CN108807625A - A kind of AlN buffer layer structures and preparation method thereof - Google Patents
A kind of AlN buffer layer structures and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000004888 barrier function Effects 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000003491 array Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052594 sapphire Inorganic materials 0.000 claims description 7
- 239000010980 sapphire Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 235000010210 aluminium Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910010936 LiGaO2 Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000002950 deficient Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract description 3
- 239000002061 nanopillar Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- -1 LaSrAlTaO6 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- H01L33/02—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
- H01L33/12—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 stress relaxation structure, e.g. buffer layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01L33/0066—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
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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
- H01L33/02—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
- H01L33/20—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 particular shape, e.g. curved or truncated substrate
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Abstract
The invention discloses a kind of AlN buffer layer structures, including substrate, AlN nano column arrays buffer layer, AlGaN buffer layers, n-GaN layers, multiple quantum wells, electronic barrier layer, P-GaN.Wherein, AlN buffer layer structures are nano-pillar array structure.Relative to film-type buffer layer, the contact area of nano column array buffer layer and substrate is small, and stress is easy to get release, is substantially shorter crack length；Nanometer column material is defective from effect is excluded, and can substantially reduce defect concentration.Based on above 2 points, using AlN nano column arrays as padded coaming, it is more easy to obtain the GaN film of flawless high quality, and then promote the overall performance of GaN base LED component.Meanwhile the invention also discloses AlN buffer layer structure preparation methods, and LED epitaxial wafer is prepared using two-step method, first use PECVD growing AIN nano-array buffer layers, then grow subsequent material with MOCVD, hence it is evident that improve the preparation efficiency of LED epitaxial wafer.
Description
Technical field
The invention belongs to technical field of semiconductors, it is related to a kind of AlN buffer layers and preparation method thereof more particularly to a kind of Si
The AlN buffer layer structures and preparation method thereof of GaN base light emitting on substrate.
Background technology
Light emitting diode (light-emitting diode, LED) because with efficiently, it is energy conservation and environmental protection, the long-life, small
The advantages that, it is expected to the lighting source for replacing traditional incandescent lamp, fluorescent lamp and gas-discharge lamp to become a new generation, causes industry
And the extensive concern of scientific research field.It is born so far from first LED in 1962, the various aspects of performance of LED is obtained for greatly
It is promoted, application field is also increasingly wider.
Currently, LED will really realize extensive extensive use, the luminous efficiency for further increasing LED chip is needed.However
Commercialized LED luminous efficiencies are still to be improved, this is primarily due to using caused by epitaxial growth in Sapphire Substrate.One
Aspect causes to form very high dislocation during extension GaN film since the lattice mismatch of sapphire and GaN are up to 13.3%
Density shortens carrier lifetime to reduce the carrier mobility of material, finally affects the performance of GaN base device.
On the other hand, due to sapphire (coefficient of thermal expansion 6.63 × 10 at room temperature-6K-1) and GaN (coefficient of thermal expansion 5.6 × 10-6K-1)
Between thermal mismatching degree it is high, after outer layer growth, device will produce from the High-temperature cooling of epitaxial growth to room temperature process
Prodigious compression is easy to cause the cracking of film and substrate.Further, since sapphire thermal conductivity is low, it is 25W/ at room temperature
MK leads to thermal accumlation it is difficult to which the heat generated in chip is discharged in time, so that the internal quantum efficiency of device is reduced, finally
Influence the performance of device.
In this context, mature production technology and can with lower cost obtain large-area high-quality Si substrates can be effective
The manufacturing cost of LED is reduced, while being also quite suitable for preparing high-power LED device.In the early period of Si substrates LED development,
Since Si substrates and GaN there are thermal mismatching, lattice mismatch and return the problems such as melting etching, the difficulty of the GaN film of flawless high quality
To obtain.For this problem, general thinking is the shape be inserted into AlN and AlGaN thin film buffer layers and carry out Comprehensive Control GaN growth
Nuclear process and stress state, but the GaN film quality obtained is still unsatisfactory.
Invention content
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of AlN buffer layer structures, it is adopted
With AlN nano column array buffer layers, relative to film-type buffer layer, the contact area of nano column array buffer layer and substrate is small,
Stress is easy to get release, is substantially shorter crack length；Nanometer column material is defective from effect is excluded, and can substantially reduce defect
Density.Based on above 2 points, using AlN nano column arrays as padded coaming, it is more easy to obtain the GaN film of flawless high quality,
And then promote the overall performance of GaN base LED component.
The second object of the present invention is to provide a kind of preparation method of AlN buffer layer structures, using two-step method preparation LED
Epitaxial wafer first uses PECVD growing AIN nano-array buffer layers, then grows subsequent material with MOCVD, hence it is evident that improves LED extensions
The preparation efficiency of piece.
An object of the present invention adopts the following technical scheme that realization：
A kind of AlN buffer layer structures, which is characterized in that it includes substrate, grows AlN nano-pillar battle arrays successively on substrate
Row buffer layer, AlGaN buffer layers, GaN three-dimension layers, n-GaN layers, InGaN/GaN multiple quantum well layers, electronic barrier layer and p-GaN
Layer.
Further, the substrate includes sapphire, Si, SiC, GaN, ZnO, LiGaO2、LaSrAlTaO6, Al or Cu.
Further, the height of the AlN nano column arrays buffer layer is 200-400nm.
Further, the thickness of the AlGaN buffer layers is respectively 400-500nm, wherein the molar ratio shared by Al components
Example is 10%-90%；The thickness of the GaN three-dimension layers is 500-1500nm.
Further, n-GaN layers of the thickness is 1500-3000nm, and Si doping concentrations are 1 × 1017-1×1019cm-3。
Further, the InGaN/GaN multiple quantum well layers are multicycle repetitive structure, each period by quantum barrier layer and
Quantum well layer forms；The material of quantum barrier layer is GaN, InGaN, AlGaN or AlInGaN, and the material of quantum well layer is InGaN；
The band gap of quantum barrier layer material is bigger than the band gap of Quantum well layer materials；The thickness of quantum barrier layer is bigger than the thickness of quantum well layer；It is more
The periodicity of Quantum Well is 3-20；Last layer of the multiple quantum wells is quantum barrier layer.
Further, the material of the electronic barrier layer is AlGaN, InAlN or AlInGaN, thickness 20-50nm, Mg
Doping concentration is 1 × 1017-1×1019cm-3。
Further, the thickness of the p-GaN layer is 200-300nm, and Mg doping concentrations are 1 × 1017-1×1019cm-3。
The second object of the present invention adopts the following technical scheme that realization：
A kind of preparation method of AlN buffer layer structures, which is characterized in that including：
1) growth step of AlN nano column arrays buffer layer：Using plasma reinforced chemical vapour deposition technique in substrate
Upper growing AIN nano column array buffer layer；
2) AlGaN buffer layers, GaN three-dimension layers, n-GaN layers of growth step：Using metal organic chemical vapor deposition work
Skill grown successively on AlN nano column array buffer layers AlGaN buffer layers, GaN three-dimension layers, n-GaN layers；
3) InGaN/GaN multiple quantum well layers growth step：It is raw at n-GaN layers using metal organic chemical vapor deposition technique
Long InGaN/GaN multiple quantum well layers；
4) electronic barrier layer, p-GaN layer growth step：Using metal organic chemical vapor deposition technique in multiple quantum wells
Electronic barrier layer, p-GaN layer are grown on layer successively.
Further,
In step 1), concrete technology condition is as follows：Reaction chamber temperature remains 750 DEG C, radio-frequency power 150W, AlCl powder
Addition be 0.500g, be passed through the ammonia of 100sccm and the argon gas of 30sccm；
In step 2), concrete technology condition is as follows：
The process conditions of AlGaN buffer layers are：Reaction chamber temperature is 1000 DEG C, and chamber pressure 100Torr is passed through
The trimethyl aluminium of the ammonia of 180sccm, the hydrogen of 60sccm, the trimethyl gallium of 300sccm and 250sccm；；
U-GaN layers of process conditions are：Reaction chamber temperature is 800 DEG C, and chamber pressure 200Torr is passed through 200sccm
Ammonia, 100sccm nitrogen and 380sccm trimethyl galliums；N-GaN layers of process conditions are：Reaction chamber temperature is 1000 DEG C, reaction
Chamber pressure is 200Torr, is passed through the trimethyl of the silane of 60sccm, the ammonia of 200sccm, the nitrogen of 100sccm, 380sccm
Gallium；In step 3), concrete technology condition is as follows：
3-1) reaction chamber temperature remains 850 DEG C, and air pressure remains 100Torr, is passed through 60sccm silane, 250sccm ammonia
Gas, 100sccm nitrogen and 380sccm trimethyl galliums grow GaN barrier layers on n-GaN layers；
3-2) reaction chamber temperature remains 750 DEG C, and air pressure remains 200Torr, is passed through 250sccm ammonias, 100sccm nitrogen
Gas, 380sccm trimethyl galliums and 80sccm trimethyl indiums grow InGaN potential well layers on GaN barrier layers；
3-3) according to the cycle-index of setting successively circulating repetition step 3-1) and step 3-2), it is more to obtain InGaN/GaN
Quantum Well；
In step 4), concrete technology condition is as follows：
The process conditions of electronic barrier layer are：Reaction chamber temperature is 900 DEG C, and chamber pressure 100Torr is passed through
The luxuriant magnesium of 50sccm bis-, 250sccm ammonias, 100sccm nitrogen, 380sccm trimethyl galliums and 150sccm trimethyl aluminiums；
The process conditions of p-GaN layer are：Reaction chamber temperature is 900 DEG C, and chamber pressure 100Torr is passed through 50sccm
Two luxuriant magnesium, 250sccm ammonias, 100sccm nitrogen and 380sccm trimethyl galliums.Compared with prior art, beneficial effects of the present invention
It is：
The present invention is using AlN nano column arrays as buffer layer, relative to film-type buffer layer, nano column array buffer layer with
The contact area of substrate is small, and stress is easy to get release, is substantially shorter crack length；Nanometer column material is defective from exclusion effect
It answers, defect concentration can be substantially reduced.Based on above 2 points, using AlN nano column arrays as padded coaming, it is more easy to obtain flawless
The GaN film of high quality, and then promote the electric property of GaN base LED component.Meanwhile LED epitaxial wafer is prepared using two-step method,
PECVD growing AIN nano-array buffer layers are first used, then subsequent material is grown with MOCVD, hence it is evident that improve the system of LED epitaxial wafer
Standby efficiency.
Description of the drawings
Fig. 1 is the structural schematic diagram of the AlN buffer layer structures in embodiment 1；
In Fig. 1：1, substrate；2, AlN nano column arrays buffer layer；3, AlGaN buffer layers；4, GaN three-dimension layers；5,n-GaN
Layer；6, InGaN/GaN multiple quantum well layers；61, InGaN potential well layers；62, GaN barrier layers；7, electronic barrier layer；8, P-GaN layers.
Fig. 2 is the vertical view of AlN nano column array buffer layers in embodiment 1.
Fig. 3 is the x-ray diffraction collection of illustrative plates using the GAN (0002) of AlN nano column array buffer layers.
Fig. 4 is the x-ray diffraction collection of illustrative plates using the GAN (0002) of AlN thin film buffer layers.
Fig. 5 is the x-ray diffraction collection of illustrative plates using the GAN (1012) of AlN nano column array buffer layers.
Fig. 6 is the x-ray diffraction collection of illustrative plates using the GAN (1012) of AlN thin film buffer layers.
Fig. 7 is the LED chip electrical test results figure using AlN nano column array buffer layers.
Fig. 8 is the LED chip electrical test results figure using AlN thin film buffer layers.
Specific embodiment mode
In the following, in conjunction with attached drawing and specific embodiment mode, the present invention is described further, it should be noted that
Under the premise of not colliding, new reality can be formed between various embodiments described below or between each technical characteristic in any combination
Apply example.In addition to specified otherwise, employed in the present embodiment to material and equipment be commercially available.
A kind of AlN buffer layer structures comprising substrate, grow successively on substrate AlN nano column arrays buffer layer,
AlGaN buffer layers, GaN three-dimension layers, n-GaN layers, InGaN/GaN multiple quantum well layers, electronic barrier layer and p-GaN layer.
As preferred embodiment, the substrate includes sapphire, Si, SiC, GaN, ZnO, LiGaO2、
LaSrAlTaO6, Al or Cu.
As preferred embodiment, the height of the AlN nano column arrays buffer layer is 200-400nm.
As preferred embodiment, the thickness of the AlGaN buffer layers is respectively 400-500nm, wherein Al components institute
The molar ratio accounted for is 10%-90%.
As preferred embodiment, the thickness of the GaN three-dimension layers is 500-1500nm.
As preferred embodiment, n-GaN layers of the thickness is 1500-3000nm, and Si doping concentrations are 1 × 1017-
1×1019cm-3。
As preferred embodiment, the InGaN/GaN multiple quantum well layers be multicycle repetitive structure, each period by
Quantum barrier layer and quantum well layer composition；The material of quantum barrier layer is GaN, InGaN, AlGaN or AlInGaN, the material of quantum well layer
Material is InGaN；The band gap of quantum barrier layer material is bigger than the band gap of Quantum well layer materials；The thickness of quantum barrier layer is than quantum well layer
Thickness is big；The periodicity of multiple quantum wells is 3-20；Last layer of the multiple quantum wells is quantum barrier layer.
As preferred embodiment, the material of the electronic barrier layer is AlGaN, InAlN or AlInGaN, and thickness is
20-50nm, Mg doping concentration are 1 × 1017-1×1019cm-3。
As preferred embodiment, the thickness of the p-GaN layer is 200-300nm, and Mg doping concentrations are 1 × 1017-1
×1019cm-3。
A kind of preparation method of AlN buffer layer structures, which is characterized in that including：
1) growth step of AlN nano column arrays buffer layer：Using plasma reinforced chemical vapour deposition technique in substrate
Upper growing AIN nano column array buffer layer；
2) AlGaN buffer layers, GaN three-dimension layers, n-GaN layers of growth step：Using metal organic chemical vapor deposition work
Skill grown successively on AlN nano column array buffer layers AlGaN buffer layers, GaN three-dimension layers, n-GaN layers；
3) InGaN/GaN multiple quantum well layers growth step：It is raw at n-GaN layers using metal organic chemical vapor deposition technique
Long InGaN/GaN multiple quantum well layers；
4) electronic barrier layer, p-GaN layer growth step：Using metal organic chemical vapor deposition technique in multiple quantum wells
Electronic barrier layer, p-GaN layer are grown on layer successively.
As preferred embodiment,
In step 1), concrete technology condition is as follows：Reaction chamber temperature remains 750 DEG C, radio-frequency power 150W, AlCl powder
Addition be 0.500g, be passed through the ammonia of 100sccm and the argon gas of 30sccm；
In step 2), concrete technology condition is as follows：
The process conditions of AlGaN buffer layers are：Reaction chamber temperature is 1000 DEG C, and chamber pressure 100Torr is passed through
The trimethyl aluminium of the ammonia of 180sccm, the hydrogen of 60sccm, the trimethyl gallium of 300sccm and 250sccm；
U-GaN layers of process conditions are：Reaction chamber temperature is 800 DEG C, and chamber pressure 200Torr is passed through 200sccm
Ammonia, 100sccm nitrogen and 380sccm trimethyl galliums；
N-GaN layers of process conditions are：Reaction chamber temperature is 1000 DEG C, and chamber pressure 200Torr is passed through 60sccm
Silane, the ammonia of 200sccm, the nitrogen of 100sccm, 380sccm trimethyl gallium；In step 3), concrete technology condition is such as
Under：
3-1) reaction chamber temperature remains 850 DEG C, and air pressure remains 100Torr, is passed through 60sccm silane, 250sccm ammonia
Gas, 100sccm nitrogen and 380sccm trimethyl galliums grow GaN barrier layers on n-GaN layers；
3-2) reaction chamber temperature remains 750 DEG C, and air pressure remains 200Torr, is passed through 250sccm ammonias, 100sccm nitrogen
Gas, 380sccm trimethyl galliums and 80sccm trimethyl indiums grow InGaN potential well layers on GaN barrier layers；
3-3) according to the cycle-index of setting successively circulating repetition step 3-1) and step 3-2), it is more to obtain InGaN/GaN
Quantum Well；
In step 4), concrete technology condition is as follows：
The process conditions of electronic barrier layer are：Reaction chamber temperature is 900 DEG C, and chamber pressure 100Torr is passed through
The luxuriant magnesium of 50sccm bis-, 250sccm ammonias, 100sccm nitrogen, 380sccm trimethyl galliums and 150sccm trimethyl aluminiums；P-GaN layer
Process conditions be：Reaction chamber temperature is 900 DEG C, chamber pressure 100Torr, is passed through the luxuriant magnesium of 50sccm bis-, 250sccm ammonia
Gas, 100sccm nitrogen and 380sccm trimethyl galliums.Embodiment 1：
Referring to Fig.1, the present invention provides a kind of AlN buffer layer structures comprising substrate is grown successively on substrate
AlN nano column arrays buffer layer, AlGaN buffer layers, GaN three-dimension layers, n-GaN layers, InGaN/GaN multiple quantum well layers, electronics resistance
Barrier and p-GaN layer.
Present embodiment discloses the crystal quality by increasing GaN epitaxy film using AlN nano column arrays as buffer layer
With the LED epitaxial wafer structure of electric property comprising Si substrates 1, the AlN nano column arrays buffer layer 2 for being highly 300nm, thickness
Degree is the Al of 400nm0.7Ga0.3GaN three-dimension layers 4 that N buffer layers 3, thickness are 500nm, thickness are 1.5 μm, Si doping concentrations are 1
×1018cm-3N-GaN layers 5, overall thickness be 100nm (wherein, the GaN multiple quantum wells potential barrier of InGaN/GaN multiple quantum well layers 6
The thickness of layer 61 is 12nm, In0.15Ga0.85The thickness of N multiple quantum wells potential well layer 62 is 8nm, grows the multiple quantum wells in 5 periods),
20nm it is thick, Mg doping concentrations be 1 × 1018cm-3Al0.15Ga0.85N electronic barrier layers 7 and thickness be 200nm it is thick, Mg mixes
Miscellaneous a concentration of 1 × 1018cm-3P-GaN layer 8.
A kind of preparation method of AlN buffer layer structures, including steps are as follows：
1) growth step of AlN nano column arrays buffer layer：Using plasma reinforced chemical vapour deposition technique in substrate
Upper growing AIN nano column array buffer layer；
At room temperature, single crystalline Si (111) substrate is put into 10% hydrofluoric acid solution and is cleaned by ultrasonic 30 seconds, then use deionization
Water is cleaned by ultrasonic 60 seconds, finally puts it into spare with the drying of high-purity drying nitrogen in dryer；Single crystalline Si (111) substrate is sent
Enter in PECVD reative cells, reaction chamber temperature remains 750 DEG C, and radio-frequency power 150W, AlCl powder 0.500g is passed through 100sccm
Ammonia and 30sccm argon gas, growing AIN nano column array buffer layer 2 on substrate, thickness 300nm；
2) AlGaN buffer layers, GaN three-dimension layers, n-GaN layers of growth step：Using metal organic chemical vapor deposition work
Skill grown successively on AlN nano column array buffer layers AlGaN buffer layers, GaN three-dimension layers, n-GaN layers；
Reaction chamber temperature remains 1000 DEG C, and air pressure remains 100Torr, is passed through the ammonia of 180sccm, the hydrogen of 60sccm
The trimethyl aluminium of gas, the trimethyl gallium of 300sccm and 250sccm grows Al on AlN nano column arrays buffer layer 20.7Ga0.3N
Buffer layer 3, thickness 400nm；
Reaction chamber temperature remains 800 DEG C, and air pressure remains 200Torr, be passed through 200sccm ammonias, 100sccm nitrogen and
380sccm trimethyl galliums grow GaN three-dimension layers 4, thickness 500nm on AlGaN buffer layers 3；
Answer room temperature to remain 1000 DEG C, air pressure remains 100Torr, be passed through 60sccm silane, 250sccm ammonias,
100sccm nitrogen, 380sccm trimethyl galliums grow n-GaN layers 5 in GaN three-dimension layers 4, and thickness is 1.5 μm, Si doping concentrations
It is 1 × 1018cm-3。
3) InGaN/GaN multiple quantum well layers growth step：It is raw at n-GaN layers using metal organic chemical vapor deposition technique
Long InGaN/GaN multiple quantum well layers；
3-1) reaction chamber temperature remains 850 DEG C, and air pressure remains 100Torr, is passed through 60sccm silane, 250sccm ammonia
Gas, 100sccm nitrogen and 380sccm trimethyl galliums, grow GaN barrier layers 61 on n-GaN layers 5, thickness 3.0nm, and Si mixes
Miscellaneous a concentration of 1 × 1018cm-3；
3-2) reaction chamber temperature remains 750 DEG C, and air pressure remains 200Torr, is passed through 250sccm ammonias, 100sccm nitrogen
Gas, 380sccm trimethyl galliums and 80sccm trimethyl indiums, grow In on GaN barrier layers 610.15Ga0.85N potential well layers 62, thickness
For 8nm；
Circulating repetition step 3-1 successively) and 3-2) each 5 times, obtain InGaN/GaN multiple quantum wells 6；
4) electronic barrier layer, p-GaN layer growth step：Using metal organic chemical vapor deposition technique in multiple quantum wells
Electronic barrier layer, p-GaN layer are grown on layer successively.
Reaction chamber temperature remains 900 DEG C, and air pressure remains 100Torr, be passed through the luxuriant magnesium of 50sccm bis-, 250sccm ammonias,
100sccm nitrogen, 380sccm trimethyl galliums and 150sccm trimethyl aluminiums；InGaN/GaN multiple quantum wells 6 described in step 8
Upper growth Al0.15Ga0.85N electronic barrier layers 7, thickness 20nm, doping concentration 1 × 1018cm-3；
Reaction chamber temperature is kept for 900 DEG C, and air pressure remains 100Torr, be passed through the luxuriant magnesium of 50sccm bis-, 250sccm ammonias,
100sccm nitrogen and 380sccm trimethyl galliums, in Al0.15Ga0.85P-GaN layer 8 is grown on N electronic barrier layers 7, thickness is
200nm, Mg doping concentration are 1 × 1018cm-3。
N-GaN layers 5 are the cores of LED epitaxial wafer, and the GaN layer for preparing flawless high quality is efficient GaN base LED epitaxial wafer
Basis.Common AlN, AlGaN thin-film material as buffer layer, though can evade Si substrates and GaN thermal mismatchings, lattice mismatch and
The problems such as melting etching is returned, but therefore the crystal quality of GaN epitaxy film and electric property then receive the matter of AlN and AlGaN films
Amount restricts.
Embodiment 2：
The characteristics of the present embodiment is：In step 3), the multiple quantum wells in 6 periods is grown；It is other same as Example 1.
Embodiment 3：
The characteristics of the present embodiment is：In step 3), the multiple quantum wells in 7 periods is grown；It is other same as Example 1.
Embodiment 4：
The characteristics of the present embodiment is：In step 3), the multiple quantum wells in 10 periods is grown；It is other same as Example 1.
Comparative example 1：
The characteristics of the present embodiment is：AlN nano column array buffer layers are replaced using AlN films, it is other with 1 phase of embodiment
Together.
Performance detection：
1, XRD, the i.e. abbreviation of X-ray diffraction, are X-ray diffractions, by carrying out X-ray diffraction to material,
Its diffracting spectrum is analyzed, the research means of the information such as the ingredient of material, the structure of material internal atom or molecule or form are obtained.
With reference to Fig. 3-6, relative to comparative example 1 using AlN films as buffer layer, embodiment 1 uses AlN nano column arrays
After buffer layer, the crystal quality of GaN film, which has, to be obviously improved：GaN (0002) improves 200arcsec, GaN
(1012) 321arcsec is improved, illustrates to be more easy to obtain the GaN film of high quality as buffer layer using AlN nano column arrays.
2.LED chip electrical performance testings：It is tested using LED point measurement machines：
With reference to Fig. 7-8, relative to comparative example 1 using AlN films as buffer layer, embodiment 1 uses AlN nano column arrays
After buffer layer, under the test condition of@5.0000mA, and emission wavelength close to 449nm when, the LED of identical size
The average canbdle power of chip improves 83mW or so, has and is obviously improved explanation using AlN nano column arrays as buffering
Layer can significantly improve the electric property of LED.
The above embodiment is merely a preferred embodiment of the present invention mode, cannot limit the model protected of the present invention with this
It encloses, the variation and replacement of any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to the present invention
Range claimed.
Claims (10)
1. a kind of AlN buffer layer structures, which is characterized in that it includes substrate, grows AlN nano column arrays successively on substrate
Buffer layer, AlGaN buffer layers, GaN three-dimension layers, n-GaN layers, InGaN/GaN multiple quantum well layers, electronic barrier layer and p-GaN layer.
2. AlN buffer layer structures as described in claim 1, which is characterized in that the substrate include sapphire, Si, SiC,
GaN、ZnO、LiGaO2、LaSrAlTaO6, Al or Cu.
3. AlN buffer layer structures as described in claim 1, which is characterized in that the height of the AlN nano column arrays buffer layer
For 200-400nm.
4. AlN buffer layer structures as described in claim 1, which is characterized in that the thickness of the AlGaN buffer layers is respectively
400-500nm, wherein the molar ratio shared by Al components is 10%-90%；The thickness of the GaN three-dimension layers is 500-
1500nm。
5. AlN buffer layer structures as described in claim 1, which is characterized in that n-GaN layers of the thickness is 1500-
3000nm, Si doping concentration are 1 × 1017-1×1019cm-3。
6. AlN buffer layer structures as described in claim 1, which is characterized in that the InGaN/GaN multiple quantum well layers are mostly all
Phase repetitive structure, each period are made of quantum barrier layer and quantum well layer；The material of quantum barrier layer be GaN, InGaN, AlGaN or
The material of AlInGaN, quantum well layer are InGaN；The band gap of quantum barrier layer material is bigger than the band gap of Quantum well layer materials；Quantum is built
The thickness of layer is bigger than the thickness of quantum well layer；The periodicity of multiple quantum wells is 3-20；Last layer of the multiple quantum wells is built for quantum
Layer.
7. AlN buffer layer structures as described in claim 1, which is characterized in that the material of the electronic barrier layer be AlGaN,
InAlN or AlInGaN, thickness 20-50nm, Mg doping concentration are 1 × 1017-1×1019cm-3。
8. AlN buffer layer structures as described in claim 1, which is characterized in that the thickness of the p-GaN layer is 200-300nm,
Mg doping concentrations are 1 × 1017-1×1019cm-3。
9. the preparation method of the AlN buffer layer structures as described in claim 1-8 any one, which is characterized in that including：
1) growth step of AlN nano column arrays buffer layer：It is given birth on substrate using plasma reinforced chemical vapour deposition technique
Long AlN nano column arrays buffer layer；
2) AlGaN buffer layers, GaN three-dimension layers, n-GaN layers of growth step：Existed using metal organic chemical vapor deposition technique
Grown successively on AlN nano column array buffer layers AlGaN buffer layers, GaN three-dimension layers, n-GaN layers；
3) InGaN/GaN multiple quantum well layers growth step：It is grown at n-GaN layers using metal organic chemical vapor deposition technique
InGaN/GaN multiple quantum well layers；
4) electronic barrier layer, p-GaN layer growth step：Using metal organic chemical vapor deposition technique on multiple quantum well layer
Electronic barrier layer, p-GaN layer are grown successively.
10. the preparation method of AlN buffer layer structures as claimed in claim 9, which is characterized in that
In step 1), concrete technology condition is as follows：Reaction chamber temperature remains 750 DEG C, and radio-frequency power 150W, AlCl powder adds
It is 0.500g to enter amount, is passed through the ammonia of 100sccm and the argon gas of 30sccm；
In step 2), concrete technology condition is as follows：
The process conditions of AlGaN buffer layers are：Reaction chamber temperature is 1000 DEG C, and chamber pressure 100Torr is passed through
The trimethyl aluminium of the ammonia of 180sccm, the hydrogen of 60sccm, the trimethyl gallium of 300sccm and 250sccm；
U-GaN layers of process conditions are：Reaction chamber temperature is 800 DEG C, and chamber pressure 200Torr is passed through 200sccm ammonia
Gas, 100sccm nitrogen and 380sccm trimethyl galliums；
N-GaN layers of process conditions are：Reaction chamber temperature is 1000 DEG C, and chamber pressure 200Torr is passed through the silicon of 60sccm
The trimethyl gallium of alkane, the ammonia of 200sccm, the nitrogen of 100sccm, 380sccm；
In step 3), concrete technology condition is as follows：
3-1) reaction chamber temperature remains 850 DEG C, and air pressure remains 100Torr, be passed through 60sccm silane, 250sccm ammonias,
100sccm nitrogen and 380sccm trimethyl galliums grow GaN barrier layers on n-GaN layers；
3-2) reaction chamber temperature remains 750 DEG C, and air pressure remains 200Torr, be passed through 250sccm ammonias, 100sccm nitrogen,
380sccm trimethyl galliums and 80sccm trimethyl indiums grow InGaN potential well layers on GaN barrier layers；
3-3) according to the cycle-index of setting successively circulating repetition step 3-1) and step 3-2), obtain InGaN/GaN Multiple-quantums
Trap；
In step 4), concrete technology condition is as follows：
The process conditions of electronic barrier layer are：Reaction chamber temperature is 900 DEG C, and chamber pressure 100Torr is passed through 50sccm bis-
Luxuriant magnesium, 250sccm ammonias, 100sccm nitrogen, 380sccm trimethyl galliums and 150sccm trimethyl aluminiums；
The process conditions of p-GaN layer are：Reaction chamber temperature is 900 DEG C, chamber pressure 100Torr, is passed through bis- cyclopentadienyls of 50sccm
Magnesium, 250sccm ammonias, 100sccm nitrogen and 380sccm trimethyl galliums.
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