CN103811601A - Method for GaN base LED multi-stage buffer layer growth with sapphire substrate serving as substrate - Google Patents

Method for GaN base LED multi-stage buffer layer growth with sapphire substrate serving as substrate Download PDF

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CN103811601A
CN103811601A CN201410090745.1A CN201410090745A CN103811601A CN 103811601 A CN103811601 A CN 103811601A CN 201410090745 A CN201410090745 A CN 201410090745A CN 103811601 A CN103811601 A CN 103811601A
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CN103811601B (en
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何成中
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Ningbo anxinmei Semiconductor Co.,Ltd.
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Hefei Irico Epilight Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier

Abstract

The invention provides a method for GaN base LED multi-stage buffer layer growth with a sapphire substrate serving as a substrate. The method for growth of a multi-stage buffer layer epitaxy structure comprises the steps of enabling the substrate to undergo high-temperature cleaning treatment in hydrogen atmosphere, cooling the temperature to 600 DEG C, adjusting the epitaxy growth atmosphere to make preparations for growth of a multi-stage LT-AlGaN/MT-GaN/HT-GaN buffer layer, growing a GaN undoped layer, growing an N type GaN layer stable in doping concentration, growing a shallow quantum well layer, growing a luminous layer multiple quantum well layer, growing a low-temperature P type GaN layer, growing a PAlGaN current barrier layer, a high-temperature P type GaN layer and a P type contact layer, and adopting pure nitrogen atmosphere to perform annealing treatment after epitaxial growth is finished. The problem of large lattice mismatch between sapphire and GaN is solved well through the multi-stage LT-AlGaN/MT-GaN/HT-GaN buffer layer, penetration dislocation is reduced, crystal quality is improved, electric leakage is reduced, the brightness of an epitaxial slice is improved, and LED light-emitting efficiency is improved.

Description

A kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate
Technical field
The present invention relates to GaN based light-emitting diode (LED) technical field of material, be specially a kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate.
Background technology
Semiconductor light-emitting-diode (light-emission diodes, LED), because it has the advantages such as volume is little, energy consumption is low, the life-span is long, environmental and durable, is well applied in fields such as indicator light, display screen, backlights.At present blue, green light LED mainly uses GaN as basis material, because of GaN be direct band gap semiconductor material with wide forbidden band, its ternary alloy three-partalloy In xga 1-xn (x=0～1) can band gap can be from 0.7eV(InN) to 3.4eV(GaN) adjustable continuously, the whole region of emission wavelength covering visible light and black light.Recently along with LED is in the extensive use in white-light illuminating field, the LED of high brightness becomes the main target that people pursue.
Take sapphire as substrate, in the epitaxial layer of gallium nitride-based light-emitting diode growth course of growth, because sapphire and GaN exist significant lattice mismatch, GaN based light-emitting diode material can the very large stress of generation in growth course.This stress can have influence on the brightness of internal quantum efficiency and the epitaxial wafer of epitaxial wafer, also can have influence on antistatic effect simultaneously, and in typical epitaxial layer structure, take low temperature GaN layer as resilient coating, this layer has great role in epitaxial growth.And for resilient coating, the effect that different growing methods plays varies in size, most important effect, as discharged the stress in crystallization process, is blocked up the threading dislocation that goes out, and improves crystal mass etc.
Summary of the invention
Technical problem solved by the invention is to provide a kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate, to solve the problem in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions: a kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate, its multi-level buffer layer epitaxial structure, order from bottom to top comprises successively: substrate, multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating, GaN non-doped layer, N-type GaN layer, shallow quantum well layer, luminescent quantum trap layer, low temperature P type GaN layer, PAlGaN current barrier layer, high temperature P type GaN layer, P type contact layer, and the growing method of its epitaxial structure comprises following concrete steps:
(1) substrate is carried out in 1000-1200 ℃ of hydrogen atmosphere to high-temperature cleaning and process 5-20min, then carry out nitrogen treatment, substrate is sapphire material;
(2) temperature is dropped to 600 ℃, adjust epitaxial growth atmosphere and prepare the multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating of growth, described multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating comprises multiple overlapping LT-AlGaN/MT-GaN/HT-GaN structures successively, at high temperature through H 2the AlGaN layer of growing on the sapphire substrate of processing, epitaxial growth under 600 ℃, reaction cavity pressure 500Torr condition, thickness is 10-30nm; After AlGaN layer growth completes, temperature is increased to 1010-1100 ℃ and carries out thermal anneal process; Afterwards, MT-GaN layer carries out epitaxial growth with 4.0-10.0 μ m/h high development speed under 950 ℃, reaction cavity pressure 400Torr condition, and thickness is 0.2-2 μ m; HT-GaN layer is to carry out epitaxial growth with the low growth rate of 2.0-4.0 μ m/h under 1080 degree, reaction cavity pressure 200Torr condition in temperature, and thickness is 0.1-2 μ m, finally under 1000-1010 ℃ of condition through H 2gas disposal epitaxial surface, prepares growth next cycle, and multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure is 2-20 the cycle of overlapping growth successively;
(3) after described multistage LT-AlGaN/MT-GaN/HT-GaN buffer growth finishes, temperature is adjusted to 1000-1200 ℃, epitaxial growth thickness is the GaN non-doped layer of 0.5-2 μ m, and growth pressure is 100-300Torr, and V/III is than being 100-3000;
(4) after described GaN non-doped layer growth finishes, the N-type GaN layer of grow doping concentration stabilize, thickness is 2.4-8.4 μ m, and growth temperature is 1000-1200 ℃, and pressure is 100-600Torr, and V/III is than being 100-3000;
(5) after described N-type GaN layer growth finishes, the shallow quantum well layer of growing, described shallow quantum well layer comprises successively overlapping quantum well structure of 3-15, growth temperature is 820-920 ℃, growth pressure is 100-500Torr, and V/III is than being 300-5000, and thickness is 10-200nm;
(6) after described shallow quantum well layer growth finishes, light-emitting layer grows multiple quantum well layer, growth temperature is 700-850 ℃, and growth pressure is 100-500Torr, and V/III mol ratio is 300-5000, and described luminescent layer Multiple Quantum Well is by the In in 6-12 cycle yga 1-yn (x<y<1)/GaN Multiple Quantum Well composition, described In yga 1-yn (x<y<1) quantum well layer thickness is 2-5nm, and growth temperature is 720-820 ℃; Described GaN barrier layer thickness is 8-15nm, and growth temperature is 820-920 ℃, and growth pressure is 100-500Torr, and V/III mol ratio is 300-5000;
(7) after described luminescent layer quantum well layer growth finishes, the low temperature P type GaN layer that growth thickness is 10-100nm, growth temperature is 620-820 ℃, and growth time is 5-35min, and growth pressure is 100-500Torr, and V/III is than being 300-5000;
(8) after described low temperature P type GaN layer growth finishes, growth thickness is the PAlGaN current barrier layer of 10-200nm, growth temperature is 800-1200 ℃, growth time is 2-18min, growth pressure is 50-500Torr, V/III is than being 10-1000, and in P type AlGaN layer, the molar constituent content of Al is 5%～30%;
(9) after described PAlGaN current barrier layer growth finishes, the high temperature P type GaN layer that growth thickness is 100-800nm, growth temperature is 850-950 ℃, and growth time is 5-40min, and growth pressure is 100-500Torr, and V/III is than being 300-5000;
(10) after described high temperature P type GaN layer growth finishes, the P type contact layer that growth thickness is 5-20nm, growth temperature is 850-1050 ℃, and growth time is 1-10min, and growth pressure is 100-500Torr, and V/III is than being 1000-20000;
(11) after epitaxial growth finishes, the temperature of reative cell is down to 650-800 ℃, adopts pure nitrogen gas atmosphere to carry out annealing in process 2-15min, be then down to room temperature, subsequently, make single small-size chips through cleaning, deposition, photoetching and etching subsequent machining technology.
In the growth course of described epitaxial structure with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH 3) respectively as Ga, Al, In and N source.
In the growth course of described epitaxial structure with silane (SiH 4) and two luxuriant magnesium (CP 2mg) respectively as N, P type dopant.
In the growth course of described epitaxial structure with hydrogen (H 2) or nitrogen (N 2) as carrier gas.
Compared with public technology, there is following advantage in the present invention: the present invention better solves the Macrolattice mismatch problem between sapphire and GaN by multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure, can reduce the stress between sapphire and GaN, reduce threading dislocation, improve crystal mass, reduce electric leakage; Simultaneously, this kind of growing method can progressively be buried in oblivion the threading dislocation from substrate and the generation of GaN interface in the process of periodicity alternating growth, further reduces threading dislocation, thereby reduces the non-radiative recombination center of active area, improve the brightness of epitaxial wafer, improve LED luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure growth of epitaxial loayer of the present invention schematic diagram.
Embodiment
In order to make technological means of the present invention, creation characteristic, workflow, using method reach object and effect is easy to understand, below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate, its multi-level buffer layer epitaxial structure, order from bottom to top comprises successively: substrate, multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating, GaN non-doped layer, N-type GaN layer, shallow quantum well layer, luminescent quantum trap layer, low temperature P type GaN layer, PAlGaN current barrier layer, high temperature P type GaN layer, P type contact layer, and the growing method of its epitaxial structure comprises following concrete steps:
(1) substrate is carried out in 1000 ℃ of hydrogen atmospheres to high-temperature cleaning and process 5min, then carry out nitrogen treatment, substrate is sapphire material;
(2) temperature is dropped to 600 ℃, adjust epitaxial growth atmosphere and prepare the multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating of growth, described multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating comprises multiple overlapping LT-AlGaN/MT-GaN/HT-GaN structures successively, at high temperature through H 2the AlGaN layer of growing on the sapphire substrate of processing, epitaxial growth under 600 ℃, reaction cavity pressure 500Torr condition, thickness is 10-30nm; After AlGaN layer growth completes, temperature is increased to 1010-1100 ℃ and carries out thermal anneal process; Afterwards, MT-GaN layer carries out epitaxial growth with 4.0 μ m/h high development speed under 950 ℃, reaction cavity pressure 400Torr condition, and thickness is 0.2 μ m; HT-GaN layer carries out epitaxial growth with the low growth rate of 2.0 μ m/h under temperature is 1080 ℃, reaction cavity pressure 200Torr condition, and thickness is 0.1 μ m, finally under 1000 ℃ of conditions through H 2gas disposal epitaxial surface, prepares growth next cycle, and multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure is 2 cycles of overlapping growth successively;
(3) after described multistage LT-AlGaN/MT-GaN/HT-GaN buffer growth finishes, temperature is adjusted to 1000 ℃, epitaxial growth thickness is the GaN non-doped layer of 0.5 μ m, and growth pressure is 100Torr, and V/III ratio is 100;
(4) after described GaN non-doped layer growth finishes, the N-type GaN layer of grow doping concentration stabilize, thickness is 2.4 μ m, and growth temperature is 1000 ℃, and pressure is 100Torr, and V/III ratio is 100;
(5) after described N-type GaN layer growth finishes, the shallow quantum well layer of growing, described shallow quantum well layer comprises 3 overlapping quantum well structures successively, and growth temperature is 820 ℃, and growth pressure is 100Torr, and V/III ratio is 300, thickness is 10nm;
(6) after described shallow quantum well layer growth finishes, light-emitting layer grows multiple quantum well layer, growth temperature is 700 ℃, and growth pressure is 100Torr, and V/III mol ratio is 300, and described luminescent layer Multiple Quantum Well is by the In in 6 cycles yga 1-yn (x<y<1)/GaN Multiple Quantum Well composition, described In yga 1-yn (x<y<1) quantum well layer thickness is 2nm, and growth temperature is 720 ℃; Described GaN barrier layer thickness is 8nm, and growth temperature is 820 ℃, and growth pressure is 100Torr, and V/III mol ratio is 300;
(7) after described luminescent layer quantum well layer growth finishes, the low temperature P type GaN layer that growth thickness is 10nm, growth temperature is 620 ℃, and growth time is 5min, and growth pressure is 100Torr, and V/III ratio is 300;
(8) after described low temperature P type GaN layer growth finishes, the PAlGaN current barrier layer that growth thickness is 10nm, growth temperature is 800 ℃, and growth time is 2min, and growth pressure is 50Torr, and V/III ratio is that the molar constituent content of Al in 10, P type AlGaN layer is 5%;
(9) after described PAlGaN current barrier layer growth finishes, the high temperature P type GaN layer that growth thickness is 100nm, growth temperature is 850 ℃, and growth time is 5min, and growth pressure is 100Torr, and V/III ratio is 300;
(10) after described high temperature P type GaN layer growth finishes, growth thickness is at the P of 5nm type contact layer, and growth temperature is 850 ℃, and growth time is 1min, and growth pressure is 100Torr, and V/III ratio is 1000;
(11) after epitaxial growth finishes, the temperature of reative cell is down to 650-800 ℃, adopts pure nitrogen gas atmosphere to carry out annealing in process 2min, be then down to room temperature, subsequently, make single small-size chips through cleaning, deposition, photoetching and etching subsequent machining technology.
In the present embodiment with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH 3) respectively as Ga, Al, In and N source; With silane (SiH 4) and two luxuriant magnesium (CP 2mg) respectively as N, P type dopant, with hydrogen (H 2) as carrier gas.
Embodiment 2
A kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate, its multi-level buffer layer epitaxial structure, order from bottom to top comprises successively: substrate, multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating, GaN non-doped layer, N-type GaN layer, shallow quantum well layer, luminescent quantum trap layer, low temperature P type GaN layer, PAlGaN current barrier layer, high temperature P type GaN layer, P type contact layer, and the growing method of its epitaxial structure comprises following concrete steps:
(1) substrate is carried out in 1200 ℃ of hydrogen atmospheres to high-temperature cleaning and process 20min, then carry out nitrogen treatment, the outer sapphire material of substrate;
(2) temperature is dropped to 600 ℃, adjust epitaxial growth atmosphere and prepare the multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating of growth, described multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating comprises multiple overlapping LT-AlGaN/MT-GaN/HT-GaN structures successively, at high temperature through H 2the AlGaN layer of growing on the sapphire substrate of processing, epitaxial growth under 600 ℃, reaction cavity pressure 500Torr condition, thickness is 30nm; After AlGaN layer growth completes, temperature is increased to 1100 ℃ and carries out thermal anneal process; Afterwards, MT-GaN layer carries out epitaxial growth with 10.0 μ m/h high development speed under 950 ℃, reaction cavity pressure 400Torr condition, and thickness is 2 μ m; HT-GaN layer carries out epitaxial growth with the low growth rate of 4.0 μ m/h under temperature is 1080 ℃, reaction cavity pressure 200Torr condition, and thickness is 2 μ m, finally under 1010 ℃ of conditions through H 2gas disposal epitaxial surface, prepares growth next cycle, and multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure is 20 cycles of overlapping growth successively;
(3) after described multistage LT-AlGaN/MT-GaN/HT-GaN buffer growth finishes, temperature is adjusted to 1200 ℃, epitaxial growth thickness is the GaN non-doped layer of 2 μ m, and growth pressure is 300Torr, and V/III ratio is 3000;
(4) after described GaN non-doped layer growth finishes, the N-type GaN layer of grow doping concentration stabilize, thickness is 8.4 μ m, and growth temperature is 1200 ℃, and pressure is 600Torr, and V/III ratio is 3000;
(5) after described N-type GaN layer growth finishes, the shallow quantum well layer of growing, described shallow quantum well layer comprises 15 overlapping quantum well structures successively, and growth temperature is 920 ℃, and growth pressure is 500Torr, and V/III ratio is 5000, thickness is 200nm;
(6) after described shallow quantum well layer growth finishes, light-emitting layer grows multiple quantum well layer, growth temperature is 850 ℃, and growth pressure is 500Torr, and V/III mol ratio is 5000, and described luminescent layer Multiple Quantum Well is by the In in 12 cycles yga 1-yn (x<y<1)/GaN Multiple Quantum Well composition, described In yga 1-yn (x<y<1) quantum well layer thickness is 5nm, and growth temperature is 820 ℃; Described GaN barrier layer thickness is 15nm, and growth temperature is 920 ℃, and growth pressure is 500Torr, and V/III mol ratio is 5000;
(7) after described luminescent layer quantum well layer growth finishes, the low temperature P type GaN layer that growth thickness is 100nm, growth temperature is 820 ℃, and growth time is 35min, and growth pressure is 500Torr, and V/III ratio is 5000;
(8) after described low temperature P type GaN layer growth finishes, the PAlGaN current barrier layer that growth thickness is 200nm, growth temperature is 1200 ℃, growth time is 18min, growth pressure is 500Torr, and V/III ratio is that the molar constituent content of Al in 1000, P type AlGaN layer is 30%;
(9) after described PAlGaN current barrier layer growth finishes, the high temperature P type GaN layer that growth thickness is 800nm, growth temperature is 950 ℃, and growth time is 40min, and growth pressure is 500Torr, and V/III ratio is 5000;
(10) after described high temperature P type GaN layer growth finishes, the P type contact layer that growth thickness is 20nm, growth temperature is 1050 ℃, and growth time is 10min, and growth pressure is 500Torr, and V/III ratio is 20000;
(11) after epitaxial growth finishes, the temperature of reative cell is down to 800 ℃, adopts pure nitrogen gas atmosphere to carry out annealing in process 15min, be then down to room temperature, subsequently, make single small-size chips through cleaning, deposition, photoetching and etching subsequent machining technology.
In the present embodiment with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH 3) respectively as Ga, Al, In and N source; With silane (SiH 4) and two luxuriant magnesium (CP 2mg) respectively as N, P type dopant, with hydrogen (H 2) as carrier gas.
Embodiment 3
A kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate, its multi-level buffer layer epitaxial structure, order from bottom to top comprises successively: substrate, multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating, GaN non-doped layer, N-type GaN layer, shallow quantum well layer, luminescent quantum trap layer, low temperature P type GaN layer, PAlGaN current barrier layer, high temperature P type GaN layer, P type contact layer, and the growing method of its epitaxial structure comprises following concrete steps:
(1) substrate is carried out in 1100 ℃ of hydrogen atmospheres to high-temperature cleaning and process 10min, then carry out nitrogen treatment, the outer sapphire material of substrate;
(2) temperature is dropped to 600 ℃, adjust epitaxial growth atmosphere and prepare the multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating of growth, described multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating comprises multiple overlapping LT-AlGaN/MT-GaN/HT-GaN structures successively, at high temperature through H 2the AlGaN layer of growing on the sapphire substrate of processing, epitaxial growth under 600 ℃, reaction cavity pressure 500Torr condition, thickness is 20nm; After AlGaN layer growth completes, temperature is increased to 1050 ℃ and carries out thermal anneal process; Afterwards, MT-GaN layer carries out epitaxial growth with 5.0 μ m/h high development speed under 950 ℃, reaction cavity pressure 400Torr condition, and thickness is 1 μ m; HT-GaN layer carries out epitaxial growth with the low growth rate of 3.0 μ m/h under temperature is 1080 ℃, reaction cavity pressure 200Torr condition, and thickness is 1 μ m, finally under 1000 ℃ of conditions through H 2gas disposal epitaxial surface, prepares growth next cycle, and multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure is 15 cycles of overlapping growth successively;
(3) after described multistage LT-AlGaN/MT-GaN/HT-GaN buffer growth finishes, temperature is adjusted to 1100 ℃, epitaxial growth thickness is the GaN non-doped layer of 1 μ m, and growth pressure is 200Torr, and V/III ratio is 1000;
(4) after described GaN non-doped layer growth finishes, the N-type GaN layer of grow doping concentration stabilize, thickness is 5.0 μ m, and growth temperature is 1100 ℃, and pressure is 500Torr, and V/III ratio is 2000;
(5) after described N-type GaN layer growth finishes, the shallow quantum well layer of growing, described shallow quantum well layer comprises 12 overlapping quantum well structures successively, and growth temperature is 850 ℃, and growth pressure is 400Torr, and V/III ratio is 4000, thickness is 100nm;
(6) after described shallow quantum well layer growth finishes, light-emitting layer grows multiple quantum well layer, growth temperature is 800 ℃, and growth pressure is 400Torr, and V/III mol ratio is 4000, and described luminescent layer Multiple Quantum Well is by the In in 10 cycles yga 1-yn (x<y<1)/GaN Multiple Quantum Well composition, described In yga 1-yn (x<y<1) quantum well layer thickness is 4nm, and growth temperature is 800 ℃; Described GaN barrier layer thickness is 10nm, and growth temperature is 900 ℃, and growth pressure is 300Torr, and V/III mol ratio is 3000;
(7) after described luminescent layer quantum well layer growth finishes, the low temperature P type GaN layer that growth thickness is 50nm, growth temperature is 720 ℃, and growth time is 30min, and growth pressure is 400Torr, and V/III ratio is 3000;
(8) after described low temperature P type GaN layer growth finishes, the PAlGaN current barrier layer that growth thickness is 100nm, growth temperature is 1000 ℃, growth time is 15min, growth pressure is 400Torr, and V/III ratio is that the molar constituent content of Al in 500, P type AlGaN layer is 25%;
(9) after described PAlGaN current barrier layer growth finishes, the high temperature P type GaN layer that growth thickness is 500nm, growth temperature is 900 ℃, and growth time is 30min, and growth pressure is 300Torr, and V/III ratio is 1000;
(10) after described high temperature P type GaN layer growth finishes, the P type contact layer that growth thickness is 10nm, growth temperature is 950 ℃, and growth time is 5min, and growth pressure is 400Torr, and V/III ratio is 10000;
(11) after epitaxial growth finishes, the temperature of reative cell is down to 700 ℃, adopts pure nitrogen gas atmosphere to carry out annealing in process 10min, be then down to room temperature, subsequently, make single small-size chips through cleaning, deposition, photoetching and etching subsequent machining technology.
In the present embodiment with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH 3) respectively as Ga, Al, In and N source; With silane (SiH 4) and two luxuriant magnesium (CP 2mg) respectively as N, P type dopant, with hydrogen (H 2) as carrier gas.
The present invention better solves the Macrolattice mismatch problem between sapphire and GaN by multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure, can reduce the stress between sapphire and GaN, reduces threading dislocation, improves crystal mass, reduces electric leakage; Simultaneously, this kind of growing method can progressively be buried in oblivion the threading dislocation from substrate and the generation of GaN interface in the process of periodicity alternating growth, further reduces threading dislocation, thereby reduces the non-radiative recombination center of active area, improve the brightness of epitaxial wafer, improve LED luminous efficiency.
More than show and described basic principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Claimed scope of the present invention is defined by appending claims and equivalent thereof.

Claims (4)

1. the GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate, its multi-level buffer layer epitaxial structure, order from bottom to top comprises successively: substrate, multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating, GaN non-doped layer, N-type GaN layer, shallow quantum well layer, luminescent quantum trap layer, low temperature P type GaN layer, PAlGaN current barrier layer, high temperature P type GaN layer, P type contact layer, is characterized in that: the growing method of its epitaxial structure comprises following concrete steps:
(1) substrate is carried out in 1000-1200 ℃ of hydrogen atmosphere to high-temperature cleaning and process 5-20min, then carry out nitrogen treatment, substrate is sapphire material;
(2) temperature is dropped to 600 ℃, adjust epitaxial growth atmosphere and prepare the multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating of growth, described multistage LT-AlGaN/MT-GaN/HT-GaN resilient coating comprises multiple overlapping LT-AlGaN/MT-GaN/HT-GaN structures successively, at high temperature through H 2the AlGaN layer of growing on the sapphire substrate of processing, epitaxial growth under 600 ℃, reaction cavity pressure 500Torr condition, thickness is 10-30nm; After AlGaN layer growth completes, temperature is increased to 1010-1100 ℃ and carries out thermal anneal process; Afterwards, MT-GaN layer carries out epitaxial growth with 4.0-10.0 μ m/h high development speed under 950 ℃, reaction cavity pressure 400Torr condition, and thickness is 0.2-2 μ m; HT-GaN layer is to carry out epitaxial growth with the low growth rate of 2.0-4.0 μ m/h under 1080 degree, reaction cavity pressure 200Torr condition in temperature, and thickness is 0.1-2 μ m, finally under 1000-1010 ℃ of condition through H 2gas disposal epitaxial surface, prepares growth next cycle, and multistage LT-AlGaN/MT-GaN/HT-GaN buffer layer structure is 2-20 the cycle of overlapping growth successively;
(3) after described multistage LT-AlGaN/MT-GaN/HT-GaN buffer growth finishes, temperature is adjusted to 1000-1200 ℃, epitaxial growth thickness is the GaN non-doped layer of 0.5-2 μ m, and growth pressure is 100-300Torr, and V/III is than being 100-3000;
(4) after described GaN non-doped layer growth finishes, the N-type GaN layer of grow doping concentration stabilize, thickness is 2.4-8.4 μ m, and growth temperature is 1000-1200 ℃, and pressure is 100-600Torr, and V/III is than being 100-3000;
(5) after described N-type GaN layer growth finishes, the shallow quantum well layer of growing, described shallow quantum well layer comprises successively overlapping quantum well structure of 3-15, growth temperature is 820-920 ℃, growth pressure is 100-500Torr, and V/III is than being 300-5000, and thickness is 10-200nm;
(6) after described shallow quantum well layer growth finishes, light-emitting layer grows multiple quantum well layer, growth temperature is 700-850 ℃, and growth pressure is 100-500Torr, and V/III mol ratio is 300-5000, and described luminescent layer Multiple Quantum Well is by the In in 6-12 cycle yga 1-yn (x<y<1)/GaN Multiple Quantum Well composition, described In yga 1-yn (x<y<1) quantum well layer thickness is 2-5nm, and growth temperature is 720-820 ℃; Described GaN barrier layer thickness is 8-15nm, and growth temperature is 820-920 ℃, and growth pressure is 100-500Torr, and V/III mol ratio is 300-5000;
(7) after described luminescent layer quantum well layer growth finishes, the low temperature P type GaN layer that growth thickness is 10-100nm, growth temperature is 620-820 ℃, and growth time is 5-35min, and growth pressure is 100-500Torr, and V/III is than being 300-5000;
(8) after described low temperature P type GaN layer growth finishes, growth thickness is the PAlGaN current barrier layer of 10-200nm, growth temperature is 800-1200 ℃, growth time is 2-18min, growth pressure is 50-500Torr, V/III is than being 10-1000, and in P type AlGaN layer, the molar constituent content of Al is 5%～30%;
(9) after described PAlGaN current barrier layer growth finishes, the high temperature P type GaN layer that growth thickness is 100-800nm, growth temperature is 850-950 ℃, and growth time is 5-40min, and growth pressure is 100-500Torr, and V/III is than being 300-5000;
(10) after described high temperature P type GaN layer growth finishes, the P type contact layer that growth thickness is 5-20nm, growth temperature is 850-1050 ℃, and growth time is 1-10min, and growth pressure is 100-500Torr, and V/III is than being 1000-20000;
(11) after epitaxial growth finishes, the temperature of reative cell is down to 650-800 ℃, adopts pure nitrogen gas atmosphere to carry out annealing in process 2-15min, be then down to room temperature, subsequently, make single small-size chips through cleaning, deposition, photoetching and etching subsequent machining technology.
2. a kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate according to claim 1, is characterized in that: in the growth course of described epitaxial structure with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH 3) respectively as Ga, Al, In and N source.
3. a kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate according to claim 1, is characterized in that: in the growth course of described epitaxial structure with silane (SiH 4) and two luxuriant magnesium (CP 2mg) respectively as N, P type dopant.
4. a kind of GaN base LED multi-level buffer layer growth method take Sapphire Substrate as substrate according to claim 1, is characterized in that: in the growth course of described epitaxial structure with hydrogen (H 2) or nitrogen (N 2) as carrier gas.
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