CN110504339B - Ultraviolet LED preparation method and ultraviolet LED - Google Patents

Ultraviolet LED preparation method and ultraviolet LED Download PDF

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CN110504339B
CN110504339B CN201910801072.9A CN201910801072A CN110504339B CN 110504339 B CN110504339 B CN 110504339B CN 201910801072 A CN201910801072 A CN 201910801072A CN 110504339 B CN110504339 B CN 110504339B
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CN110504339A (en
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黄小辉
郑远志
康建
梁旭东
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Maanshan Jiesheng Semiconductor Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
    • 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
    • H01L33/14—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
    • H01L33/145—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 with a current-blocking structure
    • 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 provides an ultraviolet LED preparation method and an ultraviolet LED, which comprise the following steps: introducing a metal source and a V-group reactant, growing a buffer layer on the substrate, growing an undoped AltGal-tN layer on the buffer layer, growing an N-type AlwGal-wN layer on the undoped AltGal-tN layer, growing a multi-quantum well structure layer on the N-type AlwGal-wN layer, performing Ga atom replacement on the multi-quantum well structure layer, growing a P-type AltGa1-tN electron blocking layer on the multi-quantum well structure layer, and growing a P-type hole injection layer on the P-type AltGa1-tN electron blocking layer to form the ultraviolet LED. The carrier recombination efficiency is improved, so that the luminous efficiency of the ultraviolet LED is improved, and the sterilization, phototherapy and curing efficiency is improved.

Description

Ultraviolet LED preparation method and ultraviolet LED
Technical Field
The invention relates to the technical field of ultraviolet LED growth methods, in particular to an ultraviolet LED preparation method for improving carrier recombination efficiency and an ultraviolet LED.
Background
The III-V compound is a compound consisting of III elements of boron, aluminum, gallium, indium and thallium in the periodic table of chemical elements and V elements of nitrogen, phosphorus, arsenic, antimony and bismuth. The III-V semiconductor is generally said to be a binary compound consisting of group IIIA and group VA elements. The III-V group compound semiconductor material has high carrier mobility and large forbidden band width, and is applied to light-emitting devices, high-speed devices, high-temperature devices, high-frequency devices, high-power devices and the like more quickly and widely.
In the prior art, an AlGaN (aluminum gallium nitride) -based Light Emitting Diode (LED) in a III-V semiconductor material can emit ultraviolet light of 200nm to 365nm, and the ultraviolet light has excellent performances such as sterilization, phototherapy, photocuring, and the like. Among them, the UVC band ultraviolet LED of 200nm to 280nm is widely used for sterilization of object surfaces, air, water, and the like at present as the most important sterilization material in the ultraviolet sterilization apparatus. Meanwhile, medical science finds that the UVB wave band of 280nm-320nm has excellent phototherapy effect, especially has very good curative effect on vitiligo, and is widely applied to the field of medical phototherapy, and the wave band of 320nm-365nm has very good photocuring function and is often applied to the curing fields of nail beautifying curing, printing curing and the like.
However, due to the problems of low electron blocking efficiency, poor hole injection and the like, the AlGaN quantum well layer with high Al composition has low carrier recombination efficiency, so that the ultraviolet LED has low luminous efficiency, and the efficiency of sterilization, phototherapy and curing is also low.
Disclosure of Invention
The invention provides an ultraviolet LED (light-emitting diode) preparation method and an ultraviolet LED, and solves the problems that in the prior art, due to the fact that an AlGaN quantum well layer with a high Al component is low in electron blocking efficiency and poor in hole injection, carrier recombination efficiency is low, the ultraviolet LED is low in luminous efficiency, and meanwhile, the sterilization efficiency, the phototherapy efficiency and the curing efficiency are low.
In order to solve the above problems, the present invention provides a method for preparing an ultraviolet LED, comprising:
introducing a metal source and a V-group reactant, and growing a buffer layer on the substrate;
growing an undoped AltGal-tN layer on the buffer layer;
growing an N-type AlwGal-wN layer on the undoped AltGal-tN layer;
growing an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer on the N-type AlwGal-wN layer;
carrying out Ga atom replacement on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer;
growing a P-type AltGa1-tN electron blocking layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer;
and growing a P-type hole injection layer on the P-type AltGa1-tN electron blocking layer to form the ultraviolet LED.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
growing AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer on N type AlwGal-wN layer includes:
cyclically and alternately growing AlxGa1-xN quantum barrier layers and AlyGa1-yN quantum well layers on the N-type AlwGal-wN layers to form an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer;
wherein the AlxGa1-xN quantum barrier layer and the AlyGa1-yN quantum well layer are arranged in a laminating way,
the first layer and the last layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer are AlxGa1-xN quantum barrier layers; or the first layer and the last layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer are AlyGa1-yN quantum well layers.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
the Ga atom replacement of the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer comprises the following steps:
stopping introducing the metal source and the V-group reactant, introducing hydrogen, performing Ga atom replacement on the AlxGa1-xN quantum barrier layer and/or the AlyGa1-yN quantum well layer, and forming an AlGaN layer with gradually changed Al components in the AlxGa1-xN quantum barrier layer and/or the AlyGa1-yN quantum well layer, wherein the Al component in the AlGaN layer is smaller than the Al component on the surface layer of the AlGaN layer.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
the Al component of the AlGaN layer in the AlxGa1-xN quantum barrier layer is larger than that of the AlGaN layer in the AlyGa1-yN quantum well layer.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
growing a P-type AltGa1-tN electron blocking layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer comprises the following steps:
at least two P-type AltGa1-tN electron blocking layers are grown on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer in a laminating mode.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
the method for performing Ga atom replacement by growing at least two P-type AltGa1-tN electron blocking layers on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer in a laminating way comprises the following steps:
stopping introducing the metal source and the V-group reactant, introducing hydrogen, performing Ga atom replacement on at least one layer of the P-type AltGa1-tN electron barrier layer, and forming an AlGaN layer with gradually changed Al components in the P-type AltGa1-tN electron barrier layer, wherein the Al components in the AlGaN layer are smaller than the Al components on the surface layer of the AlGaN layer.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
the thickness of the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer is 5-50 nm.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
the time for introducing the hydrogen is 5s-20 min.
As an optional mode, the ultraviolet LED preparation method provided by the invention,
the cycle number of alternately growing the AlxGa1-xN quantum barrier layer and the AlyGa1-yN quantum well layer is 2-100.
The invention also provides an ultraviolet LED which is prepared by adopting the ultraviolet LED preparation method.
According to the ultraviolet LED preparation method and the ultraviolet LED, the metal source and the V-group reactant are introduced, the buffer layer grows on the substrate, the undoped AltGal-tN layer grows on the buffer layer, the N-type AlwGal-wN layer grows on the undoped AltGal-tN layer, the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer grows on the N-type AlwGal-wN layer, Ga atomic replacement is carried out on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer, the P-type AltGa1-tN electron blocking layer grows on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer, and the P-type hole injection layer grows on the P-type AltGa1-tN electron blocking layer to form the ultraviolet LED. The carrier recombination efficiency is improved, so that the luminous efficiency of the ultraviolet LED is improved, and the sterilization, phototherapy and curing efficiency is improved.
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 description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a flowchart of a method for manufacturing an ultraviolet LED according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an ultraviolet LED according to a second embodiment of the present invention;
fig. 3 is a schematic structural diagram of an ideal energy band of an ultraviolet LED according to a second embodiment of the present invention;
fig. 4 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum well and a second electron blocking layer according to a second embodiment of the present invention;
fig. 5 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum well and a first electron blocking layer according to a second embodiment of the present invention;
fig. 6 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum barrier and a first electron blocking layer according to a second embodiment of the present invention;
fig. 7 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum barrier and a second electron blocking layer according to a second embodiment of the present invention.
Reference numerals
10-a substrate;
20-a buffer layer;
30-undoped AltGal-tN layer;
a 40-N type AlwGal-wN layer;
50-multiple quantum well structure layer;
a 60-P type AltGa1-tN electron blocking layer;
a 70-P type hole injection layer.
Detailed Description
The technical solutions in the embodiments of the present invention are 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 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.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
Example one
Fig. 1 is a schematic flow chart of a method for manufacturing an ultraviolet LED according to an embodiment of the present invention. As shown in fig. 1, a method for manufacturing an ultraviolet LED according to a first embodiment of the present invention includes:
s101, introducing a metal source and a V-group reactant, and growing a buffer layer on the substrate.
Specifically, when the temperature of the reaction chamber is raised to 800-950 ℃ and the pressure is 400mbar, the metal source and ammonia gas are introduced to react for 2-3min, and the metal source and ammonia gas are decomposed at the temperature and carry out chemical reaction to form an amorphous buffer growth layer with the thickness of 25 nm. When the temperature of the reaction chamber is increased to 1250-.
Specifically, the metal source reactant and the buffer layer may have the following characteristics: 1) capable of decomposing into metal atoms at high temperature; 2) the metal atoms can react with the N atoms to form an amorphous buffer layer; 3) the thickness of the buffer layer can be 0-5000 nm. A typical buffer layer material is AlN.
The metal source may be a metal organic compound such as trimethylaluminum, trimethylgallium, or the like. The substrate may be one of sapphire, silicon carbide, and the like.
Alternatively, the growth apparatus may be one of a metal organic chemical vapor deposition apparatus (MOCVD), a molecular beam epitaxy apparatus (MBE), and a hydride vapor phase epitaxy apparatus (HVPE).
S102, growing an undoped AltGal-tN layer on the buffer layer.
Specifically, the temperature of the reaction chamber is reduced to 1140 ℃, the pressure is maintained at 200mbar, hydrogen, a metal source and ammonia gas are introduced for 60-90min, and an undoped AltGal-tN layer with the thickness of 1000-1500nm is grown on the undoped buffer growth layer.
S103, growing an N-type AlwGal-wN layer on the non-doped AltGal-tN layer.
Specifically, the temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, a metal source and ammonia gas are introduced for 60-120min, silane is doped, and an N-type AlwGal-wN layer with the thickness of 1000-2000nm is grown on the undoped AltGal-tN layer.
S104, growing an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer on the N-type AlwGal-wN layer.
Specifically, the temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, a metal source and ammonia gas are introduced, and an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer grows on the N-type AlwGal-wN layer.
As an implementation mode, the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer is designed as follows:
and (3) cyclically and alternately growing AlxGa1-xN quantum barrier layers and AlyGa1-yN quantum well layers on the N-type AlwGal-wN layer to form an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer.
Wherein the AlxGa1-xN quantum barrier layer and the AlyGa1-yN quantum well layer are arranged in a laminating way,
the first layer and the last layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer are AlxGa1-xN quantum barrier layers; or the first layer and the last layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer are AlyGa1-yN quantum well layers.
And S105, carrying out Ga atom replacement on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer.
Specifically, the introduction of the metal source and ammonia gas is stopped, hydrogen gas is introduced, and Ga atom replacement is carried out on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer.
As one achievable embodiment, Ga atomic substitution of an AlxGa1-xN/AlyGa1-yN multiple quantum well structure layer comprises:
stopping introducing the metal source and the V-group reactant, introducing hydrogen, performing Ga atom replacement on the AlxGa1-xN quantum barrier layer and/or the AlyGa1-yN quantum well layer, and forming an AlGaN layer with gradually changed Al components in the AlxGa1-xN quantum barrier layer and/or the AlyGa1-yN quantum well layer, wherein the Al component in the AlGaN layer is smaller than the Al component on the surface layer of the AlGaN layer.
In addition, the step (4) and the step (5) are to grow AlxGa1-xN/AlyGa1-yN multi-quantum well structure layers on the N-type AlwGal-wN layers. And carrying out high-temperature Ga atom replacement on an AlxGa1-xN quantum barrier layer or an AlyGa1-yN quantum well layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer to form an ultra-high potential barrier energy band, wherein the ultra-high potential barrier energy band can effectively prevent electrons from overflowing, reduce hole activation energy and improve hole injection efficiency.
For example, the process of growing the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer and performing Ga atom replacement can be as follows: after growing an AlxGa1-xN quantum barrier layer, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for a period of time, performing Ga atom replacement on the AlxGa1-xN quantum barrier layer to form an AlGaN layer with gradually changed Al components on the AlxGa1-xN quantum barrier layer, introducing hydrogen gas, the metal source and ammonia gas to grow an AlyGa1-yN quantum well layer, and repeating the steps to form the periodic AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer.
Optionally, the AlxGa1-xN/AlyGa1-yN multi-quantum well structure is a periodic growth structure, and the period number is 2-100 times. Meanwhile, the thickness of the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer is controlled within the range of 5-50nm (wherein the well width is 1-10nm, and the barrier width is 5-40nm), when the AlxGa1-xN quantum barrier layer or the AlyGa1-yN quantum well layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer is subjected to high-temperature Ga atom replacement, the introduction of the metal source and ammonia gas is stopped, hydrogen gas is introduced, and the time for introducing the hydrogen gas is controlled within 5s-20 min.
Further, the Al composition of the AlGaN layer in the AlxGa1-xN quantum barrier layer is larger than that of the AlGaN layer in the AlyGa1-yN quantum well layer.
Specifically, the AlGaN layer of the gradually changed Al composition gradually raises the electron barrier, and then can play a role in blocking electrons, and simultaneously gradually lowers the hole barrier, which is beneficial to the improvement of hole injection efficiency.
S106, growing a P-type AltGa1-tN electron blocking layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer.
In particular, the temperature and pressure of the reaction chamber are maintained constantAnd introducing hydrogen, a metal source and ammonia gas, and growing a P-type AltGa1-tN electron blocking layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer. The layer can be used as electron blocking layer and high carrier mobility insertion layer, and has thickness of 0-100nm and doping concentration of 1 × 1017-1x1020cm-3。
As an achievable implementation, the structure of the P-type AltGa1-tN electron blocking layer may be:
at least two P-type AltGa1-tN electron blocking layers are grown on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer in a laminating mode.
As an alternative implementation, the Ga atom replacement of at least two P-type AltGa1-tN electron blocking layers which are grown on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer in a stacking manner comprises:
stopping introducing the metal source and the V-group reactant, introducing hydrogen, performing Ga atom replacement on at least one layer of the P-type AltGa1-tN electron barrier layer, and forming an AlGaN layer with gradually changed Al components in the P-type AltGa1-tN electron barrier layer, wherein the Al components in the AlGaN layer are smaller than the Al components on the surface layer of the AlGaN layer.
Specifically, for example: keeping the temperature and the pressure of a reaction chamber unchanged, introducing hydrogen, a metal source and ammonia gas, growing a first electron barrier layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer, stopping introducing the metal source and the ammonia gas after the growth is finished, introducing the hydrogen gas, performing Ga atom replacement on the first electron barrier layer, introducing the hydrogen gas, the metal source and the ammonia gas, growing a second electron barrier layer, and repeating the steps to form a high-barrier P-type AltGa1-tN electron barrier layer and a low-barrier P-type AltGa1-tN electron barrier layer with periodic structures so as to form an ultrahigh-barrier energy band, further effectively blocking the overflow of electrons, reducing the activation energy of low holes and further improving the injection efficiency of the holes.
S107, growing a P-type hole injection layer on the P-type AltGa1-tN electron blocking layer to form the ultraviolet LED.
Specifically, the thickness of the layer can be 5-500nm, and the hole doping concentration is 1x1017-5x1020cm-3. Wherein the P-type hole injection layer canThe GaN-based LED comprises a P-type AlwGa1-wN layer, a P-type GaN layer, a periodic AlwGa1-wN/GaN layer, a periodic P-type AlzGa1-zN/AlwGa1-wN layer and a periodic P-type AlzGa1-zN/AlwGa 1-wN/Ga.
According to the preparation method of the ultraviolet LED provided by the embodiment of the invention, a buffer layer grows on a substrate by introducing a metal source and a V-group reactant, a non-doped AltGal-tN layer grows on the buffer layer, an N-type AlwGal-wN layer grows on the non-doped AltGal-tN layer, an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer grows on the N-type AlwGal-wN layer, Ga atom replacement is carried out on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer, a P-type AltGa1-tN electron blocking layer grows on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer, and a P-type hole injection layer grows on the P-type AltGa1-tN electron blocking layer to form the ultraviolet LED. The carrier recombination efficiency is improved, so that the luminous efficiency of the ultraviolet LED is improved, and the sterilization, phototherapy and curing efficiency is improved.
On the basis of the above embodiments, the following description will be made by taking as an example a method for preparing an LED by substituting Ga atoms for an AlyGa1-yN quantum well layer and a P-type AltGa1-tN second electron blocking layer, and the preparation process of the ultraviolet LED includes the following steps:
(1) raising the temperature of the MOCVD reaction chamber to 900 ℃, leading in trimethyl aluminum (150ml/min) and ammonia gas for 3min at the same time when the pressure is 400mbar, and reacting on the sapphire to form an AlN buffer layer of 25 nm; the temperature was raised to 1250 ℃ and the pressure was reduced to 100mbar, and hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 90min, forming a 1500nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 60 min. An undoped AltGa1-tN layer with a thickness of 1000nm was grown, with the Al component of AltGa1-tN being 50%.
(3) And (3) introducing hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas for 90min while keeping the temperature and the pressure of the reaction chamber unchanged, doping silane, and growing an N-type AlwGal-wN layer with the thickness of 1500nm, wherein the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1 multiplied by 1019cm < -3 >.
(4) Keeping the temperature at 1140 ℃, adjusting the pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities with the doping concentration of 1x 1018cm < -3 >, the growth time of 50s and the thickness of 10 nm.
(5) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas are introduced to grow an AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 35%, the growth time is 10s, and the thickness is 1 nm.
(6) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 5s, and performing Ga atom replacement on the AlyGa1-yN quantum well layer to form AlGaN with gradually changed Al components on the AlyGa1-yN quantum well layer, wherein the Al component is 35-55%, and the thickness of the thin layer is about 0.1 nm.
(7) And repeating the 4 th to 6 th steps for 2 cycles to form the quantum well structure with 2 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 50s, the thickness is 10nm, and the last quantum barrier layer is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a first P-type AltGa1-tN electron blocking layer, doping Mg impurities with the Al component of the P-type AltGa1-tN electron blocking layer being 65 percent, wherein the doping concentration of Mg is 1 multiplied by 1019cm < -3 >. The growth time was 30s and the thickness was 7 nm.
(10) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (80ml/min) and ammonia gas, growing a second P-type AltGa1-tN electron blocking layer, wherein the Al component of the P-type AltGa1-tN electron blocking layer is 40%, doping Mg impurities, the doping concentration of Mg is 1 multiplied by 1019cm < -3 >, the growth time is 30s, and the thickness is 5 nm.
(11) And stopping introducing the metal source and ammonia gas after the growth is finished, introducing hydrogen gas for 5s, and performing Ga atom replacement on the second P-type AltGa1-tN electron barrier layer to form AlGaN with gradually changed Al component on the second P-type AltGa1-tN electron barrier layer, wherein the Al component is 40-55%, and the thickness of the thin layer is about 0.1 nm.
(12) And repeating the steps 9 to 11 for 8 cycles to form 8 periods of high-barrier P-type AltGa1-tN electron blocking layers and low-barrier P-type AltGa1-tN electron blocking layers.
(13) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 35%, doping Mg impurities are doped, the doping concentration of Mg is 2 multiplied by 1019cm < -3 >, the growth time is 1min, and the thickness is 30 nm.
The ultraviolet LED is processed into 1mm after growth2350mA of current is introduced into the large and small chips, the wavelength is 280nm, the brightness is 120mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
Based on the above embodiments, the following description will be made by taking as an example a method for manufacturing an LED by substituting Ga atoms for an AlxGa1-xN quantum barrier layer and a P-type AltGa1-tN first electron blocking layer, where the manufacturing process of the ultraviolet LED includes the following steps:
(1) raising the temperature of the MOCVD reaction chamber to 900 ℃, leading in trimethyl aluminum (150ml/min) and ammonia gas for 3min at the same time when the pressure is 400mbar, and reacting on the sapphire to form an AlN buffer layer of 25 nm; the temperature was raised to 1250 ℃ and the pressure was reduced to 100mbar, and hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 120min to form a 2000nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 60 min. An undoped AltGa1-tN layer with a thickness of 1000nm was grown, with the Al component of AltGa1-tN being 50%.
(3) The temperature and the pressure of the reaction chamber are unchanged, hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas are introduced for 60min, silane is doped, an N-type AlwGal-wN layer with the thickness of 1000nm grows, the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1 multiplied by 1019cm-3。
(4) The temperature is maintained at 1140 ℃ and the pressure is adjusted toIntroducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas at 200mbar, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities with the doping concentration of 2 x1018cm-3The growth time was 50s and the thickness was 10 nm.
(5) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 3min, and performing Ga atom replacement on the AlxGa1-xN quantum barrier layer to form AlGaN with gradually changed Al components on the AlxGa1-xN quantum barrier layer, wherein the Al components are 56-95%, and the thickness of the thin layer is about 3 nm.
(6) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas are introduced to grow an AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 35%, the growth time is 30s, and the thickness is 3 nm.
(7) And repeating the 4 th cycle to the 6 th cycle for 6 cycles to form the quantum well structure with 6 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 50s, the thickness is 10nm, and the last quantum barrier layer is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a first P-type AltGa1-tN electron blocking layer, doping Mg impurities with the Al component of the P-type AltGa1-tN electron blocking layer being 65 percent, wherein the doping concentration of Mg is 1 multiplied by 1019cm-3. The growth time was 15s and the thickness was 3.5 nm.
(10) And stopping introducing the metal source and ammonia gas after the growth is finished, introducing hydrogen gas for 30s, and performing Ga atom replacement on the first P-type AltGa1-tN electron barrier layer to form AlGaN with gradually changed Al component on the first P-type AltGa1-tN electron barrier layer, wherein the Al component is 65-80%, and the thickness of the thin layer is about 0.5 nm.
(11) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (80ml/min) and ammonia gas, and growing a second P-type AltGa1-tN electron blocking layer, P-type AltGa1-the Al component of the tN electron blocking layer is 40%, Mg impurities are doped, and the doping concentration of Mg is 1 multiplied by 1019cm-3The growth time was 30s and the thickness was 5 nm.
(12) And repeating the steps 9 to 11 for 5 cycles to form 5 periods of high-barrier P-type AltGa1-tN electron blocking layers and low-barrier P-type AltGa1-tN electron blocking layers.
(13) Keeping the temperature and pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 35%, doping Mg impurities, and the doping concentration of Mg is 2 multiplied by 1019cm-3The growth time is 10min, and the thickness is 60 nm.
The ultraviolet LED is processed into 1mm after growth2350mA of current is introduced into the large and small chips, the wavelength is 280nm, the brightness is 125mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
On the basis of the above embodiments, the following description will be made by taking as an example a method for preparing an LED by Ga atom replacement for an AlyGa1-yN quantum well layer and a P-type AltGa1-tN first electron blocking layer, and the preparation process of the ultraviolet LED comprises the following steps:
(1) raising the temperature of the MOCVD reaction chamber to 800 ℃, leading in trimethyl aluminum (150ml/min) and ammonia gas for 3min at the same time when the pressure is 400mbar, and reacting on the sapphire to form an AlN buffer layer of 25 nm; the temperature was raised to 1250 ℃ and the pressure was reduced to 100mbar, and hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 120min to form a 2000nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 60 min. An undoped AltGa1-tN layer with a thickness of 1000nm was grown, with the Al component of AltGa1-tN being 50%.
(3) The temperature and the pressure of the reaction chamber are unchanged, hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas are introduced for 60min, silane is doped, an N-type AlwGal-wN layer with the thickness of 1000nm grows, the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1.5 multiplied by 1019cm-3。
(4) Maintaining the temperature at 1140 ℃, adjusting the pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities with the doping concentration of 2 x1018cm-3The growth time was 70s and the thickness was 14 nm.
(5) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas are introduced to grow an AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 35%, the growth time is 50s, and the thickness is 5 nm.
(6) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 3min, and performing Ga atom replacement on the AlyGa1-yN quantum well layer to form AlGaN with gradually changed Al component on the AlyGa1-yN quantum well layer, wherein the Al component is 35-80%, and the thickness of the thin layer is about 2 nm.
(7) And repeating the 4 th cycle to the 6 th cycle for 6 cycles to form the quantum well structure with 6 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 70s, the thickness is 14nm, and the last quantum barrier layer is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a first P-type AltGa1-tN electron blocking layer, doping Mg impurities with the Al component of the P-type AltGa1-tN electron blocking layer being 65 percent, wherein the doping concentration of Mg is 1 multiplied by 1019cm-3. The growth time was 60s and the thickness was 14 nm.
(10) And stopping introducing the metal source and ammonia gas after the growth is finished, introducing hydrogen gas for 4min, and performing Ga atom replacement on the first P-type AltGa1-tN electron barrier layer to form AlGaN with gradually changed Al component on the first P-type AltGa1-tN electron barrier layer, wherein the Al component is 65-100%, and the thickness of the thin layer is about 4 nm.
(11) The temperature and pressure of the reaction chamber are kept unchanged, and hydrogen, trimethyl gallium (50ml/min) and trimethyl aluminum are introduced(80ml/min) and ammonia gas, growing a second P-type AltGa1-tN electron blocking layer, wherein the Al component of the P-type AltGa1-tN electron blocking layer is 40%, doping Mg impurities, and the doping concentration of Mg is 1 multiplied by 1019cm-3The growth time was 30s and the thickness was 5 nm.
(12) And repeating the steps 9 to 11 for 5 cycles to form 5 periods of high-barrier P-type AltGa1-tN electron blocking layers and low-barrier P-type AltGa1-tN electron blocking layers.
(13) Keeping the temperature and pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 35%, doping Mg impurities, and the doping concentration of Mg is 2 multiplied by 1019cm-3The growth time is 5min, and the thickness is 30 nm.
(14) Cooling to 1000 deg.C, regulating pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min) and ammonia gas, continuously growing GaN hole injection layer, doping Mg impurity with Mg doping concentration of 2 × 1019cm-3The growth time is 5min, and the thickness is 10 nm.
The ultraviolet LED is processed into 1mm after growth2350mA of current is introduced into the large and small chips, the wavelength is 280nm, the brightness is 110mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
Based on the above embodiments, the following description will be made by taking as an example a method for preparing an LED by substituting Ga atoms for an AlxGa1-xN quantum barrier layer and a P-type AltGa1-tN second electron blocking layer, and the preparation process of the ultraviolet LED includes the following steps:
(1) the temperature of the MOCVD reaction chamber is raised to 950 ℃, the pressure is 400mbar, and trimethyl aluminum (150ml/min) and ammonia gas are introduced for 3min at the same time to react on the sapphire to form an AlN buffer layer with the thickness of 25 nm; the temperature was raised to 1350 ℃ and the pressure was reduced to 100mbar, and hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 150min to form a 2500nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 90 min. An undoped AltGa1-tN layer with a thickness of 1500nm was grown, with the Al component of AltGa1-tN being 50%.
(3) The temperature and the pressure of the reaction chamber are unchanged, hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas are introduced for 90min, silane is doped, an N-type AlwGal-wN layer with the thickness of 1500nm grows, the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1 multiplied by 1019cm-3。
(4) Maintaining the temperature at 1140 ℃, adjusting the pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities with the doping concentration of 1 × 1018cm-3The growth time was 80s and the thickness was 16 nm.
(5) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 20min, and performing Ga atom replacement on the AlxGa1-xN quantum barrier layer to form AlGaN with gradually changed Al components on the AlxGa1-xN quantum barrier layer, wherein the Al components are 56-100%, and the thickness of the thin layer is about 10 nm.
(6) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas are introduced to grow an AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 35%, the growth time is 25s, and the thickness is 2.5 nm.
(7) And repeating the steps 4 to 6 for 100 cycles to form the quantum well structure with 100 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 80s, the thickness is 16nm, and the last quantum barrier layer is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a first P-type AltGa1-tN electron blocking layer, doping Mg impurities with the Al component of the P-type AltGa1-tN electron blocking layer being 65 percent, wherein the doping concentration of Mg is 1 multiplied by 1019cm-3. The growth time was 45s and the thickness was 10.5 nm.
(10) The temperature of the reaction chamber,Keeping the pressure unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (80ml/min) and ammonia gas, growing a second P-type AltGa1-tN electron barrier layer, wherein the Al component of the P-type AltGa1-tN electron barrier layer is 40%, doping Mg impurities, and the doping concentration of Mg is 1 multiplied by 1019cm-3The growth time was 60s and the thickness was 10 nm.
(11) And stopping introducing the metal source and ammonia gas after the growth is finished, introducing hydrogen gas for 5min, and performing Ga atom replacement on the second P-type AltGa1-tN electron barrier layer to form AlGaN with gradually changed Al component on the second P-type AltGa1-tN electron barrier layer, wherein the Al component is 40-90%, and the thickness of the thin layer is about 5 nm.
(12) And repeating the steps 9 to 11 for 7 cycles to form 7 periods of high-barrier P-type AltGa1-tN electron blocking layers and low-barrier P-type AltGa1-tN electron blocking layers.
(13) Keeping the temperature and pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 45%, doping Mg impurities, and the doping concentration of Mg is 2 multiplied by 1019cm-3The growth time is 5min, and the thickness is 30 nm.
The ultraviolet LED is processed into 1mm after growth2350mA of current is introduced into the large and small chips, the wavelength is 280nm, the brightness is 135mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
Based on the above embodiments, the following description will be made by taking as an example a method for preparing an LED by substituting Ga atoms for an AlxGa1-xN quantum barrier layer and a P-type AltGa1-tN electron blocking layer, and the preparation process of the ultraviolet LED includes the following steps:
(1) raising the temperature of the MOCVD reaction chamber to 850 ℃, leading in trimethyl aluminum (150ml/min) and ammonia gas for 3min at the same time when the pressure is 400mbar, and reacting on the sapphire to form an AlN buffer layer of 25 nm; the temperature was increased to 1300 ℃ and the pressure was reduced to 100mbar, and hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 90min, forming a 1500nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 60 min. An undoped AltGa1-tN layer with a thickness of 1000nm was grown, with the Al component of AltGa1-tN being 50%.
(3) The temperature and the pressure of the reaction chamber are unchanged, hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas are introduced for 60min, silane is doped, an N-type AlwGal-wN layer with the thickness of 1000nm grows, the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1 multiplied by 1019cm < -3 >.
(4) Maintaining the temperature at 1140 ℃, adjusting the pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities are doped, the doping concentration is 1x 1018cm < -3 >, the growth time is 40s, and the thickness is 8 nm.
(5) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 1min, and performing Ga atom replacement on the AlxGa1-xN quantum barrier layer to form AlGaN with gradually changed Al components on the AlxGa1-xN quantum barrier layer, wherein the Al components are 56-80%, and the thickness of the thin layer is about 1 nm.
(6) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas are introduced to grow an AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 35%, the growth time is 30s, and the thickness is 3 nm.
(7) And repeating the steps 4 to 6 for 7 cycles to form the quantum well structure with 7 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 40s, the thickness is 8nm, and the last quantum barrier layer is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a P-type AltGa1-tN electron blocking layer, wherein the Al component of the P-type AltGa1-tN electron blocking layer is 65%, doping Mg impurities, and the doping concentration of Mg is 1x 1019cm < -3 >. The growth time is 2min, and the thickness is 30 nm.
(10) And stopping introducing the metal source and ammonia gas after the growth is finished, introducing hydrogen gas for 6min, and performing Ga atom replacement on the P-type AltGa1-tN electron barrier layer to form AlGaN with gradually changed Al components on the P-type AltGa1-tN electron barrier layer, wherein the Al component is 65-98%, and the thickness of the thin layer is about 6 nm.
(11) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (40ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 30%, doping Mg impurities, the doping concentration of Mg is 2 multiplied by 1019cm < -3 >, the growth time is 6min, and the thickness is 30 nm.
After the growth of the ultraviolet LED is finished, the ultraviolet LED is processed into a chip with the size of 1mm2, 350mA of current is introduced, the wavelength is 280nm, the brightness is 120mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
Based on the above embodiments, the following description will be made by taking an example of a method for manufacturing an LED by replacing Ga atoms in an AlxGa1-xN quantum barrier layer, where the process for manufacturing the ultraviolet LED includes the following steps:
(1) raising the temperature of the MOCVD reaction chamber to 920 ℃, leading in trimethyl aluminum (150ml/min) and ammonia gas for 2min at the same time when the pressure is 400mbar, and reacting on the sapphire to form a 17nm AlN buffer layer; the temperature was raised to 1280 ℃ and the pressure was reduced to 100mbar, hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 120min, forming a 2000nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 60 min. An undoped AltGa1-tN layer with a thickness of 1000nm was grown, with the Al component of AltGa1-tN being 50%.
(3) And (3) introducing hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas for 120min while keeping the temperature and the pressure of the reaction chamber unchanged, doping silane, and growing an N-type AlwGal-wN layer with the thickness of 2000nm, wherein the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1 multiplied by 1019cm < -3 >.
(4) Keeping the temperature at 1140 ℃, adjusting the pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities with the doping concentration of 1x 1018cm < -3 >, the growth time of 1min and the thickness of 12 nm.
(5) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 3min, and performing Ga atom replacement on the AlxGa1-xN quantum barrier layer to form AlGaN with gradually changed Al components on the AlxGa1-xN quantum barrier layer, wherein the Al components are 56-90%, and the thickness of the thin layer is about 3 nm.
(6) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (40ml/min) and ammonia gas are introduced to grow the AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 30%, the growth time is 15s, and the thickness is 1.5 nm.
(7) And repeating the steps 4 to 6 for 10 cycles to form the quantum well structure with 10 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 1min, the thickness is 12nm, and the last layer of quantum barrier is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a first P-type AltGa1-tN electron blocking layer, doping Mg impurities with the Al component of the P-type AltGa1-tN electron blocking layer being 65 percent, wherein the doping concentration of Mg is 1 multiplied by 1019cm < -3 >. The growth time was 120s and the thickness was 28 nm.
(10) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (80ml/min) and ammonia gas, growing a second P-type AltGa1-tN electron blocking layer, wherein the Al component of the P-type AltGa1-tN electron blocking layer is 40%, doping Mg impurities, the doping concentration of Mg is 1 multiplied by 1019cm < -3 >, the growth time is 60s, and the thickness is 10 nm.
(11) And repeating the steps 9 to 10 for 2 cycles to form 2 periods of the high-barrier P-type AltGa1-tN electron blocking layer and the low-barrier P-type AltGa1-tN electron blocking layer.
(12) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 35%, doping Mg impurities are doped, the doping concentration of Mg is 2 multiplied by 1019cm < -3 >, the growth time is 5min, and the thickness is 30 nm.
After the growth of the ultraviolet LED is finished, the ultraviolet LED is processed into a chip with the size of 1mm2, 350mA of current is introduced, the wavelength is 280nm, the brightness is 125mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
On the basis of the above embodiments, the following description will be made by taking as an example a method for preparing an LED by substituting Ga atoms for an AlyGa1-yN quantum well layer, and the preparation process of the ultraviolet LED includes the following steps:
(1) the temperature of the MOCVD reaction chamber is raised to 880 ℃, the pressure is 400mbar, and trimethyl aluminum (150ml/min) and ammonia gas are introduced for 3min at the same time to react on the sapphire to form an AlN buffer layer with the thickness of 25 nm; the temperature was raised to 1250 ℃ and the pressure was reduced to 100mbar, and hydrogen, trimethylaluminum (400ml/min) and ammonia gas were fed in for 180min to form a 3000nm undoped AlN layer.
(2) The temperature was lowered to 1140 ℃ and the pressure was maintained at 200mbar, and hydrogen, trimethylgallium (100ml/min), trimethylaluminum (360ml/min) and ammonia gas were fed in for 90 min. An undoped AltGa1-tN layer with a thickness of 1500nm was grown, with the Al component of AltGa1-tN being 50%.
(3) And (3) introducing hydrogen, trimethyl gallium (100ml/min), trimethyl aluminum (360ml/min) and ammonia gas for 120min while keeping the temperature and the pressure of the reaction chamber unchanged, doping silane, and growing an N-type AlwGal-wN layer with the thickness of 2000nm, wherein the Al component of the N-type AlwGal-wN layer is 50%, and the doping concentration of the N-type AlwGal-wN layer is 1 multiplied by 1019cm < -3 >.
(4) Keeping the temperature at 1140 ℃, adjusting the pressure to 200mbar, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, doping Si impurities with the doping concentration of 1x 1018cm < -3 >, the growth time of 1min and the thickness of 12 nm.
(5) The temperature and the pressure of the reaction chamber are kept unchanged, hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (40ml/min) and ammonia gas are introduced to grow an AlyGa1-yN quantum well, the Al component of the AlyGa1-yN quantum well layer is 35%, the growth time is 30s, and the thickness is 3 nm.
(6) And after the growth is finished, stopping introducing the metal source and ammonia gas, introducing hydrogen gas for 30s, and performing Ga atom replacement on the AlyGa1-yN quantum well layer to form AlGaN with gradually changed Al component on the AlyGa1-yN quantum well layer, wherein the Al component is 35-65%, and the thickness of the thin layer is about 0.5 nm.
(7) And repeating the steps 4 to 6 for 7 cycles to form the quantum well structure with 7 periods.
(8) Keeping the temperature of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (200ml/min) and ammonia gas, growing an AlxGa1-xN quantum barrier layer, wherein the Al component of the AlxGa1-xN quantum barrier layer is 56%, the growth time is 1min, the thickness is 12nm, and the last layer of quantum barrier is grown.
(9) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (250ml/min) and ammonia gas, growing a first P-type AltGa1-tN electron blocking layer, doping Mg impurities with the Al component of the P-type AltGa1-tN electron blocking layer being 65 percent, wherein the doping concentration of Mg is 1 multiplied by 1019cm < -3 >. The growth time was 10s and the thickness was 2.3 nm.
(10) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (80ml/min) and ammonia gas, growing a second P-type AltGa1-tN electron blocking layer, wherein the Al component of the P-type AltGa1-tN electron blocking layer is 40%, doping Mg impurities, the doping concentration of Mg is 1 multiplied by 1019cm < -3 >, the growth time is 10s, and the thickness is 1.7 nm.
(11) And repeating the steps 9 to 10 for 20 cycles to form 20 periods of the high-barrier P-type AltGa1-tN electron blocking layer and the low-barrier P-type AltGa1-tN electron blocking layer.
(12) Keeping the temperature and the pressure of the reaction chamber unchanged, introducing hydrogen, trimethyl gallium (50ml/min), trimethyl aluminum (50ml/min) and ammonia gas, growing an AlGaN hole injection layer, wherein the Al component of the AlGaN hole injection layer is 35%, doping Mg impurities are doped, the doping concentration of Mg is 2 multiplied by 1019cm < -3 >, the growth time is 5min, and the thickness is 30 nm.
After the growth of the ultraviolet LED is finished, the ultraviolet LED is processed into a chip with the size of 1mm2, 350mA of current is introduced, the wavelength is 280nm, the brightness is 125mW, the external quantum efficiency exceeds 5 percent, and the forward voltage is 6.5V.
Example two
Fig. 2 is a schematic structural diagram of an ultraviolet LED according to a second embodiment of the present invention; fig. 3 is a schematic structural diagram of an ideal energy band of an ultraviolet LED according to a second embodiment of the present invention; fig. 4 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum well and a second electron blocking layer according to a second embodiment of the present invention; fig. 5 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum well and a first electron blocking layer according to a second embodiment of the present invention; fig. 6 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum barrier and a first electron blocking layer according to a second embodiment of the present invention; fig. 7 is a schematic diagram of an energy band structure of an ultraviolet LED after Ga atom replacement processing is performed on a quantum barrier and a second electron blocking layer according to a second embodiment of the present invention. As shown in fig. 2 to fig. 7, on the basis of the above embodiments, a second embodiment of the present invention further provides an ultraviolet LED.
Specifically, the ultraviolet LED is prepared by the ultraviolet LED preparation method in the first embodiment.
It should be noted that, by using the preparation method in the first embodiment, the ultraviolet LED sequentially includes, from bottom to top, a substrate 10, a buffer layer 20, an undoped AltGal-tN layer 30, an N-type AlwGal-wN layer 40, a 50-multiple quantum well structure layer 50, a P-type AltGa1-tN electron blocking layer 60, and a P-type hole injection layer 70, and finally forms the ultraviolet LED. Wherein, the ideal energy band structure schematic diagram of the ultraviolet LED is shown in fig. 3, Ga atom displacement processing is respectively performed on the AlyGa1-yN quantum well layer and the AlxGa1-xN quantum barrier layer in the multiple quantum well structure layer 50, and Ga atom displacement processing is also performed on the first electron barrier layer or the second electron barrier layer in the P-type AltGa1-tN electron barrier layer, the energy band structure schematic diagram of the ultraviolet LED after processing is shown in fig. 4-7, the AlGaN layer with gradually changed Al components formed by the ultraviolet LED after Ga atom displacement processing enables the electron barrier to gradually rise, so as to play a role of blocking electrons, and simultaneously enables the hole barrier to gradually fall, so as to facilitate the promotion of hole injection efficiency, increase of electron hole concentration, effectively promote the recombination efficiency of carriers in the quantum well, thereby improving the internal quantum efficiency of the ultraviolet LED, and the light emitting efficiency of the ultraviolet LED to some extent, and simultaneously, the sterilization, phototherapy and curing efficiency is improved.
Other technical features have been described in detail in the first embodiment, and are not described again here.
The ultraviolet LED provided by the second embodiment of the invention sequentially comprises a substrate 10, a buffer layer 20, an undoped AltGal-tN layer 30, an N-type AlwGal-wN layer 40, a 50-multi-quantum well structure layer 50, a P-type AltGa1-tN electron blocking layer 60 and a P-type hole injection layer 70 from bottom to top, and finally the ultraviolet LED is formed. Ga atom replacement processing is carried out on an AlyGa1-yN quantum well layer and an AlxGa1-xN quantum barrier layer in the multi-quantum well structure layer 50 respectively, meanwhile, Ga atom replacement processing is also carried out on a first electron barrier layer or a second electron barrier layer in a P-type AltGa1-tN electron barrier layer, an AlGaN layer with gradually changed Al components formed by the ultraviolet LED subjected to Ga atom replacement processing enables an electron barrier to be gradually increased, an electron blocking effect can be achieved, a hole barrier is gradually reduced, improvement of hole injection efficiency is facilitated, electron hole concentration is increased, recombination efficiency of carriers in quantum wells is effectively improved, inner quantum efficiency of the ultraviolet LED is improved, luminous efficiency of the ultraviolet LED is improved, and sterilization, phototherapy and curing efficiency are improved. The carrier recombination efficiency is improved, so that the luminous efficiency of the ultraviolet LED is improved, and the sterilization, phototherapy and curing efficiency is improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions fall off the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. A preparation method of an ultraviolet LED is applied to growth equipment and is characterized by comprising the following steps:
introducing a metal source and a V-group reactant, and growing a buffer layer on the substrate;
growing an undoped AltGal-tN layer on the buffer layer;
growing an N-type AlwGal-wN layer on the undoped AltGal-tN layer;
growing an AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer on the N-type AlwGal-wN layer;
carrying out Ga atom replacement on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer;
growing a P-type AltGa1-tN electron blocking layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer;
growing a P-type hole injection layer on the P-type AltGa1-tN electron blocking layer to form an ultraviolet LED;
wherein, the Ga atom replacement is carried out on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer, and the method comprises the following steps: stopping introducing the metal source and the group V reactant, introducing hydrogen, performing Ga atom replacement on the AlxGa1-xN quantum barrier layer and/or the AlyGa1-yN quantum well layer, and forming an AlGaN layer with gradually changed Al composition in the AlxGa1-xN quantum barrier layer and/or the AlyGa1-yN quantum well layer, wherein the Al composition in the AlGaN layer is smaller than that of the surface layer of the AlGaN layer.
2. The method of claim 1, wherein the growing of the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer on the N-type AlwGal-wN layer comprises:
cyclically and alternately growing AlxGa1-xN quantum barrier layers and AlyGa1-yN quantum well layers on the N-type AlwGal-wN layers to form the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer;
wherein the AlxGa1-xN quantum barrier layer and the AlyGa1-yN quantum well layer are laminated,
the first layer and the last layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer are the AlxGa1-xN quantum barrier layers; or the first layer and the last layer in the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer are the AlyGa1-yN quantum well layers.
3. The method of claim 1, wherein the Al composition of the AlGaN layer in the AlxGa1-xN quantum barrier layer is greater than the Al composition of the AlGaN layer in the AlyGa1-yN quantum well layer.
4. The method for preparing the ultraviolet LED as claimed in claim 1, wherein the growing the P-type AltGa1-tN electron blocking layer on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer comprises:
and at least two P-type AltGa1-tN electron blocking layers are grown on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer in a laminating way.
5. The method for preparing the ultraviolet LED as claimed in claim 4, wherein the step of performing Ga atom replacement on at least two P-type AltGa1-tN electron blocking layers which are grown on the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer in a laminating way comprises the following steps:
stopping introducing the metal source and the V-group reactant, introducing hydrogen, performing Ga atom replacement on at least one layer of the P-type AltGa1-tN electron barrier layer, and forming an AlGaN layer with gradually changed Al components in the P-type AltGa1-tN electron barrier layer, wherein the Al components in the AlGaN layer are smaller than the Al components on the surface layer of the AlGaN layer.
6. The UV LED manufacturing method according to claim 2, wherein the thickness of the AlxGa1-xN/AlyGa1-yN multi-quantum well structure layer is 5-50 nm.
7. The method for preparing the ultraviolet LED according to the claim 1 or 5, wherein the time for introducing the hydrogen is 5s-20 min.
8. The method for preparing the ultraviolet LED as claimed in claim 2, wherein the number of cycles for alternately growing the AlxGa1-xN quantum barrier layer and the AlyGa1-yN quantum well layer is 2-100.
9. An ultraviolet LED, characterized in that the ultraviolet LED is prepared by the method for preparing an ultraviolet LED according to any one of claims 1 to 8.
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Publication number Priority date Publication date Assignee Title
CN107195742A (en) * 2017-07-17 2017-09-22 圆融光电科技股份有限公司 The preparation method and ultraviolet LED of ultraviolet LED
CN109166910A (en) * 2018-09-06 2019-01-08 中山大学 A kind of p-type AlGaN semiconductor material and its epitaxial preparation method
CN208589459U (en) * 2018-06-29 2019-03-08 江西兆驰半导体有限公司 A kind of UV LED
CN109950371A (en) * 2019-03-13 2019-06-28 深圳市洲明科技股份有限公司 Ultraviolet LED epitaxial structure and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107195742A (en) * 2017-07-17 2017-09-22 圆融光电科技股份有限公司 The preparation method and ultraviolet LED of ultraviolet LED
CN208589459U (en) * 2018-06-29 2019-03-08 江西兆驰半导体有限公司 A kind of UV LED
CN109166910A (en) * 2018-09-06 2019-01-08 中山大学 A kind of p-type AlGaN semiconductor material and its epitaxial preparation method
CN109950371A (en) * 2019-03-13 2019-06-28 深圳市洲明科技股份有限公司 Ultraviolet LED epitaxial structure and preparation method thereof

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