CN103794687B - Gallium nitride based LED preparation method, gallium nitride based LED and chip - Google Patents
Gallium nitride based LED preparation method, gallium nitride based LED and chip Download PDFInfo
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- CN103794687B CN103794687B CN201410042037.0A CN201410042037A CN103794687B CN 103794687 B CN103794687 B CN 103794687B CN 201410042037 A CN201410042037 A CN 201410042037A CN 103794687 B CN103794687 B CN 103794687B
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 148
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000007704 transition Effects 0.000 claims abstract description 16
- 238000013021 overheating Methods 0.000 claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims description 24
- 230000012010 growth Effects 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 43
- 230000035882 stress Effects 0.000 description 21
- 229910052733 gallium Inorganic materials 0.000 description 15
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- -1 gallium nitrides Chemical class 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000034655 secondary growth Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JOTBHEPHROWQDJ-UHFFFAOYSA-N methylgallium Chemical compound [Ga]C JOTBHEPHROWQDJ-UHFFFAOYSA-N 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—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 having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
The embodiment of the present invention provides a kind of gallium nitride based LED preparation method, gallium nitride based LED and chip, and the method includes：Growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layers, SQW transition zone, multiple quantum well layer, P doped gallium nitride layers and contact layer successively on the substrate through Overheating Treatment；Wherein, reative cell growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layers, SQW transition zone, multiple quantum well layer, P doped gallium nitride layers and contact layer successively on the substrate through Overheating Treatment；Wherein, starting to grow in N doped gallium nitride layers to the time period for terminating to grow multiple quantum well layer, carrying out thermal anneal process at least one times.Extension internal stress can be largely reduced, the blue shift of LED is reduced, material antistatic property is lifted, and the luminous efficiency of SQW can be lifted.
Description
Technical field
The present embodiments relate to semiconductor light-emitting-diode（Light-Emitting Diode, LED）Field, especially relates to
And a kind of gallium nitride based LED preparation method, gallium nitride based LED and chip.
Background technology
Wide-band gap material with gallium nitride as representative, is the third generation semiconductor material after silicon Si and GaAs GaAs
Material, can extensively using with make LED and chip comprising the LED etc..Due to obtaining high-quality commercial bulk nitrogen at present
Change gallium crystal is relatively difficult, and general gallium nitride based LED can obtain gallium nitride film using foreign substrate extension.
But there is larger lattice mismatch between gallium nitride and substrate such as Sapphire Substrate or Si substrates, extension can be caused
Layer produces dislocation, and the dislocation of this epitaxial layer can extend and through whole epitaxial layer, and cause the semiconductor devices such as gallium nitride based LED
Internal stress it is excessive, cause band curvature, combined efficiency of the electron hole in area of having chance with to greatly reduce, so cause material resist
Antistatic property is low, the problems such as the luminous efficiency of SQW is low.
The content of the invention
The embodiment of the present invention provides a kind of gallium nitride based LED preparation method, gallium nitride based LED and chip, can be largely
Extension internal stress is reduced, the blue shift of LED is reduced, material antistatic property is lifted, and the luminous efficiency of SQW can be lifted.
In a first aspect, the embodiment of the present invention provides a kind of gallium nitride based LED preparation method, including：
Growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitrides successively on the substrate through Overheating Treatment
Layer, SQW transition zone, multiple quantum well layer, P doped gallium nitride layers and contact layer；
Wherein, starting to grow in the N doped gallium nitride layers to the time period for terminating to grow the multiple quantum well layer, entering
Capable thermal anneal process at least one times.
Second face, the embodiment of the present invention provides a kind of gallium nitride based LED, including：Nitridation prepared by gallium nitride based LED preparation method
Gallium LED.
3rd face, the embodiment of the present invention provides a kind of chip, including：At least one above-mentioned gallium nitride based LED.
Gallium nitride based LED preparation method provided in an embodiment of the present invention, gallium nitride based LED and chip, in the lining through Overheating Treatment
Growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layers, SQW transition zone, MQW successively on bottom
Layer, P doped gallium nitride layers and contact layer；Wherein, start grow N doped gallium nitride layers to terminate grow multiple quantum well layer when
Between in section, carry out thermal anneal process at least one times.So, it is many to growth is terminated by starting growth N doped gallium nitride layers
Thermal anneal process at least one times is carried out in the time period of quantum well layer can discharge outer before multiple quantum well layer growth terminates
The internal stress that epitaxial growth is accumulated, largely reduces extension internal stress so that the integrated stress reduction of gallium nitride based LED, enters
And mitigate because of the problem of the SQW band curvature that the stress causes, the blue shift of gallium nitride based LED is reduced, lift material antistatic behaviour
Can, and the luminous efficiency of SQW can be lifted.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are this hairs
Some bright embodiments, for those of ordinary skill in the art, without having to pay creative labor, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
The flow chart of the gallium nitride based LED preparation method that Fig. 1 is provided for the present invention；
The flow chart of another gallium nitride based LED preparation method that Fig. 2 is provided for the present invention；
The flow chart of another gallium nitride based LED preparation method that Fig. 3 is provided for the present invention；
The flow chart of the another gallium nitride based LED preparation method that Fig. 4 is provided for the present invention；
The structural representation of the gallium nitride based LED that Fig. 5 is provided for the present invention；
The structural representation of the chip that Fig. 6 is provided for the present invention；
The brightness contrast figure of sample is obtained for the gallium nitride based LED for providing of the invention for Fig. 7；
The blue shift comparison diagram of sample is obtained for the gallium nitride based LED for providing of the invention for Fig. 8.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
It should be noted that the method can be implemented in growth apparatus such as various reative cells, reative cell can be metal
Organic chemical vapor deposition equipment（Metal-organic Chemical Vapor Deposition, MOCVD）, outside molecular beam
Rolling equipment（Molecular Beam Epitaxy, MBE）Or hydride gas-phase epitaxy equipment（Hydride Vapor Phase
Epitaxy, HVPE）, it is preferred that gallium nitride based LED can be prepared using MOCVD reative cells.
The flow chart of the gallium nitride based LED preparation method that Fig. 1 is provided for the present invention, as shown in figure 1, the method includes：
S101, reative cell growing gallium nitride nucleating layer, undoped gallium nitride layer, N successively on the substrate through Overheating Treatment
Doped gallium nitride layer, SQW transition zone, multiple quantum well layer, P doped gallium nitride layers and contact layer；Wherein, start growth N mix
In miscellaneous gallium nitride layer to the time period for terminating to grow multiple quantum well layer, thermal anneal process at least one times is carried out.
Further, multiple quantum well layer includes at least one set of barrier layer, well layer and trap clad for growing successively.
Further, it is 100 DEG C~700 DEG C, preferably 500 DEG C~600 DEG C that the annealing temperature of thermal anneal process can be；
Annealing temperature rate can be 50 DEG C/min~100 DEG C/min；Annealing residence time can be 1min~10min, preferably
It is 3min~5min；The gas of annealing can be H2, can be N2, or H2And N2Mixed gas.
For example, the flow chart of another gallium nitride based LED preparation method that Fig. 2 is provided for the present invention, as shown in Fig. 2
Start to grow in N doped gallium nitride layers to the time period for terminating to grow multiple quantum well layer, carry out at least one times that thermal anneal process can
To be preferably at the end of N doped gallium nitride layers are grown, thermal anneal process is carried out.
Preferably, the present embodiment can use MOCVD reative cell next life high-brightness GaN LED long, such as can be with
Using high-purity H2, high-purity N2, or high-purity H2With high-purity N2Mixed gas do carrier gas, high-purity N H3Do N sources, metallorganic front three
Base gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N type dopant is 200ppm silane SiH4, p-type doping
Agent is two luxuriant magnesium Cp2Mg, substrate is the sapphire PSS in 002 face, wherein, multiple quantum well layer is to be grown successively according to setting cycle
Barrier layer, well layer and trap clad.The value of setting cycle can be the arbitrary value in 2-20, and the present embodiment is taken with setting cycle
Value is illustrated as a example by 7~13.
Temperature is risen to 1080 DEG C by S201, MOCVD reative cell, under 200Torr pressure, the high temperature of 5min is carried out to substrate
Treatment.
S202, MOCVD reative cell by greenhouse cooling to 530 DEG C, under 200Torr pressure, Grown 35nm's
Gallium nitride nucleating layer.
Temperature is warmed up to 1080 DEG C by S203, MOCVD reative cell, raw on gallium nitride nucleating layer under 200Torr pressure
Undoped gallium nitride layer long 1.7 μm.
S204, MOCVD reative cell are by temperature drop and are maintained at 1070 DEG C, under 200Torr pressure, in undoped p nitridation
The N doped gallium nitride layers of 3.2 μm of growth on gallium layer, wherein N doping concentrations are 5E+18atom/cm3。
S205, MOCVD reative cell reduce the temperature to 500 DEG C in 300s, and stopping 3min carries out thermal anneal process.
Temperature is raised to 850 DEG C by S206, MOCVD reative cell in 250s, under 200Torr pressure, the N after thermal annealing
The SQW transition zone of 300nm is grown in doped gallium nitride layer, wherein N doping concentrations are 8E+17atom/cm3, In components are many
The 30% of quantum well layer.
Temperature is raised to 870 DEG C by S207, MOCVD reative cell, under 200Torr pressure, grows the barrier layer of 13.5nm.
S208, MOCVD reative cell reduce the temperature to 760 DEG C, under 200Torr pressure, the trap of 2.5nm are grown in barrier layer
Layer.
S209, MOCVD reative cell maintain temperature at 760 DEG C, under 200Torr pressure, the trap bag of 2nm are grown in well layer
Coating.
It is repeated in S207, S208 and S209, number of repetition 7~13.
It should be noted that the barrier layer of the first secondary growth is in the growth of SQW transition zone, the barrier layer of the second secondary growth
It is to be grown on the trap clad of the first secondary growth, the barrier layer for growing later is by that analogy.
Temperature is increased to 870 DEG C by S210, MOCVD reative cell, under 200Torr pressure, 8nm is grown on trap clad
Last barrier layer.
It should be noted that can be as multiple quantum well layer by this part that S207 is formed to completion S210.
Temperature is increased to 980 DEG C by S211, MOCVD reative cell, under 200Torr pressure, is grown in last barrier layer
The P doped gallium nitride layers of 250nm.
S212, MOCVD reaction chamber temperature drop to 750 DEG C, under 200Torr pressure, are grown in P doped gallium nitride layers
The contact layer of 2nm, and 10min is maintained, do last thermal anneal process.
For example, contact layer can be metal contact layer.
Again for example, the flow chart of another gallium nitride based LED preparation method that Fig. 3 is provided for the present invention, as shown in figure 3,
Starting to grow in N doped gallium nitride layers to the time period for terminating to grow multiple quantum well layer, carrying out thermal anneal process at least one times
Can be preferably at the end of grown quantum trap transition zone, during the value for carrying out thermal anneal process setting cycle can be 2-20
Arbitrary value, the present embodiment is illustrated so that the value of setting cycle is 7~13 as an example.
Preferably, the present embodiment can also use MOCVD reative cell next life high-brightness GaN LED long, such as may be used
To use high-purity H2, high-purity N2, or high-purity H2With high-purity N2Mixed gas do carrier gas, high-purity N H3Do N sources, metallorganic three
Methyl gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N type dopant is 200ppm silane SiH4, and p-type is mixed
Miscellaneous dose is two luxuriant magnesium Cp2Mg, substrate is the sapphire PSS in 002 face.
Further, the present embodiment is also with setting cycle number as 1 one combination layer of growth for example, but not appointed with this
What is limited.
S301, MOCVD reaction chamber temperature rise to 1080 DEG C, under 200Torr pressure, substrate are carried out at the high temperature of 5min
Reason.
S302, MOCVD reative cell by greenhouse cooling to 530 DEG C, under 200Torr pressure, Grown 35nm's
Gallium nitride nucleating layer.
Temperature is warmed up to 1080 DEG C by S303, MOCVD reative cell, raw on gallium nitride nucleating layer under 200Torr pressure
Undoped gallium nitride layer long 1.7 μm.
S304, MOCVD reative cell are by temperature drop and are maintained at 1070 DEG C, under 200Torr pressure, in undoped p nitridation
The N doped gallium nitride layers of 3.2 μm of growth on gallium layer, wherein N doping concentrations are 5E+18atom/cm3。
S305, MOCVD reative cell reduce the temperature to 850 DEG C in 250s, under 200Torr pressure, in N doped gallium nitrides
The SQW transition zone of 300nm is grown on layer, wherein N doping concentrations are 8E+17atom/cm3, In components are multiple quantum well layer
30%。
S306, MOCVD reative cell reduce the temperature to 500 DEG C in 300s, and stopping 3min carries out thermal anneal process.
Temperature is raised to 870 DEG C by S307, MOCVD reative cell in 100~300s, under 200Torr pressure, growth
The barrier layer of 13.5nm.
S308, MOCVD reative cell reduce the temperature to 760 DEG C, under 200Torr pressure, the trap of 2.5nm are grown in barrier layer
Layer.
S309, MOCVD reative cell maintain temperature at 760 DEG C, under 200Torr pressure, the trap bag of 2nm are grown in well layer
Coating.
It is repeated in S307, S308 and S309, number of repetition 7~13.
Temperature is increased to 870 DEG C by S310, MOCVD reative cell, under 200Torr pressure, 8nm is grown on trap clad
Last barrier layer.
Temperature is increased to 980 DEG C by S311, MOCVD reative cell, under 200Torr pressure, is grown in last barrier layer
The P doped gallium nitride layers of 250nm.
S312, MOCVD reaction chamber temperature drop to 750 DEG C, under 200Torr pressure, are grown in P doped gallium nitride layers
The contact layer of 2nm, and 10min is maintained, do last thermal anneal process.
Again for example, the flow chart of the another gallium nitride based LED preparation method that Fig. 4 is provided for the present invention, as shown in figure 4,
Starting to grow in N doped gallium nitride layers to the time period for terminating to grow multiple quantum well layer, carrying out thermal anneal process at least one times
Can be preferably in multiple quantum well layer is grown, terminate to carry out a thermal anneal process during growth trap clad every time, wherein, it is many
Quantum well layer includes at least one set of barrier layer, well layer and trap clad for growing successively.During the value of setting cycle can be 2-20
Arbitrary value, the present embodiment illustrates so that the value of setting cycle is 7~13 as an example.
Preferably, the present embodiment can also use MOCVD reative cell next life high-brightness GaN LED long, such as may be used
To use high-purity H2, high-purity N2, or high-purity H2With high-purity N2Mixed gas do carrier gas, high-purity N H3Do N sources, metallorganic three
Methyl gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N type dopant is 200ppm silane SiH4, p-type mixes
Miscellaneous dose is two luxuriant magnesium Cp2Mg, substrate is the sapphire PSS in 002 face.
S401, MOCVD reaction chamber temperature rise to 1080 DEG C, under 200Torr pressure, substrate are carried out at the high temperature of 5min
Reason.
S402, MOCVD reative cell by greenhouse cooling to 530 DEG C, under 200Torr pressure, Grown 35nm's
Gallium nitride nucleating layer.
Temperature is warmed up to 1080 DEG C by S403, MOCVD reative cell, raw on gallium nitride nucleating layer under 200Torr pressure
Undoped gallium nitride layer long 1.7 μm.
S404, MOCVD reative cell are by temperature drop and are maintained at 1070 DEG C, under 200Torr pressure, in undoped p nitridation
The N doped gallium nitride layers of 3.2 μm of growth on gallium layer, wherein N doping concentrations are 5E+18atom/cm3。
S405, MOCVD reative cell reduce the temperature to 850 DEG C, under 200Torr pressure, are grown in N doped gallium nitride layers
The SQW transition zone of 300nm, wherein N doping concentrations are 8E+17atom/cm3, In components are the 30% of multiple quantum well layer.
Temperature is raised to 870 DEG C by S406, MOCVD reative cell, under 200Torr pressure, grows the barrier layer of 13.5nm.
S407, MOCVD reative cell reduce the temperature to 760 DEG C, under 200Torr pressure, the trap of 2.5nm are grown in barrier layer
Layer.
S408, MOCVD reative cell maintain temperature at 760 DEG C, under 200Torr pressure, the trap bag of 2nm are grown in well layer
Coating.
S409, MOCVD reative cell reduce the temperature to 500 DEG C in 300s, and stopping 3min carries out thermal anneal process.
It is repeated in S406, S407, S408 and S409, number of repetition 7~13.
Temperature is increased to 870 DEG C by S410, MOCVD reative cell, under 200Torr pressure, 8nm is grown on trap clad
Last barrier layer.
Temperature is increased to 980 DEG C by S411, MOCVD reative cell, under 200Torr pressure, is grown in last barrier layer
The P doped gallium nitride layers of 250nm.
S412, MOCVD reaction chamber temperature drop to 750 DEG C, under 200Torr pressure, are grown in P doped gallium nitride layers
The contact layer of 2nm, and 10min is maintained, do last thermal anneal process.
In the gallium nitride based LED preparation method that above-mentioned Fig. 1 is provided and the gallium nitride based LED preparation method that Fig. 2~Fig. 4 is enumerated
Thermal anneal process is simple, be able to can be realized on any epitaxial device, and the angularity of epitaxial wafer is influenced whether due to thermal annealing,
Therefore epitaxial wafer angularity when multiple quantum well layer is grown can be controlled by controlling annealing time, annealing temperature rate,
So as to improve wavelength uniformity.It is topmost, can effectively be discharged before multiple quantum well layer grows terminate completely by thermal annealing
The extension internal stress of accumulation so that the integrated stress of gallium nitride based LED is reduced, and then the SQW band curvature that stress causes subtracts
Gently, the luminous efficiency of SQW is lifted；And the reduction of extension internal stress can reduce the blue shift of gallium nitride based LED, lifting material resists
Antistatic property and ageing properties.Sum it up, the method can effectively reduce the internal stress of device, the luminous effect of SQW is improved
Rate, reduces the blue shift of gallium nitride based LED, lifts material antistatic property and ageing properties.
The structural representation of the gallium nitride based LED that Fig. 5 is provided for the present invention, as shown in figure 5, gallium nitride based LED 50 includes：
Growing gallium nitride nucleating layer 502, undoped gallium nitride layer 503, N are mixed successively on the substrate 501 through Overheating Treatment
Miscellaneous gallium nitride layer 504, SQW transition zone 505, multiple quantum well layer 506, P doped gallium nitride layers 507 and contact layer 508, wherein,
Multiple quantum well layer 506 is to grow barrier layer 5061, well layer 5062 and trap clad 5063 successively according to setting cycle.Setting cycle
Value is N, and N can be the arbitrary value in 2-20.
It should be noted that gallium nitride based LED 50 is the method provided using above-mentioned Fig. 1~Fig. 4 preparing.
Gallium nitride based LED provided in an embodiment of the present invention, preparation method includes：Grown successively on the substrate through Overheating Treatment
Gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layers, SQW transition zone, multiple quantum well layer, P doped gallium nitrides
Layer and contact layer；Wherein, start grow N doped gallium nitride layers to terminate grow multiple quantum well layer time period in, carry out to
A few thermal anneal process.So, by starting to grow N doped gallium nitride layers to the time for terminating growth multiple quantum well layer
What the epitaxial growth that thermal anneal process at least one times is carried out in section can be discharged before multiple quantum well layer growth terminates was accumulated
Internal stress, largely reduces extension internal stress so that the integrated stress reduction of gallium nitride based LED, and then mitigates because of the stress
The problem of the SQW band curvature for causing, reduces the blue shift of gallium nitride based LED, lifts material antistatic property, and can lifting capacity
The luminous efficiency of sub- trap.
Yet further, the structural representation of the chip that Fig. 6 is provided for the present invention, as shown in fig. 6, chip 1 is included at least
The gallium nitride based LED 50 that one Fig. 5 is provided.
For example, it is possible to use the gallium nitride based LED preparation method that Fig. 2 is provided obtains the gallium nitride of structure such as Fig. 5
LED50, is named as sample a；The gallium nitride based LED preparation method that Fig. 3 is provided can be utilized to obtain the gallium nitride of structure such as Fig. 5
LED50, is named as sample b；The gallium nitride based LED preparation method that Fig. 4 is provided can be utilized to obtain the gallium nitride of structure such as Fig. 5
LED50, is named as sample c.
The gallium nitride based LED that recycling prior art prepares a structure such as Fig. 5 under equal ambient is as a comparison sample, life
Entitled sample d.MOCVD reative cell next life high-brightness GaN LED long is used, high-purity H can be such as used2, it is high-purity
N2, or high-purity H2With high-purity N2Mixed gas do carrier gas, high-purity N H3Do N sources, metallorganic trimethyl gallium TMGa or three second
Base gallium TEGa does gallium source, and trimethyl indium does indium source, and N type dopant is 200ppm silane SiH4, P-type dopant is two luxuriant magnesium
Cp2Mg, substrate is the sapphire PSS in 002 face.Specific growth pattern is as follows：MOCVD reaction chamber temperatures rise to 1080 DEG C,
Under 200Torr pressure, the high-temperature process of 5min is carried out to substrate；By greenhouse cooling to 530 DEG C, under 200Torr pressure, in lining
The gallium nitride nucleating layer of 35nm is grown on bottom；Temperature is warmed up to 1080 DEG C, under 200Torr pressure, in gallium nitride nucleating layer
The undoped gallium nitride layer of upper 1.7 μm of growth；By temperature drop and 1070 DEG C are maintained at, under 200Torr pressure, in undoped p
3.2 μm of N doped gallium nitride layers are grown on gallium nitride layer, wherein N doping concentrations are 5E+18atom/cm3；Reduce the temperature to 850
DEG C, under 200Torr pressure, the SQW transition zone of 300nm being grown in N doped gallium nitride layers, wherein N doping concentrations are 8E
+17atom/cm3, In components are the 30% of multiple quantum well layer；Temperature is raised to 870 DEG C, under 200Torr pressure, growth
The barrier layer of 13.5nm；760 DEG C are reduced the temperature to, under 200Torr pressure, the well layer of 2.5nm is grown in barrier layer；Maintain temperature
At 760 DEG C, under 200Torr pressure, the trap clad of 2nm is grown in well layer；Be repeated in S403, S407, S408 and
S409, number of repetition 7~13；Temperature is increased to 870 DEG C, under 200Torr pressure, 8nm is grown most on trap clad
Barrier layer afterwards；Temperature is increased to 980 DEG C, under 200Torr pressure, the P doped gallium nitrides of 250nm is grown in last barrier layer
Layer；Temperature drops to 750 DEG C, under 200Torr pressure, the contact layer of 2nm is grown in P doped gallium nitride layers, and maintain
10min, does last thermal anneal process.
Above-mentioned sample a, sample b, sample c and sample d are made as the chip of 430 μm of 350 μ m respectively, Fig. 7 is this hair
The gallium nitride based LED of bright offer is obtained the brightness contrast figure of sample, as shown in fig. 7, the sample a that three embodiments of the invention are provided
Sample b and sample c brightness ratio samples d improve 1%~2%.The blue shift of sample is obtained for the gallium nitride based LED for providing of the invention for Fig. 8
Comparison diagram, as shown in figure 8, the sample a samples b and sample c brightness ratio samples d of three embodiments of the invention offer are reduced
0.2nm~0.5nm.It can be said that bright, the present invention can effectively discharge gallium nitride based LED epitaxial material by thermal anneal process method
Internal stress, reduce the SQW band curvature caused by internal stress, reduce the blue shift of LED, lift material antistatic property, and
The luminous efficiency of SQW can be lifted.
Chip including at least one gallium nitride based LED provided in an embodiment of the present invention, on the substrate through Overheating Treatment according to
Secondary growth gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layers, SQW transition zone, multiple quantum well layer, P doping
Gallium nitride layer and contact layer；Wherein, start grow N doped gallium nitride layers to terminate grow multiple quantum well layer time period in,
Carry out thermal anneal process at least one times.So, by start growth N doped gallium nitride layers to terminate grow multiple quantum well layer
Time period in carry out thermal anneal process at least one times can discharge multiple quantum well layer growth terminate before epitaxial growth institute
The internal stress of accumulation, largely reduce extension internal stress so that gallium nitride based LED integrated stress reduction, and then mitigate because
The problem of the SQW band curvature that the stress causes, reduces the blue shift of gallium nitride based LED, lifts material antistatic property, and energy
Lift the luminous efficiency of SQW.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
Pipe has been described in detail with reference to foregoing embodiments to the present invention, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (6)
1. a kind of gallium nitride based LED preparation method, it is characterised in that including：
On the substrate through Overheating Treatment successively growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layers, amount
Sub- trap transition zone, multiple quantum well layer, P doped gallium nitride layers and contact layer；
Wherein, starting to grow in the N doped gallium nitride layers to the time period for terminating to grow the multiple quantum well layer, carry out to
A few thermal anneal process；
It is described starting to grow in the N doped gallium nitride layers to the time period for terminating to grow the multiple quantum well layer, carry out to
A few thermal anneal process includes：
In the multiple quantum well layer is grown, terminate to carry out once the thermal anneal process during growth trap clad every time, wherein,
The multiple quantum well layer is at least one set of barrier layer, well layer and the trap clad grown successively according to setting cycle；
Temperature before the thermal anneal process is 760 DEG C, and the annealing temperature of the thermal anneal process is 500 DEG C~600 DEG C, annealing
Temperature rate is 50 DEG C/min~100 DEG C/min, and annealing time is 3min~5min, and the gas of annealing is hydrogen H2And/or
Nitrogen N2。
2. method according to claim 1, it is characterised in that described to start to grow the N doped gallium nitride layers to tying
In the time period of multiple quantum well layer described in Shu Shengchang, carrying out thermal anneal process at least one times includes：
At the end of the N doped gallium nitride layers are grown, the thermal anneal process is carried out.
3. method according to claim 1, it is characterised in that described to start to grow the N doped gallium nitride layers to tying
In the time period of multiple quantum well layer described in Shu Shengchang, carrying out thermal anneal process at least one times includes：
At the end of the SQW transition zone is grown, the thermal anneal process is carried out.
4. method according to claim 1, it is characterised in that the setting cycle number is arbitrary value in 2-20.
5. a kind of gallium nitride based LED, it is characterised in that prepared including the gallium nitride based LED according to any one of Claims 1 to 4
Gallium nitride based LED prepared by method.
6. a kind of chip, it is characterised in that including the gallium nitride based LED described at least one claim 5.
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| CN105355650A (en) * | 2015-10-30 | 2016-02-24 | 江苏能华微电子科技发展有限公司 | Epitaxial wafer for Schottky diodes and preparation method thereof |
| CN106981549B (en) * | 2017-04-19 | 2023-05-23 | 华南理工大学 | Gallium nitride nano-pillar LED epitaxial wafer grown on silicon substrate and preparation method thereof |
| CN113451460B (en) * | 2020-11-20 | 2022-07-22 | 重庆康佳光电技术研究院有限公司 | Light emitting device and method of manufacturing the same |
| CN112993099B (en) * | 2021-02-09 | 2022-06-10 | 厦门乾照光电股份有限公司 | Manufacturing method of LED chip with protective layer |
| CN112964976B (en) * | 2021-05-19 | 2021-08-17 | 浙江杭可仪器有限公司 | Gallium nitride device ageing oven |
| CN118053943B (en) * | 2024-04-16 | 2024-07-12 | 南昌凯迅光电股份有限公司 | Epitaxial growth method of gallium arsenide triple-junction solar cell |
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