CN1831084A - Doped rare earth element gallium oxide type fluorescent substrate material and its prepn. method - Google Patents

Doped rare earth element gallium oxide type fluorescent substrate material and its prepn. method Download PDF

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Publication number
CN1831084A
CN1831084A CNA2006100240956A CN200610024095A CN1831084A CN 1831084 A CN1831084 A CN 1831084A CN A2006100240956 A CNA2006100240956 A CN A2006100240956A CN 200610024095 A CN200610024095 A CN 200610024095A CN 1831084 A CN1831084 A CN 1831084A
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rare earth
earth element
fuel rod
gallium oxide
crystal
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夏长泰
张俊刚
徐军
周国清
吴锋
裴广庆
吴永庆
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

This invention relates to dope rare earth element gallium oxide fluorescence substrate material used to GaInN group blue light semiconductor epitaxial growth and its preparation method. The substrate single crystal molecular formula is beta-Ga2-2x(RE)2xO3, the RE equals to Ce or Tm, x equals to 0.001 to 0.1. The crystal grows by floating zone method. The substrate is propitious to epitaxial growth high quality GaInN group blue semiconductor film, LED can emit white light by it combine with GaInN group blue light.

Description

Doped rare earth element gallium oxide type fluorescent substrate material and preparation method thereof
Technical field
The present invention relates to a kind of doped rare earth element gallium oxide type β-Ga that can be used for preparing GaInN base white semiconductor diode 2-2x(RE) 2xO 3(RE=Ce, Tm) yellow fluorescence substrate material and preparation method thereof.
Background technology
Present employed light source is mainly based on incandescent light and luminescent lamp.Incandescent light and luminescent lamp have advantages such as low price, easy preparation, and the technology of preparing maturation.Yet service life of incandescent lamp is short; The luminescent lamp luminous efficiency is low, and a large amount of electric energy consumes with the heat energy form.Because photodiode (hereinafter to be referred as LED) directly is transformed into luminous energy with electric energy, therefore have very high efficient, and volume is little, the life-span long, low price.All commercializations of single color LED (LED) such as red, yellow, green, blue look.The monochromaticity light emission is the excellent specific property of semiconductor material, so semiconductor light source all is monochromatic sources in essence, and this can not launch polychromatic light with regard to having limited single light emitting semiconductor device to launch monochromatic ray.But monochromatic source can't be used as lighting source, equally also is not suitable as the background light source of liquid-crystal display.Illumination and liquid-crystal display bias light need a kind of white light source.
Producing white light with LED mainly is luminous with the GaInN base LED and YAG (yttrium aluminum garnet) phosphor combination that can produce the high-energy blue light at present (Shuji Nakamura, et al., The Blue Laser Diode (GaN Based Light Emitters and Lasers) January 1997, Springer, P 216-221)Its principle is: with active layer-GaInN of power supply excitation LED, this GaInN sends high-octane blue light.The blue light part that GaInN sends is used for encouraging YAG fluorescent material, makes fluorescent material send gold-tinted.Obtain white light emission after the yellow light mix that the remainder of the blue light that GaInN sends and YAG fluorescent material send.But still there is shortcoming in this white light LEDs:
The cost height.Use this material different fully of YAG fluorescent material, increased raw material and production cost with GaInN-LED;
Efficient is low.Because use YAG fluorescent material to cover GaInN, most blue light is all absorbed by YAG fluorescent material, the blue light that can appear seldom.Except the blue light perviousness was bad, YAG fluorescent material was also very low with the transformation efficient that blue light changes gold-tinted into, the highlyest can only reach 10%.Therefore, being badly in need of a kind of novel substrate material that can send yellow fluorescence breaks away from the dependence of white light LEDs to fluorescent material.
At present, typical GaInN base blue-ray LED is made on Sapphire Substrate.Its structure is from top to bottom successively: p-GaN/AlGaN barrer layer/InGaN-GaN quantumwells/AlGaN barrier layer/n-GaN/4 μ m GaN.Because sapphire has high resistivity, so the n-type of device and p-type electrode must be drawn from the same side.This has not only increased the manufacture difficulty of device, has also increased the volume of device simultaneously.And sapphire can't absorb blue light and launch gold-tinted.Can not launch gold-tinted by electric excitation.Thereby can't use Sapphire Substrate to realize white light LEDs separately.
In sum, technology substrate (α-Al formerly 2O 3) the remarkable shortcoming that exists is:
(1) with α-Al 2O 3Make substrate, α-Al 2O 3And the lattice mismatch between the GaN is up to 14%, and therefore the GaN film of preparation has higher dislocation desity and a large amount of point defects;
(2) α-Al 2O 3Can't realize the transformation of blue light to gold-tinted;
(3) α-Al 2O 3Substrate is non-conductive, and the element manufacturing difficulty is big, has also increased the volume of device simultaneously, has caused the waste of great deal of raw materials;
(4) can't obtain yellow emission by the mode of electric excitation.
Summary of the invention
The technical problem to be solved in the present invention is to overcome above-mentioned prior art α-Al 2O 3Make the shortcoming of substrate, provide a kind of as the epitaxially grown doped rare earth element gallium oxide type β-Ga of GaInN base blue-light semiconductor 2-2x(RE) 2xO 3(RE=Ce, Tm) yellow fluorescence substrate material and preparation method thereof.This fluorescence substrate should be suitable for epitaxy high quality GaInN base blue-light semiconductor film, combines with GaInN base blue light and can realize the white light emission of LED.
β-Ga of the present invention 2-2x(RE) 2xO 3The yellow fluorescence substrate material is actually at β-Ga 2-2x(RE) 2xO 3Mix in the single crystal and can or absorb the blue light excitation by electric excitation and send that the rare earth element ce of gold-tinted or Tm constitute, this fluorescence substrate is suitable for epitaxy high quality GaInN base blue-light semiconductor film, and can realize white light emission.
β-Ga 2O 3Belong to monoclinic structure (C2/m), its unit cell parameters is a=12.22 , b=3.04 , c=5.80 , β=103.82 °, the lattice mismatch rate of its (100) face and GaN is very little, have only about 5%, and can be by the lattice match of surfaces nitrided realization and GaN.β-Ga 2O 3Monocrystalline is isolator in essence, when growing under reductive condition, because the existence of oxygen defect in the lattice can form the n N-type semiconductorN.
Technical solution of the present invention is as follows:
A kind of gallium oxide type fluorescent substrate monocrystal body of doped rare earth element is characterized in that the molecular formula of this substrate monocrystal body is: β-Ga 2-2x(RE) 2xO 3, wherein RE=Ce or Tm, x=0.001～0.1.
A kind of preparation method of gallium oxide type fluorescent substrate monocrystal body of doped rare earth element.This crystalline growth adopts common infrared floating region stove to grow, and the synoptic diagram of this infrared floating region stove as shown in Figure 1.The floating region stove is to utilize infrared light that infrared lamp 4 sends and hang over fuel rod 10 on the bull stick 1 with platinum wire through ellipsoidal mirror 2 heating, makes fuel rod 10 fusings form melting zones 3, crystallization generation monocrystalline on the seed crystal 7 that is installed on the bull stick 6 down.Observe the crystal growth situation by watch-dog 9 and screen 8.
The preparation method of the gallium oxide type fluorescent substrate monocrystal body of this doped rare earth element follows these steps to carry out:
1. behind the doping ratio x that determines rare earth element, take by weighing purity in proportion and be higher than 99.99% Ga 2O 3And rare earth oxide (CeO 2Or Tm 2O 3) raw material;
2. the raw material thorough mixing that is taken by weighing is formed uniform mixing raw material;
3. above-mentioned mixing raw material is packed in the rubber mold, be pressed into fuel rod, the size range of fuel rod: long 1～20cm, diameter 1～20mm waiting under the static pressure of 10-100MPa;
4. the above-mentioned fuel rod that presses is hung in the silicon molybdenum stove with platinum wire, is being lower than 1500 ℃ sintering temperature more than 8 hours;
5. the fuel rod that sinters is hung on the last bull stick of floating region stove, with β-Ga with platinum wire 2O 3Seed crystal is installed on the following bull stick of floating region stove;
6. after shove charge finishes, adopt the mode of infrared lamp heating to make the fuel rod fusion, form melting zone (3); β-Ga 2-2x(RE) 2xO 3Melt temperature be about 1750 ℃, growth atmosphere is N 2+ O 2, N/ (O+N)=1%～99%, the crystalline speed of growth is 1～10mm/hr, the crystalline rotating speed is 10～20rpm, crystal through inoculation, necking down, shouldering, etc. behind neck, ending, the temperature-fall period, growth ending;
7. β-the Ga that takes out in the stove of floating region 2-2x(RE) 2xO 3The fluorescence substrate monocrystal is at N 2Atmosphere under carry out conventional annealing and handle;
Described β-Ga 2O 3Seed crystal is the β-Ga of a axle, b axle, c axle or other special crystallization direction 2O 3Single crystal.
Characteristics of the present invention are:
1, the epitaxially grown β-Ga of a kind of GaInN of being used for base blue-light semiconductor has been proposed 2-2x(RE) 2xO 3Yellow fluorescence substrate monocrystal material.This substrate is compared with substrate formerly, and the lattice mismatch of itself and GaN is little, by nitriding treatment, can realize the coupling fully with GaN, and can launch gold-tinted under the excitation of blue light or electricity, send white light thereby can merge with the blue light of GaInN.The GaInN for preparing on this fluorescence substrate can directly obtain white light output, need not fluorescent material.
2, the present invention proposes to utilize the float-zone method growing technology to prepare β-Ga 2-2x(RE) 2xO 3The method of yellow fluorescence substrate monocrystal.Thereby obtain high quality β-Ga 2-2x(RE) 2xO 3The yellow fluorescence substrate monocrystal.This method can solve because of β-Ga 2-2x(RE) 2xO 3Monocrystalline fusing point height, easily generate the growth difficulty that twin etc. is caused, and preparation technology is simple, easy to operate.
3, this kind fluorescence substrate β-Ga 2-2x(RE) 2xO 3Be suitable for the epitaxy of high quality GaN, and can simplify the preparation technology of white light LEDs, help reducing cost.
Description of drawings
Fig. 1 is the synoptic diagram of the infrared floating region stove that uses of the present invention
This infrared floating region stove does not belong to the scope of the invention, and this synoptic diagram is in order to make β-Ga of the present invention 2-2x(RE) 2xO 3The process of growth of yellow fluorescence substrate monocrystal is explained clearlyer.Among the figure:
The last bull stick 2-of 1-ellipsoidal surface mirror 3-melting zone 4-infrared lamp
Bull stick 7-seed crystal 8-display screen 9-watch-dog under the 5-silica tube 6-
The 10-fuel rod
Embodiment
Preparation method to the gallium oxide type fluorescent substrate monocrystal body of doped rare earth element of the present invention is further described below in conjunction with embodiment and accompanying drawing, but should not limit protection scope of the present invention with this.
A kind of gallium oxide type fluorescent substrate monocrystal body of doped rare earth element is characterized in that the molecular formula of this substrate monocrystal body is: β-Ga 2-2x(RE) 2xO 3, wherein RE is cerium Ce or thulium Tm, x=0.001～0.1.
The preparation method of the gallium oxide type fluorescent substrate monocrystal body of doped rare earth element of the present invention follows these steps to carry out:
1. at definite rare earth element ce O 2Or Tm 2O 3And behind the doping ratio x, take by weighing purity in proportion and be higher than 99.99% Ga 2O 3With rare earth oxide CeO 2Or Tm 2O 3Raw material;
2. the raw material thorough mixing that is taken by weighing is formed uniform mixing raw material;
3. above-mentioned mixing raw material is packed in the mould, be pressed into fuel rod 10, the size range of fuel rod: long 1～20cm, diameter 1～20mm waiting under the static pressure of 10-100MPa;
4. the above-mentioned fuel rod that presses 10 usefulness platinum wires are hung in the silicon molybdenum stove, are being lower than 1500 ℃ sintering temperature more than 8 hours;
5. the fuel rod 10 usefulness platinum wires that sinter are hung on the last bull stick 1 of floating region stove, with β-Ga 2O 3Seed crystal is installed on the following bull stick 6 of floating region stove;
6. after shove charge finishes, adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions, form melting zone 3; β-Ga 2-2x(RE) 2xO 3Melt temperature be about 1750 ℃, growth atmosphere is N 2+ O 2, N/ (O+N)=1%～99%, the crystalline speed of growth is 1～10mm/hr, the crystalline rotating speed is 10～20rpm, crystal through inoculation, necking down, shouldering, etc. behind neck, ending, the temperature-fall period, growth ending;
7. β-the Ga that takes out in the stove of floating region 2-2x(RE) 2xO 3The fluorescence substrate monocrystal is at N 2Atmosphere under carry out conventional annealing and handle;
Described β-Ga 2O 3Seed crystal is the β-Ga of a axle, b axle, c axle or other special crystallization direction 2O 3Single crystal.
Embodiment one:
According to above-mentioned processing step＜1〉take by weighing the Ga that purity is 99.999% exsiccant 0.0999mol 2O 3CeO with 0.0002mol 2Set by step＜2〉raw material is mixed.Set by step＜3〉raw material is pressed into fuel rod 10 waiting under the static pressure of 10-100MPa.Set by step＜4〉with fuel rod 10 1450 ℃ sintering temperature 12 hours.Set by step＜5〉fuel rod 10 and a axle seed crystal 7 are installed in the stove of floating region.Set by step＜6〉adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions; Growth atmosphere is N 2+ O 2, N/ (O+N)=10%.The crystalline speed of growth is 5mm/hr, and the crystalline rotating speed is 10rpm, and the crystalline growth temperature is for being 1750 ℃.Crystal through inoculation, necking down, shouldering, etc. after the processes such as neck, ending, cooling, growth ending.Set by step＜7〉with crystal at N 2Atmosphere under anneal, annealing temperature is 800 ℃, is incubated 24 hours.Intensification or rate of temperature fall are 50 ℃/hr.Resulting crystal is fit to the epitaxy of GaInN through the processing back, and can launch gold-tinted under electric excitation.
Embodiment two:
According to embodiment one processing step＜1〉take by weighing the Ga that purity is 99.999% exsiccant 0.099mol 2O 3CeO with 0.001mol 2Repeat step＜2 among the embodiment one〉＜3＜4, set by step＜5〉fuel rod 10 and a axle seed crystal 7 are installed in the stove of floating region.Set by step＜6〉adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions; Growth atmosphere is N 2+ O 2, N/ (O+N)=50%.The crystalline speed of growth is 5mm/hr, and the crystalline rotating speed is 10rpm, and the crystalline growth temperature is for being 1750 ℃.Crystal through inoculation, necking down, shouldering, etc. after the processes such as neck, ending, cooling, growth ending.Set by step＜7〉with crystal at N 2Atmosphere under anneal, annealing temperature is 1000 ℃, is incubated 30 hours.Intensification or rate of temperature fall are 50 ℃/hr.Resulting crystal process is processed the back in the epitaxy that is fit to GaInN, and can launch gold-tinted under electric excitation.
Embodiment three:
According to embodiment one processing step＜1〉take by weighing the Ga that purity is 99.999% exsiccant 0.099mol 2O 3CeO with 0.002mol 2Repeat step＜2 among the embodiment one〉＜3＜4, set by step＜5〉fuel rod 10 and a axle seed crystal 7 are installed in the stove of floating region.Set by step＜6〉adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions; Growth atmosphere is N 2+ O 2, N/ (O+N)=90%.The crystalline speed of growth is 5mm/hr, and the crystalline rotating speed is 10rpm, and the crystalline growth temperature is for being 1750 ℃.Crystal through inoculation, necking down, shouldering, etc. after the processes such as neck, ending, cooling, growth ending.Set by step＜7〉with crystal at N 2Atmosphere under anneal, annealing temperature is 1300 ℃, is incubated 30 hours.Intensification or rate of temperature fall are 50 ℃/hr.Resulting crystal process is processed the back in the epitaxy that is fit to GaInN, and can launch gold-tinted under electric excitation.
Embodiment four:
According to embodiment one processing step＜1〉take by weighing the Ga that purity is 99.999% exsiccant 0.0999mol 2O 3Tm with 0.0001mol 2O 3Repeat step＜2 among the embodiment one〉＜3＜4, set by step＜5〉fuel rod 10 and a axle seed crystal 7 are installed in the stove of floating region.Set by step＜6〉adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions; Growth atmosphere is N 2+ O 2, N/ (O+N)=10%.The crystalline speed of growth is 5mm/hr, and the crystalline rotating speed is 10rpm, and the crystalline growth temperature is 1750 ℃.Crystal through inoculation, necking down, shouldering, etc. after the processes such as neck, ending, cooling, growth ending.Set by step＜7〉with crystal at N 2Atmosphere under anneal, annealing temperature is 800 ℃, is incubated 24 hours.Intensification or rate of temperature fall are 50 ℃/hr.Resulting crystal process is processed the back in the epitaxy that is fit to GaInN, and can launch gold-tinted under the excitation of high strength blue light.
Embodiment five:
According to embodiment one processing step＜1〉take by weighing the Ga that purity is 99.999% exsiccant 0.099mol 2O 3Tm with 0.0005mol 2O 3Repeat step＜2 among the embodiment one〉＜3＜4, set by step＜5〉fuel rod 10 and a axle seed crystal 7 are installed in the stove of floating region.Set by step＜6〉adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions; Growth atmosphere is N 2+ O 2, N/ (O+N)=50%.The crystalline speed of growth is 5mm/hr, and the crystalline rotating speed is 10rpm, and the crystalline growth temperature is for being 1750 ℃.Crystal through inoculation, necking down, shouldering, etc. after the processes such as neck, ending, cooling, growth ending.Set by step＜7〉with crystal at N 2Atmosphere under anneal, annealing temperature is 1000 ℃, is incubated 30 hours.Intensification or rate of temperature fall are 50 ℃/hr.Resulting crystal process is processed the back in the epitaxy that is fit to GaInN, and can launch gold-tinted under the excitation of high strength blue light.
Embodiment six:
According to embodiment one processing step＜1〉take by weighing the Ga that purity is 99.999% exsiccant 0.099mol 2O 3Tm with 0.001mol 2O 3Repeat step＜2 among the embodiment one〉＜3＜4, set by step＜5〉fuel rod 10 and a axle seed crystal 7 are installed in the stove of floating region.Set by step＜6〉adopt the mode of infrared lamp 4 heating to make fuel rod 10 fusions; Growth atmosphere is N 2+ O 2, N/ (O+N)=90%.The crystalline speed of growth is 5mm/hr, and the crystalline rotating speed is 10rpm, and the crystalline growth temperature is for being 1750 ℃.Crystal through inoculation, necking down, shouldering, etc. after the processes such as neck, ending, cooling, growth ending.Set by step＜7〉with crystal at N 2Atmosphere under anneal, annealing temperature is 1300 ℃, is incubated 30 hours.Intensification or rate of temperature fall are 50 ℃/hr.Resulting crystal process is processed the back in the epitaxy that is fit to GaInN, and can launch gold-tinted under the excitation of high strength blue light.
The foregoing description shows: press the gallium oxide type fluorescent substrate monocrystal body of the doped rare earth element of the inventive method preparation, be suitable for epitaxy high quality GaInN base blue-light semiconductor film, combine with GaInN base blue light and can realize the white light emission of LED.

Claims (4)

1, a kind of gallium oxide type fluorescent substrate monocrystal body of doped rare earth element is characterized in that the molecular formula of this substrate monocrystal body is: β-Ga 2-2x(RE) 2xO 3, wherein RE is cerium Ce or thulium Tm, x=0.001～0.1.
2, the preparation method of the gallium oxide type fluorescent substrate monocrystal body of the described doped rare earth element of claim 1 is characterized in that this crystal by adopting float-zone method grows, and follows these steps to carry out:
1. behind the doping ratio x that determines rare earth element, take by weighing purity in proportion and be higher than 99.99% Ga 2O 3Oxide raw material with rare earth element;
2. the above-mentioned raw material thorough mixing that takes by weighing is become uniform mixing raw material;
3. above-mentioned mixing raw material is packed in the mould, be pressed into fuel rod (10), the size range of fuel rod: long 1～20cm, diameter 1～20mm waiting under the static pressure of 10-100MPa;
4. described fuel rod (10) is hung in the silicon molybdenum stove with platinum wire, is being lower than 1500 ℃ sintering temperature more than 8 hours;
5. the fuel rod (10) that sinters is hung on the last bull stick (1) of floating region stove, with β-Ga with platinum wire 2O 3Seed crystal is installed on the following bull stick (6) of floating region stove;
6. after shove charge finishes, adopt the mode of infrared lamp (4) heating to make fuel rod (10) fusion, form melting zone (3); β-Ga 2-2x(RE) 2xO 3Melt temperature be 1750 ℃, growth atmosphere is N 2+ O 2, N/ (O+N)=1%～99%, the crystalline speed of growth is 1～10mm/hr, the crystalline rotating speed is 10～20rpm, crystal through inoculation, necking down, shouldering, etc. behind neck, ending, the temperature-fall period, growth ending;
7. β-the Ga that takes out in the stove of floating region 2-2x(RE) 2xO 3The fluorescence substrate monocrystal is at N 2Atmosphere under carry out anneal routinely;
3, the preparation method of the gallium oxide type fluorescent substrate monocrystal body of doped rare earth element according to claim 2 is characterized in that described β-Ga 2O 3Seed crystal is the β-Ga of a axle, b axle or c axle crystallization direction 2O 3Single crystal.
4, according to the preparation method of the gallium oxide type fluorescent substrate monocrystal body of claim 2 or 3 described doped rare earth elements, the oxide compound that it is characterized in that described rare earth element is CeO 2Or Tm 2O 3
CNA2006100240956A 2006-02-23 2006-02-23 Doped rare earth element gallium oxide type fluorescent substrate material and its prepn. method Pending CN1831084A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021647A (en) * 2010-10-22 2011-04-20 北京工业大学 Method for rapid growth of centimeter magnitude ruby crystal
CN103230601A (en) * 2013-04-16 2013-08-07 浙江大学 Rare earth doped gallium oxide drug-loading body preparation method
CN105734498A (en) * 2016-04-13 2016-07-06 张权岳 Cobalt doped gallium oxide diluted magnetic semiconductor film and preparation method thereof
CN111739988A (en) * 2020-06-29 2020-10-02 山东大学 Vertical-structure broadband near-infrared LED and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021647A (en) * 2010-10-22 2011-04-20 北京工业大学 Method for rapid growth of centimeter magnitude ruby crystal
CN102021647B (en) * 2010-10-22 2012-05-30 北京工业大学 Method for rapid growth of centimeter magnitude ruby crystal
CN103230601A (en) * 2013-04-16 2013-08-07 浙江大学 Rare earth doped gallium oxide drug-loading body preparation method
CN105734498A (en) * 2016-04-13 2016-07-06 张权岳 Cobalt doped gallium oxide diluted magnetic semiconductor film and preparation method thereof
CN105734498B (en) * 2016-04-13 2018-06-15 张权岳 A kind of cobalt doped gallium oxide diluted semi-conductor thin-film and preparation method thereof
CN111739988A (en) * 2020-06-29 2020-10-02 山东大学 Vertical-structure broadband near-infrared LED and preparation method thereof
CN111739988B (en) * 2020-06-29 2021-11-12 山东大学 Vertical-structure broadband near-infrared LED and preparation method thereof

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