CN117374183A - Method for preparing LED (light-emitting diode) by epitaxial growth of GaN (gallium nitride) based on high-temperature refractory metal substrate - Google Patents

Method for preparing LED (light-emitting diode) by epitaxial growth of GaN (gallium nitride) based on high-temperature refractory metal substrate Download PDF

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Publication number
CN117374183A
CN117374183A CN202311585963.8A CN202311585963A CN117374183A CN 117374183 A CN117374183 A CN 117374183A CN 202311585963 A CN202311585963 A CN 202311585963A CN 117374183 A CN117374183 A CN 117374183A
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gan
layer
refractory metal
temperature refractory
metal substrate
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郭太良
朱学奇
张学文
郭成龙
吴永胜
潘魁
孙捷
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Changzhou Sujiang Electronic Material Co ltd
Fujian Acetron New Materials Co ltd
Fuzhou University
Fujian Prima Optoelectronics Co Ltd
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Changzhou Sujiang Electronic Material Co ltd
Fujian Acetron New Materials Co ltd
Fuzhou University
Fujian Prima Optoelectronics Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/02Semiconductor 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
    • H01L33/12Semiconductor 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/005Processes
    • H01L33/0062Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H01L33/007Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/02Semiconductor 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/02Semiconductor 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
    • H01L33/04Semiconductor 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
    • H01L33/06Semiconductor 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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  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Led Devices (AREA)

Abstract

The invention provides a method for preparing an LED by epitaxially growing GaN based on a high-temperature refractory metal substrate, wherein the high-temperature refractory metal substrate, an AlN buffer layer and Al x Ga 1‑x The epitaxial structure grown on the N gradual change layer comprises an N-type GaN layer, a quantum well layer and a P-type GaN layer which are sequentially stacked. The scheme uses high temperature refractory metal as a substrate, and a layer of AlN and Al is grown on the substrate in a laminated manner x Ga 1‑x N serves as a buffer layer. Compared with the method for preparing the LED by growing the GaN layer by using the traditional substrate, the new substrate scheme not only can easily obtain larger size so as to epitaxially grow the GaN layer with larger size, but also the metal substrate can be subjected to wet etching by adopting acid solutionThe GaN layer is removed conveniently and rapidly without causing excessive influence on the epitaxially grown GaN layer, so that the growth quality of GaN is improved indirectly, and the related time cost and economic cost can be reduced.

Description

Method for preparing LED (light-emitting diode) by epitaxial growth of GaN (gallium nitride) based on high-temperature refractory metal substrate
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a method for preparing an LED (light emitting diode) by epitaxially growing GaN based on a high-temperature refractory metal substrate.
Background
GaN is used as a third generation wide bandgap semiconductor, the bandgap width of the GaN is 3.4eV at room temperature, and the GaN has the advantages of high electron mobility, high thermal conductivity, high electron saturation drift speed, high thermal stability and the like, and has been widely paid attention since the advent of the prior art. The light source can emit red, green and blue light due to the forbidden bandwidth of 3.4eV, and is an ideal material for preparing LEDs. However, since the advent of artificial synthesis of GaN, how to prepare a high quality GaN epitaxial layer has become a problem for the industry, and the first thing is to select a substrate, which directly affects the growth quality of GaN. Wherein the substrate is mainly selected from the following steps: siC, si, gaN, alN and sapphire, etc.
Among them, sapphire is the most available material and is moderate in price, but sapphire itself is not electrically conductive and is poor in thermal conductivity, which results in difficulty in manufacturing electrodes and limits production of high-power devices. Meanwhile, the sapphire substrate and the GaN have larger lattice mismatch and thermal expansion mismatch, which respectively lead to the occurrence of too high dislocation density of the GaN in the growth process and cracks in the cooling process, thereby affecting the growth quality of the GaN.
SiC, while having a lattice constant and thermal expansion coefficient that are closer to those of GaN, is currently more costly making it difficult to use SiC on a large scale. Meanwhile, for GaN production using Si as a substrate, the epitaxially grown GaN layer is extremely susceptible to cracking due to lattice mismatch and thermal expansion coefficient mismatch of Si and GaN. Before solving this problem, it is still difficult to apply on a large scale. While the use of GaN itself as a substrate for the production of GaN is naturally the best choice, how to produce a GaN layer of excellent quality and large size is itself a difficult problem to solve.
However, the stripping of the epitaxial layers of GaN and LED and the recycling of the substrate are also the problems which have been plagued the industry and need to be solved. The dominant substrate stripping methods in the industry today are either laser stripping or thinning of the substrate by mechanical grinding. Taking sapphire as a substrate for growing GaN as an example, irreversible damage can be generated to a grown GaN epitaxial layer after the sapphire substrate is stripped by laser, and the performance of an LED device can be directly affected. And the peeled sapphire substrate is damaged, so that the sapphire substrate is difficult to be used for a second time.
Therefore, there is an urgent need in the market for a new substrate that can be applied in a wide range, is easy to remove, can be recycled, and can produce and prepare GaN epitaxial layers with large size and excellent quality.
Disclosure of Invention
In order to obtain a GaN epitaxial layer with larger size and better quality and prepare an LED, the invention provides a method for preparing an LED by taking high-temperature refractory metal as a substrateAlN and Al x Ga 1-x N is used as a buffer layer and a graded layer to grow GaN so as to prepare the LED.
In view of the defects and shortcomings of the prior art, the scheme firstly considers that the lattice constant of AlN is 0.3117nm, the lattice constant of GaN is 0.3189nm, the lattice mismatch of the AlN and the GaN is 2.3%, and compared with the lattice constant mismatch of 17% of a traditional sapphire substrate, the dislocation and the GaN with fewer defects can grow on the AlN. And AlN has a linear expansion coefficient of about 4.4X10 -6 K, and GaN has a linear expansion coefficient of about 5.6X10 -6 and/K, the thermal mismatch between the two is smaller, and the influence caused by thermal expansion can be effectively reduced in the growth process of GaN, so that a GaN layer with more excellent quality can be grown, and the GaN-based buffer layer is one of ideal buffer layer materials for epitaxially preparing GaN at present.
Consider again that the high temperature refractory metal has a better thermal conductivity than other conventional substrate materials. For example, tantalum has a thermal conductivity of about 138W/(mK) at room temperature. In growing GaN, the substrate is placed on a heated plate and heated. The high heat conductivity of the high-temperature refractory metal substrate can enable the overall temperature of the substrate to be more uniform, and meanwhile, the temperature of the substrate can be increased and decreased more rapidly. And the more uniform substrate temperature can lead the GaN layer to be heated more uniformly during growth, thereby obtaining GaN with better quality. Moreover, current conventional substrates, such as sapphire, are currently available in sizes of only 4 inches, and substrates that are desired to be larger would be more costly and difficult to implement. In contrast, the high temperature refractory metal used in the invention can easily obtain substrates exceeding 4 inches, thereby not only reducing the cost, but also obtaining GaN layers with larger areas in larger sizes, and further obtaining more LEDs at one time.
By combining the characteristics, the scheme of the invention can lead the laser peeling to be carried out by a laser device which does not need to be precise any more in the subsequent peeling process, and the substrate can be dissolved in the solution by using an inorganic acid solution. Compared with the damage of laser stripping to the GaN layer, the GaN epitaxial layer is difficult to be corroded by acid, and the influence on the GaN epitaxial layer caused by the corrosion of the substrate by the acid solution is almost negligible. For example, tantalum metal may be dissolved by hydrofluoric acid. Wet etching by acid solution is certainly convenient and low cost compared to tedious and costly laser lift-off. And the metal dissolved in the solution can be replaced by other processes for secondary use, thereby greatly saving the cost.
The invention provides a method for preparing an LED by epitaxially growing GaN based on a high-temperature refractory metal substrate, wherein the high-temperature refractory metal substrate, an AlN buffer layer and Al x Ga 1-x The epitaxial structure grown on the N gradual change layer comprises an N-type GaN layer, a quantum well layer and a P-type GaN layer which are sequentially stacked. The scheme uses high temperature refractory metal as a substrate, and a layer of AlN and Al is grown on the substrate in a laminated manner x Ga 1-x N serves as a buffer layer. Compared with the method for preparing the LED by growing the GaN layer by using the traditional substrate, the novel substrate scheme not only can easily obtain larger size so as to epitaxially grow the GaN layer with larger size, but also can remove the GaN layer conveniently and rapidly by adopting the acid solution for wet etching without causing excessive influence on the epitaxially grown GaN layer, thereby indirectly improving the growth quality of GaN and reducing the related time cost and economic cost.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing an LED by epitaxially growing GaN based on a high-temperature refractory metal substrate is characterized in that:
AlN buffer layer and Al on high temperature refractory metal substrate x Ga 1-x Growing an LED epitaxial structure on the N gradual change layer;
the epitaxial structure comprises an N-type GaN layer, a quantum well layer and a P-type GaN layer which are sequentially stacked.
Further, after the epitaxial structure growth is completed, the substrate is dissolved in the solution by using an acid solution to realize the peeling of the GaN epitaxial layer.
Further, the high temperature refractory metal is one of tantalum, tungsten, niobium, molybdenum and rhenium.
Further, the high temperature refractory metal substrate has a dimension of 0.1 to 100 inches.
Further, the preparation process comprises the following steps:
step one, growing an AlN buffer layer and Al on a high-temperature refractory metal substrate by adopting MOCVD x Ga 1-x An N gradual change layer;
step two, for the AlN buffer layer and Al which have been grown x Ga 1-x Cleaning the high-temperature refractory metal substrate of the N gradual change layer, and cleaning by using a solution method or a plasma cleaner;
growing an undoped GaN layer by MOCVD or MBE, and then doping to obtain an N-type GaN layer;
step four, growing a quantum well layer by MOCVD or MBE;
and fifthly, growing an undoped GaN layer by MOCVD or MBE, and then doping to obtain the P-type GaN layer.
Further, in step one, MOVCD uses TMAL as Al source, TMGa as Ga source, NH 3 As an N source.
In the second step, the solution method is specifically that acetone is adopted for cleaning, isopropanol is adopted for cleaning, absolute ethyl alcohol is adopted for cleaning, and finally nitrogen is adopted for drying.
Further, in the third step, MOCVD uses TMGa as Ga source, NH 3 As the N source, the carrier gas used was H 2 ,SiH 4 As an N-type semiconductor dopant source.
Further, in the fourth step, MOCVD uses N 2 As carrier gas, TMIn as In source, TEGa as Ga source, NH 3 As an N source.
Further, in the fifth step, MOCVD uses H 2 TMGa as a carrier gas, NH as a Ga source 3 As an N source, cp2Mg serves as a doping source for the P-type GaN layer.
As a preference, in the solution according to the invention:
the quantum well in the quantum well growth layer can be a single quantum well or a multi-quantum well with the cycle number of 2-30.
The AlN buffer layer has a thickness of 1 nm-2000 nm and a size of 0.1-100 inches.
The Al is x Ga 1-x The thickness of the N gradual change layer is 1 nm-2000 nm, and the size of the N gradual change layer is 0.1-100 inches.
The growth thickness of the N-type GaN is 50-6000nm.
The thickness of the P-type GaN growth is 20-1000nm.
The materials used for the quantum well layer comprise: inGaN-GaN, gaN-AlGaN, alGaN-AlN, and InGaN-AlGaN.
At Al x Ga 1-x The method for epitaxially growing the N-type GaN layer, the quantum well layer and the P-type GaN layer on the N gradual change layer comprises the following steps: molecular Beam Epitaxy (MBE) and Metal Organic Chemical Vapor Deposition (MOCVD).
Compared with the prior art, the method for preparing the LED based on the high-temperature refractory metal growth GaN buffer layer and the multi-quantum well growth provided by the invention and the preferred scheme thereof can well solve some problems in the current industry. Compared with the most commonly used sapphire substrate in the industry, the high-temperature refractory metals such as tantalum and tungsten are adopted, and the characteristics of excellent heat conduction performance and easiness in obtaining a large-size substrate are more beneficial to obtaining a GaN epitaxial layer with better quality and larger size, so that the problem that the large-size GaN epitaxial layer is difficult to obtain in the industry is solved. After epitaxial growth, the high temperature refractory metal substrate can be removed with an acid solution without causing excessive damage to the epitaxial layer, as compared to laser lift-off. After wet stripping, complicated laser stripping process and expensive laser stripping equipment are not needed, time and economic cost are greatly saved, and dissolved metal can be collected again through other processes for secondary use, so that economic cost is saved.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a block diagram of an LED grown in accordance with an embodiment of the invention, the structure comprising: 1. a high temperature refractory metal substrate; 2. an AlN buffer layer; 3. al (Al) x Ga 1-x An N gradual change layer; 4. an N-type GaN layer; 5. a quantum well layer; 6. and a P-type GaN layer.
Fig. 2 is a schematic diagram of LED epitaxial growth according to an embodiment of the present invention. The layers 1 to 3 are high temperature refractory metal substrate, alN buffer layer and Al x Ga 1-x And an N graded layer. On layer 3, layers 4 to 6 are grown in sequence one above the other.
Fig. 3 is a schematic diagram of MOCVD according to an embodiment of the present invention. Before starting growth, the substrate is placed on a heating plate for heating, and then required gas and MO source are sequentially introduced. After the reaction, the gas was discharged.
Detailed Description
In order to make the features and advantages of the present patent more comprehensible, embodiments accompanied with figures are described in detail below:
it should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As shown in fig. 1-3, taking MOCVD and high temperature refractory metal tantalum as examples, the method for preparing an LED by epitaxially growing GaN based on a high temperature refractory metal substrate provided by the present invention includes the following steps:
(1) And sequentially placing the high-temperature refractory metal substrate into acetone, isopropanol and deionized water for ultrasonic cleaning. TMAL is firstly used as Al source, NH 3 And growing a low AlN nucleation layer at a low temperature as an N source, and finally raising the growth temperature to 1300 ℃, and then growing to obtain the AlN buffer layer at 950 ℃ while keeping the flow rates of TMAL and NH3 at 500 sccm. Then TMGa is introduced as Ga source, TMAL and NH3 flow are kept unchanged, TMGa flow is set to 800sccm, al is obtained by growth x Ga 1-x And an N buffer layer. And then cleaning the substrate on which the layers 1 to 3 are grown, firstly putting the substrate into an acetone solution for ultrasonic treatment for 1 minute, taking out, putting the substrate into an isopropanol solution for ultrasonic treatment for 1 minute, and finally taking out and drying by nitrogen.
(2) Placing the cleaned substrate on a heating plate, initializing MOCVD system, and charging H 2 . Heating the heating plate to 500 ℃, maintaining the temperature and starting NH 3 . TMGa is turned on, and low-temperature GaN with the thickness of 30nm is grown on the substrate. During the growth process, NH 3 The flow rate was 1500sccm and the TMGa flow rate was 20sccm.
(3) After the heating plate is heated to 800 ℃, NH is increased 3 And (3) the flow rate is up to 3000sccm, and then 80sccm TMGa is introduced to perform three-dimensional growth of GaN for 30min.
(4) Increasing NH 3 The flow rate of TMGa was kept constant at a flow rate of 3500sccm and was grown at a growth rate of 2.0 μm/h for one hour to give undoped layer 4.
(5) Maintaining growth conditions, introducing SiH 4 Doping was performed at a flow rate of 2sccm to give layer 4.
(6) Changing carrier gas to N 2 Growth of the multi-quantum well structure was performed for 10 cycles. First increase NH 3 To 4800sccm, and when the well layer was grown, a flow rate of 35sccm of TEGa and 75sccm of TMIn were introduced as a Ga source and an In source of InGaN, and the growth time of each well layer was 120s. When the barrier layer grows, TEGa with flow of 60sccm is introduced as a Ga source of GaN, and meanwhile, the growth time of each barrier layer is 300s. Cycling 10 times, layer 5 was finally obtained.
(7) After the growth of the layer 5, the carrier gas is changed into H 2 Introducing TMGa with flow rate of 20sccm and NH with flow rate of 3500sccm 3 A layer 6, which is not yet doped, was grown to a thickness of 0.15 μm at a growth rate of 2.0 μm/h.
(8) Then Cp2Mg was introduced at a flow rate of 2sccm for doping to obtain layer 6. The structure after the growth is completed is shown in fig. 1.
After epitaxial growth, the high temperature refractory metal substrate can be removed with an acid solution without causing excessive damage to the epitaxial layer, as compared to laser lift-off. After wet stripping, complicated laser stripping process and expensive laser stripping equipment are not needed, time and economic cost are greatly saved, and dissolved metal can be collected again through other processes for secondary use, so that economic cost is saved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
The present patent is not limited to the above-mentioned preferred embodiments, and any person can obtain other methods of producing LEDs based on epitaxial growth of GaN on high-temperature refractory metal substrates in various forms under the teachings of the present patent, and all equivalent changes and modifications made according to the scope of the present patent should be covered by the present patent.

Claims (10)

1. A method for preparing an LED by epitaxially growing GaN based on a high-temperature refractory metal substrate is characterized in that:
AlN buffer layer and Al on high temperature refractory metal substrate x Ga 1-x Growing an LED epitaxial structure on the N gradual change layer;
the epitaxial structure comprises an N-type GaN layer, a quantum well layer and a P-type GaN layer which are sequentially stacked.
2. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 1, wherein the method comprises the following steps of: after the epitaxial structure growth is finished, the substrate is dissolved in the solution by using an acid solution, so that the GaN epitaxial layer is peeled off.
3. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 1, wherein the method comprises the following steps of: the high temperature refractory metal is one of tantalum, tungsten, niobium, molybdenum and rhenium.
4. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 1, wherein the method comprises the following steps of: the high temperature refractory metal substrate has a dimension of 0.1 to 100 inches.
5. A method of epitaxially growing GaN on a high temperature refractory metal substrate to produce an LED according to claim 1 or 2, wherein:
the preparation process comprises the following steps:
step one, growing an AlN buffer layer and Al on a high-temperature refractory metal substrate by adopting MOCVD x Ga 1-x An N gradual change layer;
step two, for the AlN buffer layer and Al which have been grown x Ga 1-x Cleaning the high-temperature refractory metal substrate of the N gradual change layer, and cleaning by using a solution method or a plasma cleaner;
growing an undoped GaN layer by MOCVD or MBE, and then doping to obtain an N-type GaN layer;
step four, growing a quantum well layer by MOCVD or MBE;
and fifthly, growing an undoped GaN layer by MOCVD or MBE, and then doping to obtain the P-type GaN layer.
6. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 5, wherein the method comprises the following steps of: in step one, MOVCD uses TMAL as Al source, TMGa as Ga source, NH 3 As an N source.
7. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 5, wherein the method comprises the following steps of: in the second step, the solution method is specifically that acetone is adopted for cleaning, isopropanol is adopted for cleaning, absolute ethyl alcohol is adopted for cleaning, and finally nitrogen is adopted for drying.
8. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 5, wherein the method comprises the following steps of: in the third step, MOCVD uses TMGa as Ga source, NH 3 As the N source, the carrier gas used was H 2 ,SiH 4 As an N-type semiconductor dopant source.
9. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 5, wherein the method comprises the following steps of: in the fourth step, MOCVD uses N 2 As carrier gas, TMIn as In source, TEGa as Ga source, NH 3 As an N source.
10. The method for preparing the LED by epitaxially growing GaN on the basis of the high-temperature refractory metal substrate according to claim 5, wherein the method comprises the following steps of: in the fifth step, MOCVD uses H 2 TMGa as a carrier gas, NH as a Ga source 3 As an N source, cp2Mg serves as a doping source for the P-type GaN layer.
CN202311585963.8A 2023-11-27 2023-11-27 Method for preparing LED (light-emitting diode) by epitaxial growth of GaN (gallium nitride) based on high-temperature refractory metal substrate Pending CN117374183A (en)

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