CN112436079A - GaN-based LED epitaxial structure of inverted triangular potential barrier and growth method thereof - Google Patents
GaN-based LED epitaxial structure of inverted triangular potential barrier and growth method thereof Download PDFInfo
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- 238000005036 potential barrier Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims description 11
- 229910002704 AlGaN Inorganic materials 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 5
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 230000005699 Stark effect Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 11
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 7
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QHGSGZLLHBKSAH-UHFFFAOYSA-N hydridosilicon Chemical compound [SiH] QHGSGZLLHBKSAH-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- H—ELECTRICITY
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- 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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- 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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- 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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- 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
- H01L33/14—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 carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
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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
- H01L33/30—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
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
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Abstract
The invention discloses a GaN-based LED epitaxial structure of an inverted triangular potential barrier and a growth method thereof x Ga 1‑x An N-GaN barrier layer (GIG barrier layer for short) composed of GaN barrier layer and In layer In sequence x Ga 1‑x N barrier and GaN barrier formed, In x Ga 1‑x In the N barrierxThe growth direction is graded from 0 to 0.1 to 0. The invention adopts a GIG inverted triangle barrier structure to replace transmissionAccording to the GaN barrier structure of the LED, the application of InGaN material in the barrier layer can effectively reduce the polarization electric field of the barrier and the quantum well, and effectively inhibit the quantum Stark effect, meanwhile, the special barrier shape provided by the invention does not reduce the effective height of the barrier, and the inverted triangle barrier can still effectively limit carriers.
Description
Technical Field
The invention relates to the field of LED design and application, in particular to an LED epitaxial structure with improved hole injection layer and luminescent layer structures and a growth method thereof.
Background
The GaN-based blue-light LED is widely used as a new generation lighting source, is widely used for background lighting, medical lighting and the like, and is one of important light sources for forming white light, but with the demand of industrial production, the GaN-based blue-light LED is increasingly required to work under high current, and consequently, the GaN-based blue-light LED has a phenomenon of large efficiency attenuation during working, the photoelectric property of the GaN-based blue-light LED is seriously reduced, and in the current research, large electron leakage and poor hole injection are important reasons for causing the efficiency attenuation.
At present, the main method for improving the carrier transport and the photoelectric efficiency is to grow an AlGaN electron blocking layer between a light emitting layer and a p-type GaN layer, however, although the growth of the AlGaN electron blocking layer can effectively improve an electron barrier and inhibit electron leakage, the growth of the AlGaN electron blocking layer can also bring about the improvement of a hole barrier, thereby causing poorer hole injection, and the photoelectric performance of the GaN-based blue light LED cannot be better improved.
Besides growing the AlGaN electron blocking layer, it is proposed in the industry to grow light emitting layer structures with different structures through band engineering to improve the carrier transport and distribution in the light emitting layer, for example, growing a barrier layer of a GaN/InGaN composite structure, which can reduce the polarization effect to a certain extent and improve the electron confinement effect of a quantum well, but cannot improve the hole injection and the light emitting layer confinement ability, and can only improve the photoelectric performance of the GaN-based blue LED to a small extent, so that the GaN-based blue LED can meet the requirements of industrial production.
Disclosure of Invention
In order to effectively reduce the problem of efficiency reduction of the GaN-based LED, the invention provides a GaN-based LED epitaxial structure with an inverted triangular potential barrier and a growth method thereof.
The technical solution for realizing the purpose of the invention is as follows: a light-emitting layer of a GaN-based LED epitaxial structure of an inverted triangular potential barrier is composed of barrier layers and quantum well layers alternately, wherein the barrier layers are GaN-In x Ga 1-x A N-GaN (GIG) barrier layer composed of a GaN barrier and In x Ga 1-x N barrier and GaN barrier formed, In x Ga 1-x In the N barrierxThe growth direction is graded from 0 to 0.1 to 0.
Preferably, the quantum well layer is In y Ga y1-An N quantum well layer is formed on the substrate,y0.1-0.3, and the thickness of each quantum well layer is 2 nm.
Preferably, the thickness of each barrier layer is 9nm to 15 nm.
A GaN-based LED epitaxial structure of an inverted triangular potential barrier sequentially comprises a substrate, a low-temperature nucleation layer GaN, an undoped u-GaN layer, a Si-doped n-GaN layer, a light emitting layer of the GIG potential barrier, an AlGaN electronic barrier layer and a p-GaN layer from bottom to top.
A growth method of a luminescent layer of a GaN-based LED epitaxial structure of an inverted triangle barrier adopts a GIG inverted triangle barrier structure to replace a traditional GaN barrier structure, and comprises the following steps:
s1 growing GIG barrier layer
S101, keeping the pressure of a reaction cavity at 100 Torr-500 Torr at the temperature of 800-950 ℃, and adopting MO sources of TEGa, TMIn and SiH4Growing a GaN barrier with the thickness of 3 nm-5 nm, and carrying out Si doping on the GaN barrier, wherein the Si doping concentration is 8 multiplied by 1016 atoms/cm3~6× 1017 atoms/cm3；
S102, using TEGa, TMIn and SiH at the reaction cavity pressure of 100 Torr-500 Torr and the temperature of 700 ℃ to 800 DEG C4As MO source, continuously growing In 3 nm-5 nm x Ga 1-x The N barrier, x gradually changes from 0 to 0.1 to 0 along the growth direction, and the growth time is 20-40 s;
s103, raising the temperature to 800-950 ℃, keeping the pressure of the reaction cavity at 100-500 Torr, and adopting MO sources TEGa, TMIn and SiH4Growing a GaN barrier with the thickness of 3 nm-5 nm, and carrying out Si doping on the GaN barrier, wherein the Si doping concentration is 8 multiplied by 1016 atoms/cm3~6× 1017 atoms/cm3；
S2 growing a quantum well layer
The pressure of a reaction cavity is 100 Torr-500 Torr, the temperature is 700 ℃ -800 ℃, and TEGa, TMIn and SiH are used4As MO source, In doped with In is grown y Ga y1-An N quantum well layer is formed on the substrate,y0.1 to 0.3;
s3, step S1 and step S2 are alternately performed to alternately grow GIG/In y Ga y1-And an N light emitting layer.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an epitaxial growth method for effectively improving luminous efficiency, which comprises the following steps: in the light emitting layer, a GIG inverted triangular barrier structure is adopted to replace a GaN barrier structure of a traditional LED, the polarization electric field of the barrier and a quantum well can be effectively reduced by applying InGaN materials in the barrier layer, the quantum Stark effect is effectively inhibited, meanwhile, the effective height of the barrier is not reduced by the special barrier shape provided by the invention, and carriers can still be effectively limited by the inverted triangular barrier.
Drawings
FIG. 1 is an energy band diagram of a conventional GaN-based LED.
Fig. 2 is an energy band diagram of a GaN-based LED containing a low In composition InGaN barrier.
Fig. 3 is a band diagram of a GaN-based LED employing a GAG barrier as proposed by the present invention.
Fig. 4 is a schematic view of a preparation flow of the epitaxial growth method of the GaN-based LED according to the present invention.
Detailed Description
The invention replaces the GaN barrier in the luminous layer with a special GIG triangular barrier.
As can be seen from fig. 1, fig. 2, and fig. 3, when the GIG inverted triangular barrier layer is grown, on one hand, after InGaN is introduced into the barrier layer, the polarization electric field between the barrier layer and the quantum well can be effectively reduced by the application of InGaN material in the barrier layer, the quantum stark effect can be effectively suppressed, and the effective radiation recombination rate of electrons and holes in the quantum well can be improved. On the other hand, after the GIG inverted triangle barrier is adopted, compared with the traditional GaN barrier, the special barrier shape provided by the invention does not reduce the effective height of the barrier, and the inverted triangle barrier can still effectively limit carriers; thereby effectively improving the photoelectric performance of the GaN-based LED.
With reference to fig. 4, the method for growing the epitaxial structure of the GaN-based LED according to the present invention is as follows:
VEECO MOCVD is used to grow high brightness GaN base LED epitaxial wafer. Using high-purity H2Or high purity N2Or high purity H2And high purity N2As a carrier gas, high purity NH3（NH399.999%) as an N source, a metal-organic source of trimethyl gallium (TMGa) and a metal-organic source of triethyl gallium (TEGa), trimethyl indium (TMIn) as an indium source, and an N-type dopant of Silane (SiH)4) Trimethylaluminum (TMAl) as the aluminum source and magnesium diclomelate (CP) as the P-type dopant2Mg), the substrate is (0001) plane sapphire, the reaction pressure is between 100 Torr and 1000 Torr, and the specific growth mode is as follows:
and annealing the sapphire substrate in a hydrogen atmosphere at 1050-1150 ℃, and cleaning the surface of the substrate.
Introducing ammonia gas and TMGa at the temperature of 500-610 ℃ and the pressure of a reaction cavity of 400-650 Torr, and growing a low-temperature nucleation layer GaN with the thickness of 20-40 nm on the sapphire substrate.
Keeping the pressure of a reaction cavity at 1050-1200 ℃ and 100-500 Torr, introducing ammonia gas and TMGa, and continuously growing an undoped u-GaN layer with the thickness of 1-3 mu m on the low-temperature nucleation layer GaN.
Keeping the pressure of the reaction cavity at 1050-1200 ℃ to be 100-600 Torr, and introducing ammonia gas, TMGa and SiH4Continuously growing a Si-doped n-GaN layer with stable doping concentration and thickness of 2-4 mu m on the undoped u-GaN layer, wherein the Si is dopedThe concentration is 8X 1018 atoms/cm3~2×1019atoms/cm3。
Keeping the pressure of a reaction cavity at 800-950 ℃ and keeping the pressure at 100-500 Torr, and adopting MO sources of TEGa, TMIn and SiH4Growing a GaN barrier with the thickness of 3 nm-5 nm, and carrying out Si doping on the GaN barrier, wherein the Si doping concentration is 8 multiplied by 1016 atoms/cm3~6× 1017 atoms/cm3；
The pressure of a reaction cavity is 100 Torr-500 Torr, the temperature is 700 ℃ -800 ℃, and TEGa, TMIn and SiH are used4As MO source, continuously growing In 3 nm-5 nm x Ga 1-x The N barrier, x gradually changes from 0 to 0.1 to 0 along the growth direction, and the growth time is 20-40 s;
raising the temperature to 800-950 ℃, keeping the pressure of the reaction cavity at 100-500 Torr, and adopting MO sources of TEGa, TMIn and SiH4Growing a GaN barrier with the thickness of 3 nm-5 nm, and carrying out Si doping on the GaN barrier, wherein the Si doping concentration is 8 multiplied by 1016atoms/cm3~6× 1017 atoms/cm3；
The pressure of a reaction cavity is 100 Torr-500 Torr, the temperature is 700 ℃ -800 ℃, and TEGa, TMIn and SiH are used4As MO source, In doped with In is grown y Ga y1-An N quantum well layer is formed on the substrate,y0.1 to 0.3;
growing the reverse triangle barrier layer of GIG repeatedly, repeating In y Ga -y1Growth of N quantum well layer, alternatively growing In containing inverted triangular potential barrier y Ga y1-N/GIG light emitting layer for controlling In y Ga -y1The growth period of the N quantum well layer was 6.
Keeping the pressure of the reaction chamber at 20 Torr-200 Torr and the temperature at 900-1100 ℃, and introducing MO source of TMAl, TMGa and CP2Mg In y Ga y1-Continuously growing a P-type AlGaN electron barrier layer with the thickness of 50 nm-200 nm on the N/GIG luminous layer for 3 min-100 min, wherein the molar component of Al is 10% -30%, and the doping concentration of Mg is 1 multiplied by 1018atoms/cm3~1×1021 atoms/cm3。
Keeping the pressure of the reaction cavity at 100-500 Torr and the temperature at 850-1050 ℃, and introducing MO sources of TEGa and CP2Mg, continuously growing a P-type GaN contact layer doped with Mg with the thickness of 200nm on the AlGaN electron barrier layer, wherein the doping concentration of the Mg is 1 multiplied by 1019 atoms/cm3~1×1022 atoms/cm3。
And after the epitaxial growth is finished, reducing the reaction temperature to 650-800 ℃, annealing for 5-10 min in a pure nitrogen atmosphere, and then reducing the temperature to room temperature to finish the growth.
Claims (5)
1. The light-emitting layer of the GaN-based LED epitaxial structure of the inverted triangular potential barrier is characterized by being composed of barrier layers and quantum well layers In an alternating mode, wherein the barrier layers are GaN-In x Ga 1-x An N-GaN barrier layer (GIG barrier layer for short) composed of GaN barrier layer and In layer In sequence x Ga 1-x N barrier and GaN barrier formed, In x Ga 1-x In the N barrierxThe growth direction is graded from 0 to 0.1 to 0.
2. The light emitting layer of claim 1, wherein the quantum well layer employs In y Ga y1-An N quantum well layer is formed on the substrate,y0.1-0.3, and the thickness of each quantum well layer is 2 nm.
3. The light-emitting layer according to claim 1, wherein each barrier layer has a thickness of 9nm to 15 nm.
4. A GaN-based LED epitaxial structure of an inverted triangular potential barrier comprises a substrate, a low-temperature nucleation layer GaN, an undoped u-GaN layer, a Si-doped n-GaN layer, a light-emitting layer containing a GIG potential barrier, an AlGaN electron blocking layer and a p-GaN layer in sequence from bottom to top, and is characterized in that the light-emitting layer containing the GIG potential barrier is the light-emitting layer according to claims 1-3.
5. A growth method of a luminous layer of a GaN-based LED epitaxial structure of an inverted triangular potential barrier is characterized by comprising the following steps:
s1 growing GIG barrier layer
S101, keeping the pressure of a reaction cavity at 100 Torr-500 Torr at the temperature of 800-950 ℃, and adopting MO sources of TEGa, TMIn and SiH4Growing a GaN barrier with the thickness of 3 nm-5 nm, and carrying out Si doping on the GaN barrier, wherein the Si doping concentration is 8 multiplied by 1016 atoms/cm3~6× 1017 atoms/cm3；
S102, using TEGa, TMIn and SiH at the reaction cavity pressure of 100 Torr-500 Torr and the temperature of 700 ℃ to 800 DEG C4As MO source, continuously growing In 3 nm-5 nm x Ga 1-x The N barrier, x gradually changes from 0 to 0.1 to 0 along the growth direction, and the growth time is 20-40 s;
s103, raising the temperature to 800-950 ℃, keeping the pressure of the reaction cavity at 100-500 Torr, and adopting MO sources TEGa, TMIn and SiH4Growing a GaN barrier with the thickness of 3 nm-5 nm, and carrying out Si doping on the GaN barrier, wherein the Si doping concentration is 8 multiplied by 1016 atoms/cm3~6× 1017 atoms/cm3；
S2 growing a quantum well layer
The pressure of a reaction cavity is 100 Torr-500 Torr, the temperature is 700 ℃ -800 ℃, and TEGa, TMIn and SiH are used4As MO source, In doped with In is grown y Ga y1-An N quantum well layer is formed on the substrate,y0.1 to 0.3;
s3, step S1 and step S2 are alternately performed to alternately grow GIG/In y Ga y1-And an N light emitting layer.
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- 2020-10-31 CN CN202011195545.4A patent/CN112436079A/en active Pending
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Application publication date: 20210302 |