CN115832132A - Deep ultraviolet UVC light-emitting diode for water sterilization and preparation method thereof - Google Patents
Deep ultraviolet UVC light-emitting diode for water sterilization and preparation method thereof Download PDFInfo
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- 230000001954 sterilising effect Effects 0.000 title claims abstract description 32
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 28
- 239000010980 sapphire Substances 0.000 claims abstract description 28
- 229910002704 AlGaN Inorganic materials 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 25
- 229910002601 GaN Inorganic materials 0.000 description 14
- 230000006798 recombination Effects 0.000 description 9
- 238000005215 recombination Methods 0.000 description 9
- 230000005684 electric field Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 108020000946 Bacterial DNA Proteins 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- 102000053602 DNA Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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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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- 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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- 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
- H01L33/12—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 stress relaxation structure, e.g. buffer layer
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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
- H01L33/02—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 deep ultraviolet UVC light-emitting diode for water sterilization and a preparation method thereof, and relates to the field of growth of semiconductor photoelectric materials. The invention grows the light emitting diode of UVC wave band on the semi-polar sapphire substrate, has realized the high stability high-power is shiny under the deep ultraviolet wave band, achieve the goal of sterilizing dynamically steadily, high-efficiently.
Description
The invention discloses a divisional application of a stable semi-polar deep ultraviolet UVC light-emitting diode and a preparation method thereof, wherein the application number of a parent case is 202010642673.2, and the application date is 2020.07.06.
Technical Field
The invention relates to the technical field of semiconductor photoelectric material growth, in particular to a deep ultraviolet UVC light-emitting diode for water sterilization and a preparation method thereof.
Background
Gallium nitride material is a polar semiconductor. Under different injection currents, a built-in electric field generated inside the device of the gallium nitride light-emitting diode greatly affects the performance of the device, for example, the wavelength of the device changes along with the change of the injection currents, the carrier recombination of the device is slow, the non-radiative recombination is more, and the light-emitting efficiency of the device is reduced.
Bacterial dna has a specific absorption wavelength in the ultraviolet band. The principle of ultraviolet sterilization is that bacteria absorb ultraviolet light, so that bonds of deoxyribonucleic acid of the bacteria are broken, and the bacteria die. Therefore, we need specific wavelength and powerful leds to achieve dynamic sterilization. However, if high power is required, the injection current of the light emitting diode needs to be increased. Due to the influence of the built-in electric field of gallium nitride, the light-emitting wavelength of gallium nitride changes, which is not favorable for high-power dynamic sterilization.
The invention patent application with the publication number of CN108321280A discloses a non-polar ultraviolet LED, which sequentially comprises an r-face sapphire substrate, a low-temperature AlGaN buffer layer, a high-temperature AlGaN buffer layer, a non-doped AlGaN layer, an n-type doped AlGaN layer, an AlGaN/AlGaN superlattice layer, an AlGaN/AlGaN multi-quantum well active region, a non-doped AlGaN cap layer, a low-temperature p-type doped AlGaN layer, a p-type doped AlGaN layer and a p-type heavily doped AlGaN layer from bottom to top. The AlGaN material is used as a basic material of the device in the whole structure, so that the light polarization characteristic of the nonpolar III-nitride light-emitting device is effectively utilized, and the light-emitting wavelength of the LED can be effectively regulated and controlled.
Although the application can regulate and control the light-emitting wavelength to a certain extent, when the applied voltage changes, the light-emitting wavelength still has larger fluctuation, and the carrier recombination curves of devices on the corresponding substrate also have great difference, so that the stability of the light-emitting diode is poor, and the dynamic sterilization of high power is still not facilitated. Therefore, how to realize a stable deep ultraviolet LED is a problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to provide a deep ultraviolet UVC light-emitting diode for water sterilization and a preparation method thereof, which can achieve the aim of stably and efficiently dynamically sterilizing by realizing high-stability and high-power light emission under a deep ultraviolet band.
In order to achieve the purpose, the invention provides the following scheme:
a deep ultraviolet UVC light emitting diode for water sterilization, which is applied to water sterilization;
the deep ultraviolet UVC light-emitting diode sequentially comprises a semipolar M-plane sapphire substrate, a low-temperature AlN buffer layer, an AlN/AlGaN superlattice layer, an n-type heavily doped AlGaN layer, an AlGaN/AlGaN multi-quantum well active region, a p-type doped AlInGaN layer and a p-type heavily doped GaN layer from bottom to top;
the thickness of the low-temperature AlN buffer layer is 10-40 nm; the superlattice period of the AlN/AlGaN superlattice layer is 10-20, and the thickness of each layer is 3nm; the thickness of the n-type heavily doped AlGaN layer is 1-3 mu m; the AlGaN/AlGaN multi-quantum well active region has 7 periods, wherein the thickness of the well layer is 12nm, and the thickness of the barrier layer is 3nm; the thickness of the p-type doped AlInGaN layer is 60-80 nm; the thickness of the p-type heavily doped GaN layer is 0.5-1 μm.
In order to achieve the purpose, the invention also provides the following technical scheme:
a preparation method of a deep ultraviolet UVC light-emitting diode for water sterilization comprises the following steps:
placing a semipolar M-plane sapphire substrate in H 2 Heating at 1050 ℃ for 5min in the atmosphere, and then performing nitridation treatment to obtain a cleaned and nitrided sapphire substrate;
growing a low-temperature AlN buffer layer on the cleaned and nitrided sapphire substrate under a first growing condition; the first growth conditions are: the growth temperature is 670 ℃, the pressure of the reaction chamber is 40torr, the flow of ammonia gas is 8000-9000 mu mol/min, the molar ratio of V/III is 5000-5500, and the growth thickness is 25nm;
growing an AlN/AlGaN superlattice layer on the low-temperature AlN buffer layer under a second growth condition; the second growth conditions are: the temperature in the reaction chamber is 1250 ℃, the air pressure is 30mbar, the flow of white ammonia is 1200sccm, the flow of an Al source is 35 mu mol/min, and the flow of a gallium source is 22 mu mol/min;
growing an n-type heavily doped AlGaN layer on the AlN/AlGaN superlattice layer under a third growth condition; the third growth condition is: the doping concentration of Si is 1E 18-5E 19, the growth temperature is 900-1300 ℃, the growth pressure is 200-50mbar 3 The flow ratio of (TMGa + TMAl) is 40-200, and the flow ratio of TMGa/TMAl is 0.1-10;
growing an AlGaN/AlGaN multi-quantum well active region on the n-type heavily doped AlGaN layer;
growing a p-type doped AlInGaN layer in the AlGaN/AlGaN multi-quantum well active region under a fourth growth condition; the fourth growth condition is: the growth temperature is 750-850 ℃, the pressure is 100-300 torr, and TMGa, TMIn, TMAl and NH are introduced 3 And a p-type dopant with a doping concentration of 1X 10 19 cm -3 ；
Growing a p-type heavily doped GaN layer on the p-type doped AlInGaN layer under a fifth growth condition; the fifth growth condition is: the growth temperature is 950-1050 ℃, the pressure is 100-700 torr, ga source, N source and p-type dopant are introduced, the doping concentration is 1 x 10 19 cm -3 。
Optionally, the nitriding treatment specifically includes:
keeping the temperature of 1050 ℃ unchanged, and introducing NH 3 The surface of the semipolar M-plane sapphire substrate was nitrided for 10 min.
Optionally, the low-temperature growth thickness of the low-temperature AlN buffer layer is 10-40 nm.
Optionally, the superlattice period of the AlN/AlGaN superlattice layer is 10 to 20.
Optionally, the growth conditions of the AlGaN/AlGaN multi-quantum well active region are as follows: growth temperature is 750 ℃ in N 2 Under the atmosphere, the AlGaN barrier layer in the first 6 periods from bottom to top is an n-type doped layer, the doping source is Si, and the doping concentration is 10 17 cm -3 In the 7 th cycle, doping is not performed, and the well layer is not doped.
Optionally, the growth thickness of the p-type heavily doped GaN layer is 0.5-1 μm.
Compared with the prior art, the invention provides the deep ultraviolet UVC light-emitting diode for water sterilization, which is applied to the aspect of water sterilization; the deep ultraviolet UVC light-emitting diode sequentially comprises a semipolar M-plane sapphire substrate, a low-temperature AlN buffer layer, an AlN/AlGaN superlattice layer, an n-type heavily doped AlGaN layer, an AlGaN/AlGaN multi-quantum well active region, a p-type doped AlInGaN layer and a p-type heavily doped GaN layer from bottom to top; the thickness of the low-temperature AlN buffer layer is 10-40 nm; the superlattice period of the AlN/AlGaN superlattice layer is 10-20, and the thickness of each layer is 3nm; the thickness of the n-type heavily doped AlGaN layer is 1-3 mu m; the AlGaN/AlGaN multi-quantum well active region has 7 periods, wherein the thickness of a well layer is 12nm, and the thickness of a barrier layer is 3nm; the thickness of the p-type doped AlInGaN layer is 60-80 nm; the thickness of the p-type heavily doped GaN layer 1 is 0.5-1 μm. The deep ultraviolet UVC light-emitting diode obtained by sequentially growing on the semi-polar sapphire substrate can simultaneously realize the following aims: 1) the influence of a built-in electric field of a device is reduced, 2) the stability of the light-emitting wavelength of the light-emitting diode under different injection currents is improved, and 3) the light in a deep ultraviolet waveband can be emitted, so that dynamic water sterilization is facilitated, and the stable and efficient operation of a sterilization process is ensured. In conclusion, the invention can stabilize the luminous wavelength of the device, can also accelerate the service life of the carrier of the device by controlling the built-in electric field in the material, is beneficial to the preparation and application of the high-stability high-power deep ultraviolet UVC wave band light-emitting diode, and can also be used for dynamic water sterilization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a deep ultraviolet UVC light emitting diode for water sterilization according to an embodiment;
FIG. 2 is a flow chart of a method for preparing a deep ultraviolet UVC light-emitting diode for water sterilization provided by the second embodiment;
FIG. 3 is a graph of emission wavelength versus light intensity for a polar deep ultraviolet UVC light emitting diode at different voltage reductions;
FIG. 4 is a graph of the variation of the emission wavelength and light intensity of a semi-polar deep ultraviolet UVC light emitting diode at different voltage reductions;
FIG. 5 is a graph of emission wavelength versus light intensity for different voltage increments for a polar deep ultraviolet UVC light emitting diode;
FIG. 6 is a graph of emission wavelength versus light intensity for a semi-polar deep ultraviolet UVC light emitting diode at different voltage increments;
FIG. 7 is a graph of carrier recombination rate changes for a polar deep ultraviolet UVC light emitting diode at different voltage changes;
fig. 8 is a graph of carrier recombination rate changes under different voltage changes of a semi-polar deep ultraviolet UVC light-emitting diode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, the present invention is described in detail with reference to the accompanying drawings and the detailed description thereof.
Example one
As shown in fig. 1, the present embodiment provides a deep ultraviolet UVC light emitting diode for water sterilization, which sequentially includes, from bottom to top, a semipolar sapphire substrate 1, a low-temperature AlN buffer layer 2 grown on the sapphire substrate, an AlN/AlGaN superlattice layer 3, an n-type heavily doped AlGaN layer 4, an AlGaN/AlGaN multi-quantum well active region 5, a p-type doped AlInGaN layer 6, and a p-type heavily doped GaN layer 7. The light-emitting diode of the deep ultraviolet UVC wave band uses semi-polar sapphire as a substrate, so that the light-emitting wavelength of a device can be stabilized, the service life of a device carrier can be prolonged by controlling a built-in electric field in the material, and the preparation and the application of the light-emitting diode of the high-stability high-power deep ultraviolet UVC wave band are facilitated.
Specifically, sapphire (Al) 2 O 3 ) The crystal face comprises a polar C face, a semipolar M face, an R face and a nonpolar A face, and a C face substrate is generally adopted and is easy to grow. Stress is generated due to lattice mismatch, causing internal polarization fields to tie up carriers, resulting in low internal quantum efficiency. The defect density can be greatly reduced by adopting a nonpolar or semipolar substrate. The semipolar substrate is more stable than the nonpolar substrate, and therefore, the present invention employs a semipolar sapphire substrate, such as
And crystal plane sapphire.
Ultraviolet light requires sufficient energy, including sufficient intensity and time of irradiation, and the appropriate wavelength band if effective sterilization is to be achieved. The ultraviolet band is divided into UVA, UVB and UVC according to wavelength from long to short, wherein UVC is a band having the shortest wavelength and the highest energy, and is often called deep ultraviolet band. For sterilization, the most effective is indeed UVC. Therefore, the invention grows the light-emitting diode of UVC wave band on the semi-polar sapphire substrate.
The thickness of the low-temperature AlN buffer layer is 10-40nm, the superlattice period of the AlN/AlGaN superlattice layer is 10-20, the thickness of each layer is 3nm, the thickness of the n-type heavily doped AlGaN layer is 1-3 mu m, the active region of the AlGaN/AlGaN multiple quantum well is 7 periods, the thickness of the well layer is 12nm, and the thickness of the barrier layer is 3nm. The thickness of the p-type doped AlInGaN layer is 60-80nm, and the thickness of the p-type heavily doped GaN layer is 0.5-1 μm.
Example two
As shown in fig. 2, this embodiment provides a method for preparing a deep ultraviolet UVC light emitting diode for water sterilization, which specifically includes the following steps:
s1, cleaning and desalting the semi-polar sapphire substrate.
Specifically, a semipolar sapphire substrate is placed in H 2 Heating to 1050 ℃ in the atmosphere and maintaining for 5min to remove pollutants on the surface of the sapphire substrate; keeping the temperature constant and introducing NH 3 The substrate surface was nitrided for 10 min.
And S2, growing an AlN buffer layer on the semi-polar sapphire substrate by using low temperature.
Specifically, a low-temperature aluminum nitride (AlN) buffer layer with the thickness of 10-40 nm is grown on a semi-polar sapphire substrate at a low temperature, and the growth conditions are as follows: the growth temperature is 670 ℃, the pressure of the reaction chamber is 40torr, the flow of ammonia gas is 8000-9000 mu mol/min, the molar ratio of V/III is 5000-5500, and the growth thickness is 25nm.
And S3, growing an AlN/AlGaN superlattice layer on the low-temperature AlN buffer layer.
Specifically, an AlN/AlGaN superlattice layer grows on the low-temperature AlN buffer layer, the superlattice period of the AlN/AlGaN superlattice layer is 10-20, and the growth conditions are as follows: the temperature in the reaction chamber is 1250 ℃, the air pressure is 30mbar, the white ammonia flow is 1200sccm, the Al source flow is 35 mu mol/min, and the gallium source flow is 22 mu mol/min.
And S4, growing an n-type heavily doped AlGaN layer on the AlN/AlGaN superlattice layer.
Specifically, the growth conditions were: si doping concentration is 1E 18-5E 19, growth temperature is 900-1300 ℃, growth pressure is 200-50mbar 3 The flow rate ratio of (TMGa + TMAl) is 40-200, and the flow rate ratio of TMGa/TMAl is 0.1-10.
And S5, growing an AlGaN/AlGaN multi-quantum well active region on the n-type heavily doped AlGaN layer.
Specifically, the growth conditions were: growth temperature is 750 ℃ in N 2 Under the atmosphere, the AlGaN barrier layer in the first 6 periods from bottom to top is an n-type doped layer, the doping source is Si, and the doping concentration is 10 17 cm -3 In the 7 th cycle, doping is not performed, and the well layer is not doped.
And S6, growing a p-type doped AlInGaN layer in the AlGaN/AlGaN multi-quantum well active region.
Specifically, the growth conditions were: the growth temperature is 750-850 deg.C, and the pressure is 100-300 torr, introducing Ga source (such as TMGa or TEGa), in source (such as TMIn), al source (such as TMAl), N source (such as NH) 3 ) And a p-type dopant (e.g., cp) 2 Mg) with a doping concentration of 1X 10 19 cm -3 And growing a p-type doped AlInGaN layer.
And S7, growing a p-type heavily doped GaN layer on the p-type doped AlInGaN layer.
Specifically, the growth conditions were: the growth temperature is 950-1050 ℃, the pressure is 100-700 torr, ga source, n source and p-type dopant are introduced, the doping concentration is 1 x 10 19 cm -3 And growing a p-type GaN layer.
To further determine the performance of the semi-polar deep ultraviolet UVC leds prepared in example two, the present invention compares the semi-polar deep ultraviolet UVC leds with existing polar deep ultraviolet UVC leds. Specifically, the performance of the light emitting diode is evaluated by adopting the light emitting wavelength, the light intensity and the carrier recombination rate.
Fig. 3 and 4 respectively show the light emitting wavelength and the light intensity of the polar deep ultraviolet UVC light emitting diode and the semi-polar deep ultraviolet UVC light emitting diode under different voltage reduction amounts; fig. 5 and 6 respectively show the light emitting wavelength and the light intensity of the polar deep ultraviolet UVC light emitting diode and the semi-polar deep ultraviolet UVC light emitting diode under different voltage increment amounts. It can be known from the figure that both the polar deep ultraviolet UVC light emitting diode and the semi-polar deep ultraviolet UVC light emitting diode have good light emitting performance, but the semi-polar deep ultraviolet UVC light emitting diode is more stable under different voltage effects, and the influence of the voltage change on the light emitting wavelength and the light intensity is small.
Fig. 7 and 8 respectively show carrier recombination rates of the polar deep ultraviolet UVC light emitting diode and the semi-polar deep ultraviolet UVC light emitting diode under different voltage changes, and obviously, along with the voltage change, the carrier recombination rate corresponding to the semi-polar deep ultraviolet UVC light emitting diode changes less, and the carrier recombination rate of the polar deep ultraviolet UVC light emitting diode increases with increasing wavelength with time under the effect of the voltage change.
Therefore, the deep ultraviolet UVC light-emitting diode for water sterilization and the preparation method thereof provided by the invention have the advantages that the light-emitting diode with the UVC wave band grows on the semipolar sapphire substrate, the influence of a built-in electric field of a device is reduced, and the stability of the light-emitting wavelength of the light-emitting diode under different injection currents is improved. The light-emitting diode of the deep ultraviolet UVC wave band uses semi-polar sapphire as a substrate, so that the light-emitting wavelength of a device can be stabilized, the service life of a device carrier can be prolonged by controlling a built-in electric field in the material, the preparation and the application of the light-emitting diode of the high-stability high-power deep ultraviolet UVC wave band are facilitated, and the light-emitting diode can also be used for dynamic water sterilization.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the system disclosed by the embodiment, the description is relatively simple because the system corresponds to the method disclosed by the embodiment, and the relevant points can be referred to the description of the method part.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (7)
1. A deep ultraviolet UVC light emitting diode for water sterilization, wherein the deep ultraviolet UVC light emitting diode is applied to water sterilization;
the deep ultraviolet UVC light-emitting diode sequentially comprises a semipolar M-plane sapphire substrate, a low-temperature AlN buffer layer, an AlN/AlGaN superlattice layer, an n-type heavily doped AlGaN layer, an AlGaN/AlGaN multi-quantum well active region, a p-type doped AlInGaN layer and a p-type heavily doped GaN layer from bottom to top;
the thickness of the low-temperature AlN buffer layer is 10-40 nm; the superlattice period of the AlN/AlGaN superlattice layer is 10-20, and the thickness of each layer is 3nm; the thickness of the n-type heavily doped AlGaN layer is 1-3 mu m; the AlGaN/AlGaN multi-quantum well active region has 7 periods, wherein the thickness of a well layer is 12nm, and the thickness of a barrier layer is 3nm; the thickness of the p-type doped AlInGaN layer is 60-80 nm; the thickness of the p-type heavily doped GaN layer is 0.5-1 μm of the thickness of the type heavily doped GaN layer 1.
2. A preparation method of a deep ultraviolet UVC light-emitting diode for water sterilization is characterized by comprising the following steps:
placing a semipolar M-plane sapphire substrate in H 2 Heating at 1050 ℃ for 5min in the atmosphere, and then performing nitridation treatment to obtain a cleaned and nitrided sapphire substrate;
growing a low-temperature AlN buffer layer on the cleaned and nitrided sapphire substrate under a first growing condition; the first growth conditions are: the growth temperature is 670 ℃, the pressure of the reaction chamber is 40torr, the flow of ammonia gas is 8000-9000 mu mol/min, the molar ratio of V/III is 5000-5500, and the growth thickness is 25nm;
growing an AlN/AlGaN superlattice layer on the low-temperature AlN buffer layer under a second growth condition; the second growth conditions are: the temperature in the reaction chamber is 1250 ℃, the air pressure is 30mbar, the flow of white ammonia is 1200sccm, the flow of an Al source is 35 mu mol/min, and the flow of a gallium source is 22 mu mol/min;
growing an n-type heavily doped AlGaN layer on the AlN/AlGaN superlattice layer under a third growth condition; the third growth condition is: the doping concentration of Si is 1E 18-5E 19, the growth temperature is 900-1300 ℃, the growth pressure is 200-50mbar 3 The flow ratio of TMGa + TMAl is 40-200, and the flow ratio of TMGa/TMAl is 0.1-10;
growing an AlGaN/AlGaN multi-quantum well active region on the n-type heavily doped AlGaN layer;
growing a p-type doped AlInGaN layer in the AlGaN/AlGaN multi-quantum well active region under a fourth growth condition; the fourth growth condition is: the growth temperature is 750-850 ℃, the pressure is 100-300 torr, and TMGa, TMIn, TMAl and NH are introduced 3 And a p-type dopant with a doping concentration of 1X 10 19 cm -3 ；
In the fifth birthGrowing a p-type heavily doped GaN layer on the p-type doped AlInGaN layer under a long condition; the fifth growth condition is: the growth temperature is 950-1050 ℃, the pressure is 100-700 torr, ga source, N source and p-type dopant are introduced, the doping concentration is 1 x 10 19 cm -3 。
3. The method for preparing the deep ultraviolet UVC light-emitting diode for water sterilization according to claim 2, wherein said nitriding treatment is specifically:
keeping the temperature of 1050 ℃ unchanged, and introducing NH 3 The surface of the semipolar M-plane sapphire substrate was nitrided for 10 min.
4. The method of claim 2, wherein the low-temperature AlN buffer layer has a low-temperature growth thickness of 10 to 40nm.
5. The method of claim 2, wherein the AIN/AlGaN superlattice layer has a superlattice period of 10 to 20.
6. The method of manufacturing a deep ultraviolet UVC light emitting diode for water sterilization according to claim 2, wherein the growth conditions of the AlGaN/AlGaN multi-quantum well active region are as follows: growth temperature is 750 ℃ in N 2 Under the atmosphere, the AlGaN barrier layers in the first 6 periods from bottom to top are n-type doped layers, the doping source is Si, and the doping concentration is 10 17 cm -3 In the 7 th cycle, doping is not performed, and the well layer is not doped.
7. The method of claim 2, wherein the p-type heavily doped GaN layer is grown to a thickness of 0.5-1 μm.
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