and Arena under one's name 2010 Method disclosed in international publication the WO2010/101715A1st disclosed on JIUYUE 10, is formed.
See Fig. 4 A, source gas 128A to can be used in HVPE method, form metal nitride nucleation template layer 18 (figure , and source gas 128B can be used for being formed block III-nitride semiconductor material in follow-up HVPE method 2) 22。
As limiting examples, metal nitride nucleation template layer 18 (Fig. 2) can comprise aluminium nitride (AlN), and Source of the gas 128A can comprise AlCl3Gas source.AlCl3Gas source can include being maintained at the temperature of at least 190 DEG C (such as, About 195 DEG C) and liquid AlCl of about 2.5 atmospheric pressures3Storage tank, and can include for strengthening described alternatively Liquid AlCl3The physical location of evaporation rate.This type of physical location can include, such as, is configured to stir liquid AlCl3Device, be configured to spray liquid AlCl3Device, be configured to make carrier gas flow fast through liquid AlCl3 Top device, be configured to make carrier gas pass through liquid AlCl3The device of bubbling, it is configured to make liquid AlCl3Super The scattered device of sound (such as piezo-electric device) etc..As limiting examples, carrier gas such as He, N2、H2Or Ar Or its mixture (such as, N2And H2Mixture) liquid AlCl can be passed through3Bubbling, simultaneously by liquid AlCl3Protect Holding is the temperature of at least 195 DEG C, so that source gas can include one or more carrier gas.Optionally, AlCl3With Containing H2Carrier gas can supply to transconversion into heat syringe 150A, AlCl in transconversion into heat syringe 150A3Decomposable asymmetric choice net forms AlCl And HCl.HCl can react with the liquid aluminium of receiving in transconversion into heat syringe 150A thus form extra AlCl.Institute State gas can to import subsequently in reative cell 102, in reative cell 102 AlCl can with supplied by source of the gas 128C NH3React thus on matrix, form AlN.
As another limiting examples, metal nitride nucleation template layer 18 (Fig. 2) can comprise titanium nitride (TiN), And source of the gas 128A can comprise TiCl4Gas source.TiCl4Gas source can include the liquid being maintained at the temperature of at least 80 DEG C State TiCl4Storage tank, and can include as above for strengthening described liquid TiCl alternatively4Evaporation rate Physical location.As limiting examples, carrier gas such as He, N2、H2Or Ar or its mixture (such as, N2 And H2Mixture) liquid TiCl can be passed through4Bubbling, simultaneously by liquid TiCl4Remain the temperature of at least 137 DEG C, So that source gas can include one or more carrier gas.TiCl4Steam can import in reative cell 102 subsequently, in reaction TiCl in room 1024Can be with the NH supplied by source of the gas 128C3React thus on matrix, form TiN.This mistake Cheng Zhongyu is found in aforesaid U.S. Patent No. for other particular contents that the processing parameter forming TiN is relevant No. 6,221,174.
After utilizing above-mentioned HVPE method to form metal nitride nucleation template layer 18 in reative cell 102, can be in order to Partly lead with forming block group III-nitride in same reative cell 102 above with reference to the HVPE method described in Fig. 3 and 8 Body material 22.The block III of deposition after forming metal nitride nucleation template layer 18 and on growing substrate 20 Before nitride semi-conductor material 22, in the case of not taking out growing substrate 20 from reative cell 102, forming gold Block III-nitride semiconductor material 22 can be deposited on growing substrate 20 after belonging to nitride nucleation template layer 18.
The embodiment of the inventive method makes it possible to the manufacture of block III-nitride semiconductor material without using Mocvd method dystopy forms metal nitride nucleation template layer.Therefore, compared with known method before this, the present invention At least some embodiment of method more cost efficiency in terms of forming block III-nitride semiconductor material.
Other non-limiting example embodiment of the present invention is described below.
Embodiment 1: a kind of method of the block III-nitride semiconductor material of deposition on growing substrate, described Method includes: forms metal nitride nucleation template layer on matrix, thus forms described growing substrate；With utilize halogen Compound vapour phase epitaxy (HVPE) method deposits described block III-nitride semiconductor material on described growing substrate, The process depositing described block III-nitride semiconductor material on described growing substrate includes: make metal terchoride It is decomposed to form metal chloride Group III precursor steam with at least one in metal tetrachloride, and makes described metal chlorine Compound Group III precursor steam with Group V precursor vapor reaction thus forms described block III on described growing substrate Nitride semi-conductor material.
Embodiment 2: method as tdescribed in embodiment 1, wherein, forms described nitride metal on the matrix The process of thing nucleation template layer includes utilizing nonmetal organic chemical vapor deposition (MOCVD) method to form described metal Nitride nucleation template layer.
Embodiment 3: method as tdescribed in embodiment 1, wherein, forms described nitride metal on the matrix The process of thing nucleation template layer includes utilizing plasma enhanced chemical vapor deposition (PECVD) method to form described gold Belong to nitride nucleation template layer.
Embodiment 4: the method as described in embodiment 3, wherein, utilizes described plasma-enhanced chemical gas The process of deposition (PECVD) method formation metal nitride nucleation template layer includes mutually: deposit metal nitrogen on the matrix Compound material；Deposited gold is strengthened with the metal nitride materials deposited is carried out one or many heat treatment Belong to the crystallinity of nitride material.
Embodiment 5: the method as described in embodiment 4, wherein, is carried out the metal nitride materials deposited One or many heat treatment thus strengthen the crystalline process of deposited metal nitride materials and include being deposited Metal nitride materials carry out rapid thermal anneal methods.
Embodiment 6: method as tdescribed in embodiment 1, wherein, forms metal nitride on the matrix and becomes The process of core template layer includes utilizing halide gas phase extension (HVPE) method to form described metal nitride nucleation template Layer.
Embodiment 7: the method as described in embodiment 6, wherein, utilizes halide gas phase extension (HVPE) method shape The process becoming metal nitride nucleation template layer includes: make GaCl3、InCl3、AlCl3And TiCl4In at least one It is decomposed to form terchoride Group III precursor steam, dichloride Group III precursor steam and monochloride Group III precursor to steam At least one in gas, and make described Group III precursor steam and NH3Precursor vapor reaction is formed on the matrix Described metal nitride nucleation template layer.
Embodiment 8: the method as according to any one of embodiment 1～7, described method also includes: first Chamber is formed described metal nitride nucleation template layer；Sink on described growing substrate with in the second different chambers Long-pending described block III-nitride semiconductor material.
Embodiment 9: the method as according to any one of embodiment 1～7, described method also includes: at chamber Middle formation described metal nitride nucleation template layer；With the described chamber at the described metal nitride nucleation template layer of formation In on described growing substrate, deposit described block III-nitride semiconductor material.
Embodiment 10: a kind of method of the block III-nitride semiconductor material of deposition on growing substrate, described Method includes: utilize nonmetal organic chemical vapor deposition (MOCVD) method to be formed on matrix in the first chamber Metal nitride nucleation template layer, thus form described growing substrate；Utilize outside halide gas phase with in the second chamber (HVPE) method of prolonging deposits described block III-nitride semiconductor material on described growing substrate, at described growth base The process depositing described block III-nitride semiconductor material on body includes making metal terchoride and metal four chlorination At least one in thing and NH3Flow to described second chamber.
Embodiment 11: the method as described in embodiment 10, described method also includes described matrix is chosen as bag Include sapphire substrates.
Embodiment 12: the method as described in embodiment 10 or embodiment 11, described method also includes institute State metal nitride nucleation template layer to be chosen as comprising at least one in aluminium nitride and titanium nitride.
Embodiment 13: the method as according to any one of embodiment 10～12, wherein, utilizes nonmetal organic Thing chemistry vapour deposition (MOCVD) method forms the process bag of described metal nitride nucleation template layer on the matrix Include and utilize plasma enhanced processes method to form described metal nitride nucleation template layer on the matrix.
Embodiment 14: the method as according to any one of embodiment 10～13, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition be included on described growing substrate deposition GaN, At least one in InN, AlN, InGaN, GaAlN, GaAlN and InAlN.
Embodiment 15: the method as according to any one of embodiment 10～14, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition include with at least about 10 microns (10 μm)/hour Speed deposits described block III-nitride semiconductor material on described growing substrate.
Embodiment 16: the method as described in embodiment 15, wherein, with at least about 10 microns (10 μm)/hour Speed on described growing substrate, deposit the process of described block III-nitride semiconductor material include with at least about 20 microns (20 μm)/hour speed on described growing substrate, deposit described block III-nitride semiconductor material.
Embodiment 17: the method as according to any one of embodiment 10～16, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition is included on described growing substrate deposition average thickness It is at least about the layer of the block III-nitride semiconductor material of 2 microns.
Embodiment 18: the method as according to any one of embodiment 10～17, wherein, shape on the matrix The process becoming described metal nitride nucleation template layer includes that forming average thickness is about 50 nanometers (50nm) institute below State metal nitride nucleation template layer.
Embodiment 19: the method as described in embodiment 18, wherein, forms average thickness and is about 50 nanometers (50nm) The process of following described metal nitride nucleation template layer includes that forming average thickness is about 10 nanometers (10nm) below Described metal nitride nucleation template layer.
Embodiment 20: the method as according to any one of embodiment 10～19, wherein, makes metal terchoride With at least one in metal tetrachloride and NH3The process flowing to described second chamber includes making GaCl3、InCl3、 AlCl3And TiCl4In at least one flow to described second chamber.
Embodiment 21: the method as described in embodiment 20, wherein, makes metal terchoride and metal four chlorination At least one in thing and NH3The process flowing to described second chamber also includes making metal terchoride and metal tetrachloro At least one in compound is with the second chamber described in the flow rate and direction of about below 100sccm.
Embodiment 22: the method as described in embodiment 21, wherein, makes metal terchoride and metal four chlorination At least one in thing includes making metal trichlorine with the process of the second chamber described in the flow rate and direction of about below 100sccm At least one in compound and metal tetrachloride is with the second chamber described in the flow rate and direction of about below 80sccm.
Embodiment 23: the method as according to any one of embodiment 20～22, described method also includes described At least one in metal terchoride and metal tetrachloride is chosen as including GaCl3。
Embodiment 24: the method as according to any one of embodiment 10～23, wherein, deposits described block III The process of hi-nitride semiconductor material makes the master meter mask that the block III-nitride semiconductor material deposited is exposed There is about 10 nanometers (10nm) rms surface roughness below.
Embodiment 25: the method as according to any one of embodiment 10～24, wherein, deposits described block III The process of hi-nitride semiconductor material makes the master meter mask that the block III-nitride semiconductor material deposited is exposed Have about 5 × 108/ square centimeter～9 × 108Average dislocation density below/square centimeter.
Embodiment 26: a kind of method of the block III-nitride semiconductor material of deposition on growing substrate, described Method includes: utilize metal-organic chemical vapor deposition equipment (MOCVD) method to form metal nitrogen on matrix in the chamber Compound nucleation template layer, thus form described growing substrate；Utilize halide gas phase extension in the same chamber (HVPE) method deposits described block III-nitride semiconductor material on described growing substrate；Wherein, halogenation is utilized Thing vapour phase epitaxy (HVPE) method deposits the process of described block III-nitride semiconductor material on described growing substrate Including at least one made in metal terchoride and metal tetrachloride and NH3Flow to described same chamber.
Embodiment 27: the method as described in embodiment 26, described method also includes described matrix is chosen as bag Include sapphire substrates.
Embodiment 28: the method as described in embodiment 26 or embodiment 27, described method also includes institute State metal nitride nucleation template layer be chosen as comprising gallium nitride, aluminium nitride, aluminium gallium nitride alloy, hafnium nitride, chromium nitride, At least one in tungsten nitride and titanium nitride.
Embodiment 29: the method as according to any one of embodiment 26～28, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition be included on described growing substrate deposition GaN, At least one in InN, AlN, InGaN, GaAlN, GaAlN and InAlN.
Embodiment 30: the method as according to any one of embodiment 26～29, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition include with at least about 10 microns (10 μm)/hour Speed deposits described block III-nitride semiconductor material on described growing substrate.
Embodiment 31: the method as described in embodiment 30, wherein, with at least about 10 microns (10 μm)/hour Speed on described growing substrate, deposit the process of described block III-nitride semiconductor material include with at least about 20 microns (20 μm)/hour speed on described growing substrate, deposit described block III-nitride semiconductor material.
Embodiment 32: the method as according to any one of embodiment 26～31, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition is included on described growing substrate deposition average thickness It is at least about the layer of the block III-nitride semiconductor material of 2 microns (2 μm).
Embodiment 33: the method as according to any one of embodiment 26～32, wherein, shape on the matrix The process becoming described metal nitride nucleation template layer also includes that forming average thickness is about half nanometer (0.5nm)～about 2 The metal nitride nucleation template layer of micron (2.0 μm).
Embodiment 34: the method as according to any one of embodiment 26～33, wherein, makes metal terchoride With at least one in metal tetrachloride and NH3The process flowing to described same chamber includes making GaCl3、InCl3、 AlCl3And TiCl4In at least one flow to described same chamber.
Embodiment 35: the method as described in embodiment 34, wherein, makes GaCl3、InCl3、AlCl3And TiCl4 In at least one process flowing to described same chamber also include making GaCl3、InCl3、AlCl3And TiCl4In extremely Few a kind of with same chamber described in the flow rate and direction of about below 100sccm.
Embodiment 36: the method as described in embodiment 35, wherein, makes GaCl3、InCl3、AlCl3And TiCl4 In at least one include making GaCl with the process of same chamber described in the flow rate and direction of about below 100sccm3、 InCl3、AlCl3And TiCl4In at least one with same chamber described in the flow rate and direction of about below 80sccm.
Embodiment 37: the method as according to any one of embodiment 26～36, described method also includes described At least one in metal terchoride and metal tetrachloride is chosen as including GaCl3。
Embodiment 38: the method as according to any one of embodiment 26～37, wherein, deposits described block III The process of hi-nitride semiconductor material makes the master meter mask that the block III-nitride semiconductor material deposited is exposed There is about 2 nanometers (2.0nm) rms surface roughness below.
Embodiment 39: the method as according to any one of embodiment 26～38, wherein, deposits described block III The process of hi-nitride semiconductor material makes the master meter mask that the block III-nitride semiconductor material deposited is exposed Have about 5 × 108Average dislocation density below/square centimeter.
Embodiment 40: a kind of method of the block III-nitride semiconductor material of deposition on growing substrate, described Method includes: utilize halide gas phase extension (HVPE) method to form metal nitride nucleation mould on matrix in the chamber Flaggy, thus form described growing substrate；Utilize halide gas phase extension (HVPE) method in institute in the same chamber State and on growing substrate, deposit described block III-nitride semiconductor material；Wherein, halide gas phase extension is utilized (HVPE) method deposits the process of described block III-nitride semiconductor material on described growing substrate and includes making metal At least one in terchoride and metal tetrachloride and NH3Flow to described same chamber.
Embodiment 41: the method as described in embodiment 40, described method also includes described matrix is chosen as bag Include sapphire substrates.
Embodiment 42: the method as described in embodiment 40 or embodiment 41, described method also includes institute State metal nitride nucleation template layer to be chosen as comprising at least one in aluminium nitride and titanium nitride.
Embodiment 43: the method as according to any one of embodiment 40～42, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition be included on described growing substrate deposition GaN, At least one in InN, AlN, InGaN, GaAlN, GaAlN and InAlN.
Embodiment 44: the method as according to any one of embodiment 40～43, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition include with at least about 10 microns (10 μm)/hour Speed deposits described block III-nitride semiconductor material on described growing substrate.
Embodiment 45: the method as described in embodiment 44, wherein, with at least about 10 microns (10 μm)/hour Speed on described growing substrate, deposit the process of described block III-nitride semiconductor material include with at least about 20 microns (20 μm)/hour speed on described growing substrate, deposit described block III-nitride semiconductor material.
Embodiment 46: the method as according to any one of embodiment 40～45, wherein, at described growing substrate The process of the described block III-nitride semiconductor material of upper deposition is included on described growing substrate deposition average thickness It is at least about the layer of the block III-nitride semiconductor material of 2 microns (2 μm).
Embodiment 47: the method as according to any one of embodiment 40～46, wherein, shape on the matrix Become the process of described metal nitride nucleation template layer also to include being formed average thickness and be about 50 nanometers (50nm) below Metal nitride nucleation template layer.
Embodiment 48: the method as described in embodiment 47, wherein, makes metal terchoride and metal four chlorination At least one in thing and NH3The process flowing to described same chamber also includes making metal terchoride and metal tetrachloro At least one in compound is with same chamber described in the flow rate and direction of about below 100sccm.
Embodiment 49: the method as described in embodiment 48, wherein, makes metal terchoride and metal four chlorination At least one in thing includes making described metal with the process of same chamber described in the flow rate and direction of about below 100sccm At least one in terchoride and metal tetrachloride is with same chamber described in the flow rate and direction of about below 80sccm.
Embodiment 50: the method as according to any one of embodiment 40～49, described method also includes described At least one in metal terchoride and metal tetrachloride is chosen as comprising GaCl3、InCl3、AlCl3And TiCl4 In at least one.
Embodiment 51: the method as according to any one of embodiment 40～50, wherein, deposits described block III The process of hi-nitride semiconductor material makes the master meter mask that the block III-nitride semiconductor material deposited is exposed There is about 10 nanometers (10.0nm) rms surface roughness below.
Embodiment 52: the method as according to any one of embodiment 40～51, wherein, deposits described block III The process of hi-nitride semiconductor material makes the master meter mask that the block III-nitride semiconductor material deposited is exposed Have about 5 × 108Average dislocation density below/square centimeter.
Embodiment 53: the method as according to any one of embodiment 40～52, wherein, at described same chamber In utilize halide gas phase extension (HVPE) method to deposit described block III nitride semiconductor on described growing substrate The process of material includes, forms described metal nitride nucleation template layer on the matrix thus forms described growth base Before depositing described block III-nitride semiconductor material after body and on described growing substrate, not from described same In the case of chamber takes out described growing substrate, described growing substrate deposits described block group III-nitride half Conductor material.
Embodiment 54: a kind of structure comprising block III-nitride semiconductor material, described structure according to Method according to any one of embodiment 1～53 is made.

Claims (9)

1. a method for the block III-nitride semiconductor material of deposition on growing substrate, described method includes:
Matrix is formed metal nitride nucleation template layer, thus forms described growing substrate；With
Utilize halide gas phase extension (HVPE) method to deposit described block group III-nitride on described growing substrate partly to lead Body material, the process depositing described block III-nitride semiconductor material on described growing substrate includes:
Make at least one in metal terchoride and metal tetrachloride be decomposed to form metal chloride Group III precursor to steam Gas, and
Make described metal chloride Group III precursor steam and Group V precursor vapor reaction thus on described growing substrate shape Become described block III-nitride semiconductor material.
Form described metal nitride nucleation mould the most on the matrix The process of flaggy includes utilizing nonmetal organic chemical vapor deposition (MOCVD) method to form described metal nitride Core template layer.
Form described metal nitride nucleation mould the most on the matrix The process of flaggy includes utilizing plasma enhanced chemical vapor deposition (PECVD) method to form described metal nitride Nucleation template layer.
4. method as claimed in claim 3, wherein, utilizes described plasma enhanced chemical vapor deposition (PECVD) method forms the process of described metal nitride nucleation template layer and includes:
Deposit metal nitride materials on the matrix；With
The metal nitride materials deposited is carried out one or many heat treatment thus strengthens deposited nitride metal The crystallinity of thing material.
5. method as claimed in claim 4, wherein, is carried out once or many metal nitride materials deposited Secondary heat treatment thus strengthen the crystalline process of deposited metal nitride materials and include the metal nitrogen deposited Compound material carries out rapid thermal anneal methods.
Form described metal nitride nucleation mould the most on the matrix The process of flaggy includes utilizing halide gas phase extension (HVPE) method to form described metal nitride nucleation template layer.
7. method as claimed in claim 6, wherein, utilizes halide gas phase extension (HVPE) method to form described gold The process belonging to nitride nucleation template layer includes:
Make GaCl3、InCl3、AlCl3And TiCl4In at least one be decomposed to form terchoride Group III precursor steam, At least one in dichloride Group III precursor steam and monochloride Group III precursor steam, and
Make described Group III precursor steam and NH3Precursor vapor reaction forms described metal nitride on the matrix Nucleation template layer.
8. the method as according to any one of claim 1～7, described method also includes:
Form described metal nitride nucleation template layer in the first chamber；With
On described growing substrate, described block III-nitride semiconductor material is deposited in the second different chambers.
9. the method as according to any one of claim 1～7, described method also includes:
Form described metal nitride nucleation template layer in the chamber；With
On described growing substrate, described piece is deposited in the described chamber forming described metal nitride nucleation template layer Shape III-nitride semiconductor material.
CN201180056320.3A 2010-11-23 2011-11-23 The method forming block III-nitride material on metal nitride growth templates layer and the structure formed by described method Expired - Fee Related CN103221586B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US41652510P 2010-11-23 2010-11-23
US61/416,525 2010-11-23
FR1060271A FR2968831B1 (en) 2010-12-08 2010-12-08 METHODS OF FORMING NITRIDE III MASSIVE MATERIALS ON METAL NITRIDE GROWTH MATRIX LAYERS AND STRUCTURES FORMED THEREFROM
FR1060271 2010-12-08
PCT/EP2011/070771 WO2012069520A1 (en) 2010-11-23 2011-11-23 Methods of forming bulk iii-nitride materials on metal-nitride growth template layers, and structures formed by such methods

Publications (2)

Publication Number Publication Date
CN103221586A CN103221586A (en) 2013-07-24
CN103221586B true CN103221586B (en) 2016-08-10

Family

ID=43920644

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180056320.3A Expired - Fee Related CN103221586B (en) 2010-11-23 2011-11-23 The method forming block III-nitride material on metal nitride growth templates layer and the structure formed by described method

Country Status (7)

Country Link
JP (1) JP5892447B2 (en)
KR (1) KR20130122640A (en)
CN (1) CN103221586B (en)
DE (1) DE112011103869T5 (en)
FR (1) FR2968831B1 (en)
TW (1) TWI436409B (en)
WO (1) WO2012069520A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101713718B1 (en) 2015-02-23 2017-03-08 현대자동차 주식회사 Coating method of seperator for fuel cell and seperator for fuel cell
CN106012022A (en) * 2016-08-01 2016-10-12 中国电子科技集团公司第四十六研究所 Fe doping method capable of enhancing resistivity uniformity of semi-insulating gallium nitride monocrystals
JP7180984B2 (en) * 2018-03-01 2022-11-30 株式会社ニューフレアテクノロジー Vapor growth method
CN109468680A (en) * 2018-12-19 2019-03-15 东莞市中镓半导体科技有限公司 A kind of gas preheating unit applied to hydride gas-phase epitaxy equipment
TWI832407B (en) * 2022-09-01 2024-02-11 財團法人金屬工業研究發展中心 Plasma auxiliary annealing system and annealing method thereof
KR102546997B1 (en) * 2022-12-02 2023-06-23 이상주 Treatment device for waste gas from semiconductor manufacturing process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101816061A (en) * 2007-10-04 2010-08-25 应用材料股份有限公司 Parasitic particle suppression in the growth of III-V nitride films using MOCVD and HVPE

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5610106A (en) 1995-03-10 1997-03-11 Sony Corporation Plasma enhanced chemical vapor deposition of titanium nitride using ammonia
US6221174B1 (en) 1999-02-11 2001-04-24 Applied Materials, Inc. Method of performing titanium/titanium nitride integration
US6179913B1 (en) 1999-04-16 2001-01-30 Cbl Technologies, Inc. Compound gas injection system and methods
JP2001217193A (en) * 2000-02-01 2001-08-10 Namiki Precision Jewel Co Ltd METHOD OF FORMING AIN BUFFER LAYER, AND AlN BUFFER LAYER, AND METHOD OF FORMING GaN SINGLE CRYSTAL FILM AND GaN SINGLE CRYSTAL FILM
WO2002044444A1 (en) 2000-11-30 2002-06-06 Kyma Technologies, Inc. Method and apparatus for producing miiin columns and miiin materials grown thereon
JP3946448B2 (en) * 2001-02-08 2007-07-18 日亜化学工業株式会社 Manufacturing method of nitride semiconductor substrate
WO2002069376A1 (en) * 2001-02-27 2002-09-06 Cbl Technologies Hybrid deposition system & methods
US7427555B2 (en) * 2002-12-16 2008-09-23 The Regents Of The University Of California Growth of planar, non-polar gallium nitride by hydride vapor phase epitaxy
AU2003256522A1 (en) * 2002-12-16 2004-07-29 The Regents Of University Of California Growth of planar, non-polar a-plane gallium nitride by hydride vapor phase epitaxy
JP4361747B2 (en) * 2003-03-04 2009-11-11 東京エレクトロン株式会社 Thin film formation method
JP4765025B2 (en) * 2004-02-05 2011-09-07 農工大ティー・エル・オー株式会社 AlN epitaxial layer growth method and vapor phase growth apparatus
JP2005343736A (en) * 2004-06-02 2005-12-15 Crystal System:Kk Method and apparatus for manufacturing single crystal
JP2006096588A (en) * 2004-09-28 2006-04-13 Sumitomo Electric Ind Ltd Method for manufacturing gallium nitride self-supporting substrate
US7777217B2 (en) * 2005-12-12 2010-08-17 Kyma Technologies, Inc. Inclusion-free uniform semi-insulating group III nitride substrate and methods for making same
JP4860309B2 (en) * 2006-03-17 2012-01-25 日本碍子株式会社 Group III nitride crystal manufacturing apparatus and group III nitride crystal multilayer structure manufacturing method
WO2008064077A2 (en) 2006-11-22 2008-05-29 S.O.I.Tec Silicon On Insulator Technologies Methods for high volume manufacture of group iii-v semiconductor materials
KR101353334B1 (en) * 2006-11-22 2014-02-18 소이텍 Abatement of reaction gases from gallium nitride deposition
US7915147B2 (en) 2007-09-21 2011-03-29 Seoul Opto Device Co., Ltd. Group III nitride compound semiconductor device
WO2009108221A2 (en) 2008-02-27 2009-09-03 S.O.I.Tec Silicon On Insulator Technologies Thermalization of gaseous precursors in cvd reactors
SG173052A1 (en) 2009-03-03 2011-08-29 Soitec Silicon On Insulator Gas injectors for cvd systems with the same
JP2010251705A (en) * 2009-03-24 2010-11-04 Nuflare Technology Inc Coating apparatus and coating method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101816061A (en) * 2007-10-04 2010-08-25 应用材料股份有限公司 Parasitic particle suppression in the growth of III-V nitride films using MOCVD and HVPE

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Plasma-excited organometallic vapor phase epitaxy of GaN on (0001)sapphire;Takashi Tokuda et al.;《Journal of Crystal Growth》;19970401;第173卷(第3-4期);237-243 *
Yoshinao Kumagai et al..Thermodynamics on tri-halide vapor-phase epitaxy of GaN and InxGa1 xN using GaCl3 and InCl3.《Journal of Crystal Growth》.2001,第231卷(第1-2期),57-67. *

Also Published As

Publication number Publication date
DE112011103869T5 (en) 2013-08-22
WO2012069520A1 (en) 2012-05-31
FR2968831A1 (en) 2012-06-15
KR20130122640A (en) 2013-11-07
FR2968831B1 (en) 2012-12-21
JP2014502246A (en) 2014-01-30
CN103221586A (en) 2013-07-24
TWI436409B (en) 2014-05-01
JP5892447B2 (en) 2016-03-23
TW201250791A (en) 2012-12-16

Similar Documents

Publication Publication Date Title
CN103238203B (en) For utilizing the template layer of the improvement of HVPE technique heteroepitaxial deposition III-nitride semiconductor material
RU2718927C2 (en) Method of producing a two-dimensional material
CN103221586B (en) The method forming block III-nitride material on metal nitride growth templates layer and the structure formed by described method
US7906411B2 (en) Deposition technique for producing high quality compound semiconductor materials
EP2038456B1 (en) System and process for high volume deposition of gallium nitride
US8491720B2 (en) HVPE precursor source hardware
US8486192B2 (en) Thermalizing gas injectors for generating increased precursor gas, material deposition systems including such injectors, and related methods
US9023721B2 (en) Methods of forming bulk III-nitride materials on metal-nitride growth template layers, and structures formed by such methods
US20090223441A1 (en) High volume delivery system for gallium trichloride
TW200924854A (en) Multi-gas spiral channel showerhead
CN104067374B (en) Multiple complementary gas distribution assemblies
TW201443302A (en) Low carbon group-III nitride crystals
US9481943B2 (en) Gallium trichloride injection scheme
CN104821348B (en) The growing method and annealing device of gallium nitride crystallization
JP2012080082A (en) System and method for forming semiconductor material by atomic layer deposition
JP7349341B2 (en) Vapor phase growth apparatus and vapor phase growth method
JP5759690B2 (en) Film forming method, semiconductor device manufacturing method, and substrate processing apparatus
TW201829308A (en) A method of producing a two-dimensional material
KR20190097585A (en) Hydride Vapour Phase Epitaxy Reactor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160810

Termination date: 20181123