CN104733571B - A kind of LED epitaxial growth methods - Google Patents
A kind of LED epitaxial growth methods Download PDFInfo
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- CN104733571B CN104733571B CN201510068384.5A CN201510068384A CN104733571B CN 104733571 B CN104733571 B CN 104733571B CN 201510068384 A CN201510068384 A CN 201510068384A CN 104733571 B CN104733571 B CN 104733571B
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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
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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
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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
- H01L33/04—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
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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
- H01L33/26—Materials of the light emitting region
- H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table
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Abstract
The present invention provides a kind of new LED epitaxial growth methods, can effectively lift LED internal quantum efficiency, improve the luminous intensity of LED, and be improved LED emission wavelength stability.The LED epitaxial growth methods, including low temperature buffer layer, non-impurity-doped high-temperature gan layer, the high-temperature gan layer for mixing Si, In are carried out successivelyxGa1‑xN/AlyGa1‑yN multiple quantum well layers, p AlGaN layers and mix Mg p GaN layers growth, 0≤x≤1,0≤y≤1；The In at least one cyclexGa1‑xMultiple In of lattice constant smaller are inserted during N quantum trap growthsaGa1‑aN thin layers, 0≤a ＜ x≤1；The Al at least one cycleyGa1‑yN quantum build multiple Al that lattice constant bigger is inserted in growth coursebGa1‑bN thin layers, 0≤b ＜ y≤1.
Description
Technical field：
The invention belongs to semi-conductor electronic device technology of preparing, more particularly to a kind of new LED epitaxial growth methods.
Background technology：
In recent years, tri-nitride is widely used in the photoelectric devices such as light emitting diode, laser and detector and shows
Go out good development prospect.GaN base light emitting (LEDs) is to be applied to the most promising solid state light emitter of general illumination in future,
Its extensive use can save mass energy.Common LED epitaxial growth technologies are：Using MOCVD device, first blue precious
Stone Grown buffer cushions, then grow one layer of non-impurity-doped high-temperature gan layer, the high temperature n- that Si is mixed in one layer of regrowth
GaN, to provide compound electronics, then grows InxGa1-xN/AlyGa1-yN (0≤x≤1,0≤y≤1) multiple quantum well layer, connects
One layer p-AlGaN layers of regrowth, last one layer of p-GaN layer for mixing Mg of regrowth, to provide luminous compound hole.Growth
During most critical link be multiple quantum well layer growth, the design of multiple quantum well layer directly determines the emission wavelength of LED,
The key parameter such as brightness and device stability, therefore, the design of multiple quantum well layer enjoys people to pay close attention to always.
At present, growing GaN is grown along the C faces direction of hexagonal crystal mostly, since crystal is this side up
Lack inversion symmetry, there is strong spontaneous polarization, and in multiple quantum wells, quantum is built and the lattice of quantum-well materials
Size has differences, this causes in this two layers of interface there are stress, so that piezoelectric polarization is produced, spontaneous polarization and piezoelectricity pole
Change collective effect, the strong polarized electric field produced in the direction of growth of GaN.The polarized electric field that this polarity effect produces is not
Effective energy gap can only be changed so that blue shift occurs under the conditions of Bulk current injection for LED emission wavelengths, reduces the stabilization of device
Property, also separate will the both hole and electron spatial distribution wave function in Quantum Well, cause LED internal quantum efficiency to reduce, shine
Intensity decreases.
The content of the invention：
The present invention provides a kind of new LED epitaxial growth methods, can effectively lift LED internal quantum efficiency, improve the hair of LED
Luminous intensity, and it is improved LED emission wavelength stability.
Technical scheme is as follows：
A kind of LED epitaxial growth methods, including low temperature buffer layer, non-impurity-doped high-temperature gan layer, the high temperature for mixing Si are carried out successively
GaN layer, InxGa1-xN/AlyGa1-yN multiple quantum well layers, p-AlGaN layers and mix Mg p-GaN layer growth, 0≤x≤1,0≤
y≤1；Be different from the prior art is：The In at least one cyclexGa1-xIt is normal that lattice is inserted during N quantum trap growths
Multiple In of number smalleraGa1-aN thin layers, 0≤a ＜ x≤1；The Al at least one cycleyGa1-yN quantum, which are built in growth course, to be inserted
Multiple Al of lattice constant bigger are enteredbGa1-bN thin layers, 0≤b ＜ y≤1.
Also optimized as follows based on the above scheme present invention：
In the In of a cyclexGa1-xThe In of 1~5 insertion is shared during N quantum trap growthsaGa1-aN thin layers, it is each
InaGa1-aThe thickness of N thin layers is 0.3~2.0nm；In the Al of a cycleyGa1-yN quantum, which are built in growth course, shares 1~20
The Al of insertionbGa1-bN thin layers, every AlbGa1-bThe thickness of N thin layers is 0.3~2.0nm.
InxGa1-xAll cycles of N Quantum Well are inserted into multiple InaGa1-aN thin layers, and/or AlyGa1-yThe institute that N quantum are built
There is the cycle to be inserted into multiple AlbGa1-bN thin layers.
InxGa1-xThe growth course in each cycle of N Quantum Well is identical, AlyGa1-yThe growth in each cycle that N quantum are built
Process is identical.
In the In of a cyclexGa1-xThe In of 2 insertions is shared during N quantum trap growthsaGa1-aN thin layers, it is each
InaGa1-aThe thickness of N thin layers is 0.8nm；In the Al of a cycleyGa1-yN quantum build growth course in share 5 insertion
AlbGa1-bN thin layers, every AlbGa1-bThe thickness of N thin layers is 1.0nm.
Correspondingly, the present invention also provides a kind of LED epitaxial structure, including the low temperature buffer layer, the non-impurity-doped that grow successively are high
Warm GaN layer, the high-temperature gan layer for mixing Si, InxGa1-xN/AlyGa1-yN multiple quantum well layers, p-AlGaN layers and mix the p-GaN of Mg
Layer, 0≤x≤1,0≤y≤1；It is characterized in that：The In at least one cyclexGa1-xInserted with lattice constant in N Quantum Well
Multiple In of smalleraGa1-aN thin layers, 0≤a ＜ x≤1；The Al at least one cycleyGa1-yN quantum are normal inserted with lattice in building
Multiple Al of number biggerbGa1-bN thin layers, 0≤b ＜ y≤1.For the LED epitaxial structure, also as foregoing epitaxial growth method is made
Corresponding optimization.
Beneficial effects of the present invention are as follows：
The present invention is in InxGa1-xThe In of lattice constant smaller is inserted in N Quantum WellaGa1-aN (0≤a ＜ x≤1) layer, has
Effect make use of interfacial polarization effect, and the electric field opposite with former polarized electric field direction is formd in Quantum Well, weakens electric field pair
The influence of electron hole distribution.Again because insertion layer thickness is sufficiently thin, so that carrier can be freely from insert layer potential barrier
Tunnelling, can be neglected the presence of potential barrier.Two kinds of factor collective effects, so that producing such as Fig. 3 effects, Quantum Well is divided into multiple portions
Point, but macroscopic quantum trap angle of inclination is obviously reduced compared with Fig. 1 (traditional quantum well structure), that is, adds electron hole in Quantum Well
Wave function overlap area, improves LED internal quantum efficiency, luminescence enhancement.And in Bulk current injection, effective energy gap becomes
Change and reduce, even if the stability of LED emission wavelengths is improved.
The present invention is in AlyGa1-yN quantum insert the Al of lattice constant bigger in buildingbGa1-bN, (0≤b ＜ y≤1) thin layer,
Principle is same as above, and macroscopical can be improved quantum and be built tilt phenomenon, so as to make in limitation of the guarantee quantum barrier layer to quantum well layer carrier
With while, the height of quantum barrier layer is reduced, so that the operating voltage of LED is reduced.
Brief description of the drawings：
Fig. 1 is that traditional quantum well structure can band schematic diagram.
Fig. 2 is quantum well structure design diagram of the present invention.
Fig. 3 can band final effect schematic diagram for quantum well structure of the present invention.
Embodiment：
The present invention is described in further detail below in conjunction with the accompanying drawings.
The present invention uses metallo-organic compound chemical gaseous phase deposition (MOCVD) growth technology, using trimethyl gallium
(TMGa), triethyl-gallium (TEGa), and trimethyl indium (TMIn), trimethyl aluminium (TMAl) and ammonia (NH3) silane (SiH4) and two
Luxuriant magnesium (cp2mg) provides growth required gallium source, indium source, silicon source, nitrogen source, silicon source and magnesium source respectively.
As shown in Fig. 2, in InxGa1-xThe thin layer of lattice constant smaller is inserted in N quantum well layers, is such as inserted into InaGa1-aN,
0≤a ＜ x≤1；In AlyGa1-yThe thin layer of lattice constant bigger is inserted in N quantum barrier layers, is such as inserted into AlbGa1-bN, 0≤b ＜ y
≤1。
The In of insertionaGa1-aThe thickness of N thin layers is 0.3~2.0nm, and the number of plies for being inserted into Quantum Well is 1~5 layer, different
The number of plies of Quantum Well insertion can be different, and the optimal number of plies of being inserted into is to be inserted into 2 layers with about 0.8nm thickness.
The Al of insertionbGa1-bThe thickness of N thin layers is 0.3~2.0nm, and the number of plies that insertion quantum is built is 1~20 layer, different
The number of plies that quantum builds insertion can be different, and the optimal number of plies of being inserted into is to be inserted into 5 layers with 1.0nm thickness.
Using the polarized electric field formed between insert layer and quantum well layer, inclined energy band is adjusted, increases quantum
Electron-hole wave functions overlapping area in trap, so as to improve LED internal quantum efficiency, enhancing shines.
Insert layer in quantum base macroscopical can improve quantum and build tilt phenomenon, so as to ensure quantum barrier layer to Quantum Well
While the restriction effect of layer carrier, the height of quantum barrier layer is reduced, effectively reduces LED operation voltage.
Embodiment one (present invention)
1. the Sapphire Substrate after cleaning is put into MOCVD device, toasted 10 minutes at 1100 DEG C.
2. the low-temperature gan layer that 620 DEG C of growth a layer thickness of cooling degree are 10nm, growth pressure 500torr.
3. it is warming up to u-GaN layers of the non-impurity-doped of 1165 DEG C of growth a layer thickness 1.5um, growth pressure 200torr.
4. being warming up to 1170 DEG C, growth a layer thickness adulterates the n-GaN layers of silane for 2.0um, and growth pressure is
200torr。
5. switching carrier gas, nitrogen, pressure 200torr are changed into from hydrogen.1065 DEG C are cooled to, first growth thickness is 1nm
In0.42Ga0.58N quantum well layers, regrowth thickness are the In of 0.8nm0.15Ga0.85Two cycles are grown in N insert layers, such symbiosis,
The In that last growth thickness is 1nm0.42Ga0.58N quantum well layers, complete quantum trap growth；(i.e. structure is 1nm+0.8nm+1nm+
0.8nm+1nm)
6. then heating to 1175 DEG C, first growth thickness is the Al of 4nm0.1Ga0.9N layers, then with 1nm thickness
Al0.05Ga0.95N adds the Al of 1nm thickness0.1Ga0.9N modes, grow 5 cycles, and last regrowth thickness is the Al of 3nm0.1Ga0.9N
Layer, so completes the growth that quantum is built.(i.e. structure is 4nm+2nm*5+3nm)
7. being then cooled to 1065 DEG C, repeat step 5 and step 6 start to grow lower a pair of Quantum Well, such Quantum Well
Quantum builds growth pattern, and 5 pairs of Quantum Well are grown in symbiosis.
8. switching carrier gas, hydrogen is changed into from nitrogen, temperature grows one layer of p-type AlGaN layer to 1185 DEG C, 150torr, thick
Spend 20nm, growth pressure 100torr.
9. 1080 DEG C of temperature, one thickness of growth adulterates the p-type GaN, growth pressure 100torr of Mg for 150nm.
10. switching gas, nitrogen is changed into from hydrogen, anneal in 1200 DEG C 20min under nitrogen atmosphere.
Growth course terminates.
Embodiment two (traditional scheme)
1. the Sapphire Substrate after cleaning is put into MOCVD device, toasted 10 minutes at 1100 DEG C.
2. the low-temperature gan layer that 620 DEG C of growth a layer thickness of cooling degree are 10nm, growth pressure 500torr.
3. it is warming up to u-GaN layers of the non-impurity-doped of 1165 DEG C of growth a layer thickness 1.5um, growth pressure 200torr.
4. being warming up to 1170 DEG C, growth a layer thickness adulterates the n-GaN layers of silane for 2.0um, and growth pressure is
200torr。
5. switching carrier gas, nitrogen is changed into from hydrogen, pressure 200torr, grows In0.42Ga0.58N/Al0.1Ga0.9N volumes
Sub- well layer.Specific method is：1065 DEG C are cooled to, growth thickness is the In of 3nm0.42Ga0.58N quantum well layers；1175 are warming up to again
DEG C, growth thickness is the Al of 10nm0.1Ga0.9N quantum barrier layers, complete the growth of a pair of of Quantum Well.1065 DEG C then are cooled to, is opened
Begin the lower a pair of Quantum Well of growth, and 5 pairs of Quantum Well are grown in such symbiosis.
6. switching carrier gas, hydrogen is changed into from nitrogen, temperature grows one layer of p-type AlGaN layer to 1185 DEG C, 150torr, thick
Spend 20nm, growth pressure 100torr.
7. 1080 DEG C of temperature, one thickness of growth adulterates the p-type GaN, growth pressure position 100torr of Mg for 150nm.
8. switching gas, nitrogen is changed into from hydrogen, anneal in 1200 DEG C 20min under nitrogen atmosphere.
Growth course terminates.
Epitaxial wafer (the embodiment that contrast epitaxial growth method (embodiment one) of the present invention prepares with conventional epitaxial growth method
Two) chip data prepared under the conditions of equal chip technology, the present invention prepare the light efficiency that chip prepares chip compared with conventional method
Improve about 28%, hence it is evident that improve the luminous intensity of LED.Under 0~120mA Injection Currents, chip light emitting wavelength of the present invention
Change turns to 5nm, and traditional structure chip light emitting wavelength change is 13nm, and during using the present invention, LED emission wavelength stability is obvious
Improve.
Claims (8)
1. a kind of LED epitaxial growth methods, including low temperature buffer layer, non-impurity-doped high-temperature gan layer, the high temperature for mixing Si are carried out successively
GaN layer, InxGa1-xN/AlyGa1-yN multiple quantum well layers, p-AlGaN layers and mix Mg p-GaN layer growth, 0 ＜ x≤1,0 ＜
y≤1；It is characterized in that：The In at least one cyclexGa1-xLattice constant smaller is inserted during N quantum trap growths
Multiple InaGa1-aN thin layers, 0 ＜ a ＜ x≤1；The Al at least one cycleyGa1-yN quantum, which are built in growth course, inserts lattice
Multiple Al of constant biggerbGa1-bN thin layers, 0 ＜ b ＜ y≤1；
In the In of a cyclexGa1-xThe In of 1~5 insertion is shared during N quantum trap growthsaGa1-aN thin layers, it is each
InaGa1-aThe thickness of N thin layers is 0.3~2.0nm；In the Al of a cycleyGa1-yN quantum, which are built in growth course, shares 1~20
The Al of insertionbGa1-bN thin layers, every AlbGa1-bThe thickness of N thin layers is 0.3~2.0nm.
2. LED epitaxial growth methods according to claim 1, it is characterised in that：InxGa1-xAll cycles of N Quantum Well are equal
It is inserted into multiple InaGa1-aN thin layers, and/or AlyGa1-yAll cycles that N quantum are built are inserted into multiple AlbGa1-bN thin layers.
3. LED epitaxial growth methods according to claim 2, it is characterised in that：InxGa1-xEach cycle of N Quantum Well
Growth course is identical, AlyGa1-yThe growth course in each cycle that N quantum are built is identical.
4. LED epitaxial growth methods according to any one of claims 1 to 3, it is characterised in that：In the In of a cyclexGa1- xThe In of 2 insertions is shared during N quantum trap growthsaGa1-aN thin layers, every InaGa1-aThe thickness of N thin layers is 0.8nm；One
The Al in a cycleyGa1-yN quantum build the Al that 5 insertions are shared in growth coursebGa1-bN thin layers, every AlbGa1-bThe thickness of N thin layers
Spend for 1.0nm.
5. a kind of LED epitaxial structure, including low temperature buffer layer, non-impurity-doped high-temperature gan layer, the high temperature GaN for mixing Si grown successively
Layer, InxGa1-xN/AlyGa1-yN multiple quantum well layers, p-AlGaN layers and the p-GaN layer of Mg is mixed, 0 ＜ x≤1,0 ＜ y≤1；It is special
Sign is：The In at least one cyclexGa1-xMultiple In inserted with lattice constant smaller in N Quantum WellaGa1-aN thin layers, 0
＜ a ＜ x≤1；The Al at least one cycleyGa1-yMultiple Al inserted with lattice constant bigger during N quantum are builtbGa1-bN is thin
Layer, 0 ＜ b ＜ y≤1；
The In of a cyclexGa1-xThe In of 1~5 insertion is shared in N Quantum WellaGa1-aN thin layers, every InaGa1-aN thin layers
Thickness is 0.3~2.0nm；The Al of a cycleyGa1-yN quantum share the Al of 1~20 insertion in buildingbGa1-bN thin layers, it is each
AlbGa1-bThe thickness of N thin layers is 0.3~2.0nm.
6. LED epitaxial structure according to claim 5, it is characterised in that：InxGa1-xAll cycles of N Quantum Well are inserted into
There are multiple InaGa1-aN thin layers, and/or AlyGa1-yAll cycles that N quantum are built are inserted with multiple AlbGa1-bN thin layers.
7. LED epitaxial structure according to claim 6, it is characterised in that：InxGa1-xThe insertion in each cycle of N Quantum Well
Structure is identical, AlyGa1-yThe insert structure in each cycle that N quantum are built is identical.
8. according to any LED epitaxial structure of claim 5 to 7, it is characterised in that：The In of a cyclexGa1-xN quantum
The In of 2 insertions is shared in trapaGa1-aN thin layers, every InaGa1-aThe thickness of N thin layers is 0.8nm；The Al of a cycleyGa1-yN
Quantum shares the Al of 5 insertions in buildingbGa1-bN thin layers, every AlbGa1-bThe thickness of N thin layers is 1.0nm.
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| CN102103990A (en) * | 2009-12-17 | 2011-06-22 | 上海蓝光科技有限公司 | Preparation method of multiple quantum well structure for photoelectric device |
| CN102623595A (en) * | 2012-04-23 | 2012-08-01 | 中国科学院物理研究所 | Epitaxial material structure of light-emitting diode |
| CN103633209A (en) * | 2013-12-06 | 2014-03-12 | 苏州新纳晶光电有限公司 | LED (light emitting diode) epitaxy structure and application thereof |
| CN103794690A (en) * | 2014-02-18 | 2014-05-14 | 佛山市国星半导体技术有限公司 | GaN-based light-emitting diode and manufacturing method thereof |
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| CN102103990A (en) * | 2009-12-17 | 2011-06-22 | 上海蓝光科技有限公司 | Preparation method of multiple quantum well structure for photoelectric device |
| CN102623595A (en) * | 2012-04-23 | 2012-08-01 | 中国科学院物理研究所 | Epitaxial material structure of light-emitting diode |
| CN103633209A (en) * | 2013-12-06 | 2014-03-12 | 苏州新纳晶光电有限公司 | LED (light emitting diode) epitaxy structure and application thereof |
| CN103794690A (en) * | 2014-02-18 | 2014-05-14 | 佛山市国星半导体技术有限公司 | GaN-based light-emitting diode and manufacturing method thereof |
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