CN106972086B - The epitaxial structure and its growing method of ultraviolet LED with gallium nitride quantum dot - Google Patents
The epitaxial structure and its growing method of ultraviolet LED with gallium nitride quantum dot Download PDFInfo
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 59
- 239000002096 quantum dot Substances 0.000 title claims abstract description 50
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 62
- 230000012010 growth Effects 0.000 claims description 33
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 229910021529 ammonia Inorganic materials 0.000 claims description 28
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 27
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- 229910052594 sapphire Inorganic materials 0.000 claims description 5
- 239000010980 sapphire Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910016920 AlzGa1−z Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000000407 epitaxy Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 229910002704 AlGaN Inorganic materials 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002477 rna polymer Polymers 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000024241 parasitism Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- H01L33/005—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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Led Devices (AREA)
Abstract
The present invention provides a kind of epitaxial structure and its growing method of the ultraviolet LED with gallium nitride quantum dot, and growing method includes the following steps：1) on substrate, grown buffer layer, non-doped layer, n-type doping layer successively from bottom to up；2) Q quantum well structure is grown in the n-type doping layer, each quantum well structure includes quantum well layer and quantum barrier layer AlyGa1‑yN, and the quantum well layer includes M AlxGa1‑xN GaN quantum dots, wherein 1≤Q≤50,1≤M≤10,0 ＜ x ＜ 1,0 ＜ y ＜ 1, x ＜ y, and Q, M are positive integer；3) on the Q quantum well structure, electronic barrier layer is grown successively from bottom to up, p-type adulterates AlvGa1‑vN layers and p-type doped gan layer, wherein 0 ＜ v ＜ 1, v ＞ y.The present invention can greatly improve electron-hole recombinations probability, improve the luminous efficiency of ultraviolet LED.
Description
Technical field
The present invention relates to a kind of epitaxial structure of ultraviolet LED more particularly to a kind of ultraviolet LEDs with gallium nitride quantum dot
Epitaxial structure and its growing method, belong to light emitting diode (Light-Emitting Diode, abbreviation LED) technical field.
Background technology
With the progress of China's scientific and technological level, manufacturing sustainable development, living standard is also constantly improved, substance
Life and cultural life, which have, significantly to be promoted.However the exacerbation of haze, water pollution etc. is to the life water increasingly improved in recent years
Flat to add flaw, the bacterium of the carryings such as air and water is corroding our health.It is various to disappear in order to protect the health of itself
Malicious sterilizing unit arises, such as air purifier, hydrotreater.And the main sterilizing function component of these sterilizing units is
Ultraviolet lamp, more popular at present is to use deep ultraviolet LED light.
The principle of ultraviolet LED sterilization is to utilize the appropriate length ultraviolet line of LED generations to the DNA of bacterium
(DNA) it is destroyed with the molecular link of ribonucleic acid (RNA), destroy original bacterial clump and the duplication of bacterium is prevented to breed, reached
To the purpose for killing bacterium.Ultraviolet-sterilization technology is irradiated using high intensity deep UV, can be by various bacteriums, virus, parasitism
Worm, algae and other pathogens are directly killed, and are widely used in the people's livelihood, medical treatment at present and are manufactured industry.
Because of the sterilizing function of deep ultraviolet LED, hot topic is also tended to the research of deep ultraviolet LED now.Deep ultraviolet LED master at present
It to use AlGaN as main growth material, required light emitting structure is grown using CVD epitaxial growth methods.Fig. 1 is existing
There are the ultraviolet AlGaN LED epitaxial structures in technology, as shown in Figure 1, the structure includes buffer layer 101, undoped AltGa1-tN
Layer 102, n-type doping AluGa1-uN layers 103, AlxGa1-xNAl quantum well layers 104, AlyGa1-yNAl quantum barrier layers 105, AlzGa1- zN electronic barrier layers 106, p-type adulterate AlvGa1-vN layers 107 and p-type doped gan layer 108.
Although current ultraviolet deep ultraviolet aluminum gallium nitride AlGaN LED are widely used.But there is also application is upper by AlGaN LED
Some problems.1, luminous efficiency is low, at present the chip of 15milx15mil light emission luminance about 2mW under 20mA driving currents, hair
Light efficiency is low to cause germicidal efficiency also relatively low；2, lead to electron hole because AlGaN quantum dots can not be formed in AlGaN Quantum Well
Recombination probability is very low.
Invention content
Based on the above reason, the present invention provides a kind of epitaxial structure of ultraviolet LED with gallium nitride quantum dot and its
Growing method, which has the quantum well structure for providing quantum dot, to improve electron-hole recombinations probability, solves
Caused by the no quantum dot low-down problem of recombination probability in AlGaN Quantum Well.
The present invention provides a kind of growing method of the epitaxial structure of the ultraviolet LED with gallium nitride quantum dot, including as follows
Step：
1) on substrate, grown buffer layer, non-doped layer, n-type doping layer successively from bottom to up；
2) in the n-type doping layer grow Q quantum well structure, each quantum well structure include quantum well layer with
Quantum barrier layer AlyGa1-yN, and the quantum well layer includes M AlxGa1-xN-GaN quantum dots, wherein 1≤Q≤50,1≤M
≤ 10,0 ＜ x ＜ 1,0 ＜ y ＜ 1, x ＜ y, and Q, M are positive integer；
3) on the Q quantum well structure, electronic barrier layer is grown successively from bottom to up, p-type adulterates AlvGa1-vN layers
With p-type doped gan layer, wherein 0 ＜ v ＜ 1, v ＞ y.
It is grown buffer layer on substrate first in step 1).Since LED epitaxial structure is mostly the nitride of metal, because
This before being passed through reactant, need in reative cell temperature and pressure controlled to enable ammonia and source metal
It resolves into respective atom and the nitride that combination reaction generates metal occurs.In specific implementation process, by the temperature of reaction chamber substrate
At 600~1000 DEG C, pressure is 100~500torr, ammonia and source metal is passed through on substrate, in the reaction condition for degree control
Under, source metal is decomposed into corresponding metallic atom, and ammonia is decomposed into nitrogen-atoms, and epitaxial structure is formed to generate metal nitride
Buffer layer.In order to control the thickness of buffer layer, in general, the injection rate of source metal is 1~300mL/min, logical
Enter after above-mentioned reactant and react 3~10min, you can on substrate at growing buffering of the thickness more than 0 and less than or equal to 100nm
Layer.Wherein, source metal can be selected as one or more in trimethyl gallium, trimethyl indium and trimethyl aluminium, then can be thought
To therefore the composition of buffer layer can be one or more of gallium nitride, indium nitride and aluminium nitride.Preferably, in order to
Avoid extinction, source metal that from being selected as trimethyl aluminium.
Secondly, after buffering grown layer growth, the temperature of reative cell can be improved to 1000~1350 DEG C, pressure
30~100torr is maintained, under the protection of hydrogen atmosphere, is passed through trimethyl gallium, trimethyl aluminium and ammonia.The step can not only
Enough make buffer layer decompose polymerization formed it is equally distributed at nuclear island, additionally it is possible to so that the reactant being newly passed through is decomposed into atom simultaneously
Chemical combination is metal nitride, to merge and grow up with nucleus island, to grow the undoped layer for being not incorporated into any impurity
AltGa1-tN.In order to control the thickness of undoped layer, in general, the injection rate of trimethyl gallium and trimethyl aluminium be 50~
1000mL/min, be passed through above-mentioned reactant and react 10~180min after, you can on the buffer layer at grow thickness be 50~
The undoped layer of 3000nm.It is 1000~3000nm n-type dopings to be subsequently introduced N-type impurity and grow thickness on undoped layer
Layer AluGa1-uN.The hetero atom introduced in the present invention is silicon atom, and the doping concentration of silicon atom is 1x1017~5x1019A cm-3。
It is the Q quantum well structure of growth in n-type doping layer in step 2).The present invention is in each quantum well structure
Quantum well layer designs, and makes to include GaN quantum dots in each quantum well layer, i.e.,：
As M=1, quantum well layer is specially AlxGa1-xN-GaN quantum dots；
As M ＞ 1, quantum well layer is specially AlxGa1-xN-GaN quantum dots/AlxGa1-xN-GaN quantum dots
......AlxGa1-xN-GaN quantum dots/AlxGa1-xN-GaN quantum dots.
Also, the aluminium content y in quantum barrier layer is required to be more than the aluminium content x in quantum well layer in the present invention.
In step 3), first, in the Al grownxGa1-xN/AlyGa1-yOne layer of 5- is grown on N multi-quantum pit structures
The electronic barrier layer Al of 100nm thicknesszGa1-zN.The purpose of this layer can also be used as high carrier simultaneously as electronic barrier layer and move
Shifting rate insert layer.Secondly, the thickness for growing high carrier concentration on this basis is more than 0 and the p-type less than 500nm is adulterated
AlvGa1-vN layers, the doping concentration of this layer is 1 × 1018~5 × 1020A cm-3.Finally, growing P-type doped gan layer, this layer
Thickness is 2~15nm, and the doping concentration of this layer is 5 × 1019~8 × 1020A cm-3, to form good Ohmic contact.
More than, just complete the growth of the completely ultraviolet LED epitaxial structure containing gallium nitride quantum dot.
The present invention effectively improves the quantity of quantum dot in aluminium gallium nitride alloy AlGaN Quantum Well, to improve electron hole
Recombination probability improves the luminescent properties of ultraviolet LED, effectively realizes the germicidal efficiency of ultraviolet LED.
Specifically, work as M=1, then the step 2) includes：
A. adjust temperature be 900~1200 DEG C, pressure be 30~200torr, be passed through hydrogen, trimethyl gallium, trimethyl aluminium,
Silicon atom and ammonia, grown quantum barrier layer AlyGa1-yN, wherein the quantum barrier layer AlyGa1-yThe base width of N is 2~25nm；
B. it is passed through hydrogen, trimethyl gallium, trimethyl aluminium and ammonia, grows the Al in the quantum well layerxGa1-xN,
Described in AlxGa1-xThe trap width of N is 1~5nm；
C. 800~1200 DEG C are cooled to, pressure is 30~200torr, is passed through hydrogen, trimethyl gallium and ammonia, is grown
The thickness of GaN quantum dots in the quantum well layer, the GaN quantum dots is 1~20 atomic level；
D. step a~c is repeated Q times.
It includes single Al that the growing method, which specifically grows quantum well layer,xGa1-xThe Quantum Well knot of N-GaN quantum-dot structures
Structure.
In addition, when 2≤M≤10, then the step 2) includes：
A. adjust temperature be 900~1200 DEG C, pressure be 30~200torr, be passed through hydrogen, trimethyl gallium, trimethyl aluminium,
Silicon atom and ammonia, grown quantum barrier layer AlyGa1-yN, wherein the quantum barrier layer AlyGa1-yThe base width of N is 2~25nm；
B. it is passed through hydrogen, trimethyl gallium, trimethyl aluminium and ammonia, grows the Al in the quantum well layerxGa1-xN,
Described in AlxGa1-xThe trap width of N is 1~5nm；
C. 800~1200 DEG C are cooled to, pressure is 30~200torr, is passed through hydrogen, trimethyl gallium and ammonia, is grown
The thickness of GaN quantum dots in the quantum well layer, the GaN quantum dots is 1~20 atomic level；
D. step B~C is repeated M times；
E. step A~D is repeated Q times.
It includes Al that the growing method, which specifically grows quantum well layer,xGa1-xN-GaN quantum dots ... AlxGa1-xN-GaN quantum
The quantum well structure of the periodic structure of point.Wherein step A, B, C is identical as step a, b, c.
It is worth noting that, in the present invention quantum dot thickness can by growth time in step c or step C and
Reactant is passed through the size of flow to adjust.
Further, the present invention is also Al to non-doped layertGa1-tN, n-type doping layer is AluGa1-uN, electronic barrier layer are
AlzGa1-zGallium aluminium content in N is limited, wherein 0 ＜ t ＜, 1,0 ＜ u ＜, 1,0 ＜ z ＜ 1, and z ＞ y.
Further, in the present invention, the foreign atom of n-type doping layer is silicon atom, and the p-type adulterates AlvGa1-vN
Layer and the foreign atom of p-type doped layer are magnesium atom, and the form that two luxuriant magnesium specifically may be used is passed through reative cell as reactant,
Wherein, the flow velocity of two luxuriant magnesium is 10~1000ml/min.
Further, the present invention is not limited the growth apparatus of light emitting diode epitaxial structure, can be that metal is organic
One kind in chemical vapor depsotition equipment, molecular beam epitaxial device or hydride gas-phase epitaxy equipment.
Meanwhile the substrate layer in sapphire, graphical sapphire, silicon, silicon carbide, glass, copper, nickel and chromium one
Kind.
The growing method of the epitaxial structure of ultraviolet LED provided by the invention with gallium nitride quantum dot, by by GaN amounts
Son point is introduced into quantum well layer, effectively improves the quantity of quantum dot in aluminium gallium nitride alloy AlGaN Quantum Well, improves electronics sky
Cave recombination probability improves the luminescent properties of uv-LED device, to make the fungicidal effectiveness of ultraviolet LED been significantly enhanced.
The present invention also provides a kind of epitaxial structures of the ultraviolet LED with gallium nitride quantum dot, should have gallium nitride quantum
The epitaxial structure of the ultraviolet LED of point is obtained according to above-mentioned growing method.
The present invention also provides a kind of ultraviolet LEDs with gallium nitride quantum dot, should be with the ultraviolet LED of gallium nitride quantum dot
Include the epitaxial structure of the above-mentioned ultraviolet LED with gallium nitride quantum dot.
The implementation of the present invention includes at least following advantage：
1) the invention has the advantages of simple structure and easy realization, and required source material is that can be realized easily needed for common production；
2) introducing of GaN quantum dots can greatly improve electron-hole recombinations probability, improve the luminous effect of ultraviolet LED
Rate；
3) wavelength of required ultraviolet LED can be controlled by controlling the thickness of GaN quantum dots.
Description of the drawings
Fig. 1 is ultraviolet AlGaN LED epitaxial structures in the prior art；
Fig. 2 is the ultraviolet AlGaN LED epitaxial structures in the embodiment of the present invention 1；
Fig. 3 is the ultraviolet AlGaN LED epitaxial structures in the embodiment of the present invention 2.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of the every other embodiment that is obtained, shall fall within the protection scope of the present invention.
Embodiment 1
1, the growth of buffer layer
MOCVD reaction chamber temperatures rise to 600 DEG C, pressure 100torr, at the same be passed through trimethyl aluminium (150ml/min) and
NH3, grow 10 minutes, in Sapphire Substrate (Al2O3) on react, generate thickness be 50nm GaN buffer layers；
2, the growth of non-doped layer
By 10 minutes, temperature is increased to 1200 DEG C, pressure is down to 50torr, is passed through hydrogen, trimethyl gallium (65ml/
Min), trimethyl aluminium (300ml/min) and NH3, it growing 120 minutes, aluminum gallium nitride nucleus is formed and is grown up in gold particle bottom,
AlGaN cross growths, it is the undoped AlGaN layers of 2um, Al content 75% to generate thickness；
3, the growth of n-type doping layer
Reaction chamber temperature is increased to 1250 DEG C, and pressure keeps 50mtorr, is passed through hydrogen, trimethyl gallium (80ml/min), three
Aluminium methyl (300ml/min) and ammonia are grown 90 minutes, the N-type AlGaN layer that generation thickness is 1500nm, Al content 75%,
The doping concentration of N-type GaN is 1 × 1019A cm-3；
4, the growth of multi-quantum pit structure
A. reaction chamber temperature is down to 1000 DEG C, pressure 50mtorr, is passed through hydrogen, trimethyl gallium (20ml/min), three
Aluminium methyl (60ml/min) and ammonia mix Si impurity, grow 2 minutes, generate the doping AlGaN quantum that thickness is 12nm and build,
Doping concentration is 1 × 1018A cm-3, Al content 60%；
B.1000 DEG C, pressure 50mtorr is passed through hydrogen, trimethyl gallium (10ml/min), trimethyl aluminium (40ml/min)
And ammonia, this layer do not mix Si, grow 0.75 minute, generate the AlGaN quantum well layers that thickness is 3nm, Al content 50%；
C. reaction chamber temperature is down to 900 DEG C, pressure 50mtorr, is passed through hydrogen, trimethyl gallium (10ml/min) and ammonia
Gas is grown 5 seconds, and growth thickness is the GaN quantum dots of 5 atomic levels；
D. repeat a-c totally 13 cycles, form the quantum well structure in 13 periods, i.e. Q=13, M=1；
5, the growth of electronic barrier layer
Reaction chamber temperature is increased to 1100 DEG C, pressure 50torr, is passed through hydrogen, trimethyl gallium (17ml/min), three
Aluminium methyl (60ml/min) and ammonia, growth time 15min generate the AlGaN electronic barrier layers that thickness is 30nm, Al content
It is 70%；
6, p-type adulterates AlvGa1-vN layers
Temperature is reduced to 950 DEG C, pressure is adjusted to 200torr, is passed through hydrogen, trimethyl gallium (40ml/min), two luxuriant magnesium
(150ml/min), ammonia are grown 25 minutes, wherein the doping concentration of Mg is 5.5 × 1019A cm-3, the thickness of this layer is
150nm；
7, the growth of p-type doped layer
950 DEG C of temperature is maintained, pressure is adjusted to 200torr, is passed through hydrogen, trimethyl gallium (40ml/min), two luxuriant magnesium
(450ml/min), ammonia, growth time are 1 minute, and the doping concentration of Mg is 2 × 1020A cm-3, generate the weight that thickness is 5nm
Mix p-type GaN layer.
So far, the epitaxial structure for the ultraviolet LED with gallium nitride quantum dot that the wavelength for completing the present embodiment is 255nm
Growth.Fig. 2 is the ultraviolet AlGaN LED epitaxial structures in the embodiment of the present invention 1.
The epitaxial structure of the present embodiment is tested as follows：
1, by the LED with this epitaxial structure, 350 μ m, 350 μm of chips are fabricated to, are passed through the electric current of 20mA, work electricity
Pressure is 6.0V, light emission luminance 4mW；
2, the uv-LED device service life with this epitaxial structure is 10,000 hours.
Embodiment 2
1, the growth of buffer layer
MOCVD reaction chamber temperatures rise to 600 DEG C, pressure 100torr, at the same be passed through trimethyl aluminium (150ml/min) and
NH3, grow 10 minutes, in Sapphire Substrate (Al2O3) on react, generate thickness be 50nm GaN buffer layers；
2, the growth of non-doped layer
By 10 minutes, temperature is increased to 1200 DEG C, pressure is down to 50torr, is passed through hydrogen, trimethyl gallium (45ml/
Min), trimethyl aluminium (300ml/min) and NH3, it growing 120 minutes, aluminum gallium nitride nucleus is formed and is grown up in gold particle bottom,
AlGaN cross growths, it is the undoped AlGaN layers of 2um, Al content 50% to generate thickness；
3, the growth of n-type doping layer
Reaction chamber temperature is increased to 1250 DEG C, and pressure keeps 50mtorr, is passed through hydrogen, trimethyl gallium (50ml/min), three
Aluminium methyl (300ml/min) and ammonia are grown 90 minutes, the N-type AlGaN layer that generation thickness is 1500nm, Al content 50%,
The doping concentration of N-type GaN is 1 × 1019A cm-3；
4, the growth of multi-quantum pit structure
A. reaction chamber temperature is down to 1000 DEG C, pressure 50mtorr, is passed through hydrogen, trimethyl gallium (12ml/min), three
Aluminium methyl (60ml/min) and ammonia mix Si impurity, grow 2 minutes, generate the doping AlGaN quantum that thickness is 12nm and build,
Doping concentration is 1 × 1018A cm-3, Al content 35%；
B.1000 DEG C, pressure 50mtorr is passed through hydrogen, trimethyl gallium (4ml/min), trimethyl aluminium (40ml/min)
And ammonia, this layer do not mix Si, grow 0.25 minute, generate the AlGaN quantum well layers that thickness is 1nm, Al content 22%；
C. reaction chamber temperature is down to 900 DEG C, pressure 50mtorr, is passed through hydrogen, trimethyl gallium (10ml/min) and ammonia
Gas is grown 1 second, and growth thickness is the GaN quantum dots of 1 atomic level；
D. repeat B-C totally 3 cycles, form AlxGa1-xN-GaN quantum dots/AlxGa1-xN-GaN quantum dots/
AlxGa1-xThe quantum well structure of N-GaN quantum dots, i.e. M=3；
E. repeat A-D totally 8 cycles, form the quantum well structure in 8 periods, i.e. Q=8；
5, the growth of electronic barrier layer
Reaction chamber temperature is increased to 1100 DEG C, pressure 50mtorr, is passed through hydrogen, trimethyl gallium (12ml/min), three
Aluminium methyl (60ml/min) and ammonia, growth time 15min generate the AlGaN electronic barrier layers that thickness is 30nm, Al content
It is 50%；
6, p-type adulterates AlvGa1-vN layers of growth
Temperature is reduced to 950 DEG C, pressure is adjusted to 200torr, is passed through hydrogen, trimethyl gallium (40ml/min), two luxuriant magnesium
(150ml/min), ammonia are grown 15 minutes, wherein the doping concentration of Mg is 5.5 × 1019A cm-3, the thickness of this layer is
90nm；
7, the growth of p-type doped layer
950 DEG C of temperature is maintained, pressure is adjusted to 200torr, is passed through hydrogen, trimethyl gallium (40ml/min), two luxuriant magnesium
(450ml/min), ammonia, growth time are 1 minute, and the doping concentration of Mg is 2 × 1020A cm-3, generate the weight that thickness is 5nm
Mix p-type GaN layer.
So far, the epitaxial structure for the ultraviolet LED with gallium nitride quantum dot that the wavelength for completing the present embodiment is 310nm
Growth, Fig. 3 are the ultraviolet AlGaN LED epitaxial structures in the embodiment of the present invention 2.
The epitaxial structure of the present embodiment is tested as follows：
1, by the LED with this epitaxial structure, 350 μ m, 350 μm of chips are fabricated to, are passed through the electric current of 20mA, work electricity
Pressure is 6.0V, light emission luminance 4mW；
2, the uv-LED device service life with this epitaxial structure is 10,000 hours.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of growing method of the epitaxial structure of the ultraviolet LED with gallium nitride quantum dot, which is characterized in that including walking as follows
Suddenly：
1) on substrate, grown buffer layer, non-doped layer, n-type doping layer successively from bottom to up；
2) Q quantum well structure is grown in the n-type doping layer, each quantum well structure includes quantum well layer and quantum
Barrier layer AlyGa1-yN, and the quantum well layer includes M AlxGa1-xN-GaN quantum dots, wherein 1≤Q≤50,1≤M≤10,
0 ＜ x ＜ 1,0 ＜ y ＜ 1, x ＜ y, and Q, M are positive integer；
3) on the Q quantum well structure, electronic barrier layer is grown successively from bottom to up, p-type adulterates AlvGa1-vN layers and p-type
Doped gan layer, wherein 0 ＜ v ＜ 1, v ＞ y.
2. growing method according to claim 1, which is characterized in that if M=1, the step 2) includes：
A. it is 900~1200 DEG C to adjust temperature, and pressure is 30~200torr；It is former to be passed through hydrogen, trimethyl gallium, trimethyl aluminium, silicon
Son and ammonia, grown quantum barrier layer AlyGa1-yN, wherein the quantum barrier layer AlyGa1-yThe base width of N is 2~25nm；
B. it is passed through hydrogen, trimethyl gallium, trimethyl aluminium and ammonia, grows the Al in the quantum well layerxGa1-xN, wherein described
AlxGa1-xThe trap width of N is 1~5nm；
C. 800~1200 DEG C are cooled to, pressure is 30~200torr；Hydrogen, trimethyl gallium and ammonia are passed through, described in growth
The thickness of GaN quantum dots in quantum well layer, the GaN quantum dots is 1~20 atomic level；
D. step a~c is repeated Q times.
3. growing method according to claim 1, which is characterized in that if 2≤M≤10, the step 2) includes：
A. it is 900~1200 DEG C to adjust temperature, and pressure is 30~200torr, and it is former to be passed through hydrogen, trimethyl gallium, trimethyl aluminium, silicon
Son and ammonia, grown quantum barrier layer AlyGa1-yN, wherein the quantum barrier layer AlyGa1-yThe base width of N is 2~25nm；
B. it is passed through hydrogen, trimethyl gallium, trimethyl aluminium and ammonia, grows the Al in the quantum well layerxGa1-xN, wherein described
AlxGa1-xThe trap width of N is 1~5nm；
C. 800~1200 DEG C are cooled to, pressure is 30~200torr, is passed through hydrogen, trimethyl gallium and ammonia, described in growth
GaN quantum dots in quantum well layer, 1~20 atomic level of thickness of the GaN quantum dots；
D. step B~C is repeated M times；
E. step A~D is repeated Q times.
4. according to any growing method of claim 2~3, which is characterized in that the non-doped layer is AltGa1-tN, N-type
Doped layer is AluGa1-uN, electronic barrier layer AlzGa1-zN, wherein 0 ＜ t ＜, 1,0 ＜ u ＜, 1,0 ＜ z ＜ 1, and z ＞ y.
5. growing method according to claim 4, which is characterized in that the buffer layer be selected from gallium nitride, indium nitride and
One or more of aluminium nitride.
6. growing method according to claim 5, which is characterized in that the foreign atom of the n-type doping layer is silicon atom,
The p-type adulterates AlvGa1-vThe foreign atom of N layers and p-type doped gan layer is magnesium atom.
7. growing method according to claim 6, which is characterized in that the growth apparatus of the epitaxial structure has selected from metal
One kind in chemical machine vapor deposition apparatus, molecular beam epitaxial device or hydride gas-phase epitaxy equipment.
8. growing method according to claim 7, which is characterized in that the substrate is selected from sapphire, silicon, silicon carbide, glass
One kind in glass, copper, nickel and chromium.
9. a kind of epitaxial structure of the ultraviolet LED with gallium nitride quantum dot, which is characterized in that according to the claims 1~8
The growing method obtains.
10. a kind of ultraviolet LED with gallium nitride quantum dot, which is characterized in that including there is nitrogen described in the claims 9
Change the epitaxial structure of the ultraviolet LED of gallium quantum dot.
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