CN108987540B - Manufacturing method of light emitting diode epitaxial wafer and light emitting diode epitaxial wafer - Google Patents

Manufacturing method of light emitting diode epitaxial wafer and light emitting diode epitaxial wafer Download PDF

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CN108987540B
CN108987540B CN201810550077.4A CN201810550077A CN108987540B CN 108987540 B CN108987540 B CN 108987540B CN 201810550077 A CN201810550077 A CN 201810550077A CN 108987540 B CN108987540 B CN 108987540B
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stress release
release layer
type semiconductor
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CN108987540A (en
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葛永晖
郭炳磊
刘旺平
吕蒙普
胡加辉
李鹏
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HC Semitek Zhejiang Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • H01L33/0062Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/12Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/14Semiconductor 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
    • H01L33/145Semiconductor 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26Materials of the light emitting region
    • H01L33/30Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen

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Abstract

The invention discloses a manufacturing method of a light-emitting diode epitaxial wafer and the light-emitting diode epitaxial wafer, and belongs to the technical field of semiconductors. The manufacturing method comprises the following steps: growing a buffer layer, an N-type semiconductor layer and a stress release layer on a substrate in sequence by adopting a chemical vapor deposition technology; carrying out ion irradiation on the surface of the stress release layer to reduce the resistivity of the stress release layer; and sequentially growing an active layer and a P-type semiconductor layer on the stress release layer by adopting a chemical vapor deposition technology. According to the invention, the surface of the stress release layer is subjected to ion irradiation, the microstructure of the stress release layer crystal is changed, the form and the number of defects in the stress release layer are influenced, the resistivity of the stress release layer is reduced, electrons provided by the N-type semiconductor layer are favorably transferred to the active layer to carry out composite luminescence, the number of electrons injected into the active layer is increased, the internal quantum efficiency of the LED is further improved, and the luminous efficiency of the LED is further improved.

Description

Manufacturing method of light emitting diode epitaxial wafer and light emitting diode epitaxial wafer
Technical Field
The invention relates to the technical field of semiconductors, in particular to a manufacturing method of a light-emitting diode epitaxial wafer and the light-emitting diode epitaxial wafer.
Background
A Light Emitting Diode (LED) is a semiconductor electronic component capable of Emitting Light. The LED has received much attention because of its advantages of energy saving, environmental protection, high reliability, long service life, etc., and in recent years, the LED has been widely used in the fields of backlight and display screen, and has started to advance to the civil illumination market. For civil illumination, the lighting effect and the service life are main measurement standards, so that the increase of the luminous efficiency and the improvement of the antistatic capability of the LED are particularly critical to the wide application of the LED.
The epitaxial wafer is a primary finished product in the LED preparation process. The conventional LED epitaxial wafer comprises a substrate, a buffer layer, an N-type semiconductor layer, an active layer and a P-type semiconductor layer, wherein the buffer layer, the N-type semiconductor layer, the active layer and the P-type semiconductor layer are sequentially laminated on the substrate. The P-type semiconductor layer is used for providing holes for carrying out compound luminescence, the N-type semiconductor layer is used for providing electrons for carrying out compound luminescence, the active layer is used for carrying out compound luminescence of the electrons and the holes, the substrate is used for providing a growth surface for epitaxial materials, and the buffer layer is used for relieving lattice mismatch between the substrate and the N-type semiconductor layer.
In the process of implementing the invention, the inventor finds that the prior art has at least the following problems:
the substrate is made of sapphire, the N-type semiconductor layer is made of gallium nitride, the sapphire and the gallium nitride are heterogeneous materials, large lattice mismatch exists between the sapphire and the gallium nitride, stress and defects generated by the lattice mismatch extend along with epitaxial growth, carriers (electrons or holes) provided by the N-type semiconductor and the P-type semiconductor layer are influenced to be injected into the active layer to perform compound light emission, and the light emitting efficiency of the LED is reduced.
In order to avoid the stress and defect generated by lattice mismatch from extending to the active layer for compound light emission, a stress release layer is usually disposed between the N-type semiconductor layer and the active layer, and the stress release layer can release the stress generated by lattice mismatch and improve the defect generated by lattice mismatch, which is beneficial to improving the light emission efficiency of the LED. However, the stress release layer has many defects, which can restrict electrons provided by the N-type semiconductor layer from migrating to the active layer, reduce the number of electrons injected into the active layer for recombination and light emission, and reduce the luminous efficiency of the LED, so the luminous efficiency of the LED still needs to be improved.
Disclosure of Invention
The embodiment of the invention provides a manufacturing method of a light-emitting diode epitaxial wafer and the light-emitting diode epitaxial wafer, which can solve the problems that in the prior art, a stress release layer restricts electron injection into an active layer and reduces the light-emitting efficiency of an LED. The technical scheme is as follows:
in one aspect, an embodiment of the present invention provides a method for manufacturing an epitaxial wafer of a light emitting diode, where the method includes:
growing a buffer layer, an N-type semiconductor layer and a stress release layer on a substrate in sequence by adopting a chemical vapor deposition technology;
carrying out ion irradiation on the surface of the stress release layer to reduce the resistivity of the stress release layer;
and sequentially growing an active layer and a P-type semiconductor layer on the stress release layer by adopting a chemical vapor deposition technology.
Optionally, the performing ion irradiation on the surface of the stress release layer to reduce the resistivity of the stress release layer includes:
irradiating the surface of the stress release layer with accelerated ions in a vacuum environment, the ions including at least one of oxygen ions and silver ions.
Preferably, when the ions include oxygen ions, the radiation dose of the oxygen ions is 1011ions/cm2~1012ions/cm2
More preferably, when the ions include oxygen ions, the radiation energy of the oxygen ions is 50MeV to 150 MeV.
Preferably, when the ions comprise silver ions, the radiation dose of the silver ions is 1010ions/cm2~1013ions/cm2
More preferably, when the ions include silver ions, the radiation energy of the silver ions is 150MeV to 250 MeV.
Preferably, the temperature of the vacuum environment is 20 ℃ to 100 ℃.
Optionally, the manufacturing method further includes:
and after the surface of the stress release layer is subjected to ion irradiation, annealing treatment is carried out on the P-type stress release layer.
On the other hand, the embodiment of the invention provides a light emitting diode epitaxial wafer, which comprises a substrate, a buffer layer, an N-type semiconductor layer, a stress release layer, an active layer and a P-type semiconductor layer, wherein the buffer layer, the N-type semiconductor layer, the stress release layer, the active layer and the P-type semiconductor layer are sequentially laminated on the substrate, and the surface of the stress release layer is the surface after ion irradiation.
Optionally, the ions include at least one of oxygen ions and silver ions.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the surface of the stress release layer is subjected to ion irradiation, the microstructure of crystals of the stress release layer is changed, the form and the number of defects in the stress release layer are influenced, on one hand, the stress release layer is favorable for releasing stress generated by lattice mismatch and improving the defects generated by lattice mismatch, on the other hand, the resistivity of the stress release layer is reduced, electrons provided by the N-type semiconductor layer are favorable for migrating to the active layer to perform composite luminescence, the number of electrons injected into the active layer is increased, the internal quantum efficiency of the LED is improved, and therefore the luminous efficiency of the LED is improved. And the resistivity of the stress release layer is reduced, the series resistance of the epitaxial wafer can be reduced, and finally the forward voltage of the LED is reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced 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 based on these drawings without creative efforts.
Fig. 1 is a flowchart of a method for manufacturing an epitaxial wafer of a light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an led epitaxial wafer according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The embodiment of the invention provides a method for manufacturing a light emitting diode epitaxial wafer, and fig. 1 is a flow chart of the method for manufacturing the light emitting diode epitaxial wafer provided by the embodiment of the invention, and referring to fig. 1, the method for manufacturing the light emitting diode epitaxial wafer comprises the following steps:
step 101: and sequentially growing a buffer layer, an N-type semiconductor layer and a stress release layer on the substrate by adopting a chemical vapor deposition technology.
Specifically, the step 101 may include:
controlling the temperature to be 400-600 ℃ (preferably 500 ℃), and the pressure to be 400-600 torr (preferably 500torr), and growing a buffer layer with the thickness of 15-35 nm (preferably 25nm) on the substrate;
controlling the temperature to be 1000-1200 ℃ (preferably 1100 ℃), the pressure to be 400-600 Torr (preferably 500Torr), the duration to be 5-10 minutes (preferably 8 minutes), and carrying out in-situ annealing treatment on the buffer layer;
an N-type semiconductor layer having a thickness of 1 to 5 [ mu ] m (preferably 3 [ mu ] m) is grown on the buffer layer at a temperature of 1000 to 1200 ℃ (preferably 1100 ℃) and a pressure of 100to 500torr (preferably 300torr), and the N-type semiconductor layer has an N-type dopant doping concentration of 1018cm-3~1019cm-3(preferably 5 x 10)18cm-3);
Controlling the temperature to be 800-1100 ℃ (preferably 950 ℃), and the pressure to be 100-500 torr (preferably 300torr), and growing a stress release layer with the thickness of 50-500 nm (preferably 275nm) on the N-type semiconductor layer, wherein the stress release layer comprises a plurality of first sub-layers and a plurality of second sub-layers which are alternately grown; the number of the first sub-layers is the same as that of the second sub-layers, and the number of the second sub-layers is 3-9; the thickness of the first sub-layer is 1 nm-3 nm, and the thickness of the second sub-layer is 20 nm-40 nm.
Specifically, the substrate may be made of sapphire having a crystal orientation, and the buffer layer may be made of gallium nitride (GaN). The material of the N-type semiconductor layer can adopt N-type doped gallium nitride. The material of the first sub-layer can adopt indium gallium nitride (InGaN), and the molar content of an indium component in the first sub-layer is less than or equal to 0.05; the material of the second sub-layer can adopt aluminum gallium nitride (AlGaN), and the molar content of the aluminum component in the second sub-layer is less than or equal to 0.2.
Optionally, before step 101, the manufacturing method may further include:
annealing the substrate in a hydrogen atmosphere for 1 minute to 10 minutes (preferably 8 minutes);
the nitriding treatment is carried out at a temperature of 1000 ℃ to 1200 ℃ (preferably 1100 ℃).
The surface of the substrate is cleaned by adopting the steps, so that the phenomenon that impurities are doped into the epitaxial wafer to influence the overall crystal quality is avoided, and the luminous efficiency of the LED is reduced.
Optionally, before growing the N-type semiconductor layer on the buffer layer, the manufacturing method may further include:
an undoped gallium nitride layer having a thickness of 1 to 5 μm (preferably 3 μm) is grown on the buffer layer under a temperature of 1000 to 1100 deg.C (preferably 1050 deg.C) and a pressure of 100to 500torr (preferably 300 torr).
Accordingly, an N-type semiconductor layer is grown on the undoped gallium nitride layer.
The lattice mismatch between the substrate and the N-type semiconductor layer is mitigated with an undoped gallium nitride layer.
In a specific implementation, the buffer layer is a thin layer of gan that is first grown on the substrate at a low temperature, and is therefore also referred to as a low temperature buffer layer. Then, the longitudinal growth of gallium nitride is carried out on the low-temperature buffer layer, and a plurality of mutually independent three-dimensional island-shaped structures called three-dimensional nucleation layers can be formed; then, transverse growth of gallium nitride is carried out on all the three-dimensional island structures and among the three-dimensional island structures to form a two-dimensional plane structure which is called a two-dimensional recovery layer; and finally, growing a thicker gallium nitride layer called a high-temperature buffer layer on the two-dimensional growth layer at a high temperature. The three-dimensional nucleation layer, the two-dimensional recovery layer, and the high-temperature buffer layer are collectively referred to as an undoped gallium nitride layer in this embodiment.
Step 102: and carrying out ion irradiation on the surface of the stress release layer to reduce the resistivity of the stress release layer.
In this embodiment, ion irradiation is a treatment method that ions are used to collide atoms from their normal positions, so as to generate crystal defects such as vacancies and ion gaps, thereby affecting the macroscopic properties of the material. The ion irradiation process is carried out by irradiating the solid material with ions of accelerated atoms in a vacuum system to form a surface layer having specific properties in selected areas.
According to the embodiment of the invention, the surface of the stress release layer is subjected to ion irradiation, the microstructure of the stress release layer crystal is changed, and the form and the number of defects in the stress release layer are influenced, so that the stress release layer is favorable for releasing stress generated by lattice mismatch and improving the defects generated by lattice mismatch, the resistivity of the stress release layer is reduced, electrons provided by the N-type semiconductor layer are favorably migrated into the active layer for composite luminescence, the number of electrons injected into the active layer is increased, the internal quantum efficiency of the LED is increased, and the luminous efficiency of the LED is increased. And the resistivity of the stress release layer is reduced, the series resistance of the epitaxial wafer can be reduced, and finally the forward voltage of the LED is reduced.
Specifically, this step 102 may include:
in a vacuum environment, the surface of the stress release layer is irradiated with accelerated ions including at least one of oxygen ions and silver ions.
Experiments prove that the forward voltage of the LED can be effectively reduced and the luminous efficiency of the LED can be improved by irradiating oxygen ions on the surface of the stress release layer, or irradiating silver ions on the surface of the stress release layer, or simultaneously irradiating the oxygen ions and the silver ions on the surface of the stress release layer.
Alternatively, when the ions irradiating the surface of the stress relieving layer include oxygen ions, the radiation dose of the oxygen ions may be 1011ions/cm2~1012ions/cm2
If the radiation dose of oxygen ions is less than 1011ions/cm2The resistivity of the stress release layer may not be effectively reduced due to too small radiation dose of oxygen ions, and the light emitting efficiency and the forward voltage of the LED are hardly changed; if oxygen ionThe radiation dose is more than 1012ions/cm2Therefore, a new defect may be introduced into the stress release layer due to too much radiation dose of oxygen ions, which affects the overall crystal quality of the epitaxial wafer and reduces the light emitting efficiency of the LED.
Preferably, when the ions irradiating the surface of the stress relieving layer include oxygen ions, the irradiation energy of the oxygen ions may be 50MeV to 150 MeV.
If the radiation energy of the oxygen ions is less than 50MeV, the oxygen ions may not effectively act on the stress release layer due to too low radiation energy of the oxygen ions, and thus the resistivity of the stress release layer is not changed, and finally the light emitting efficiency and the forward voltage of the LED are not changed; if the radiation energy of the oxygen ions is more than 150MeV, adverse effects may be caused due to too high radiation energy of the oxygen ions, reducing the luminous efficiency of the LED.
Alternatively, when the ions irradiating the surface of the stress relieving layer include silver ions, the radiation dose of the silver ions may be 1010ions/cm2~1013ions/cm2
If the radiation dose of silver ions is less than 1010ions/cm2The resistivity of the stress release layer may not be effectively reduced due to too small radiation dose of silver ions, and the light emitting efficiency and the forward voltage of the LED are hardly changed; if the radiation dose of silver ions is more than 1013ions/cm2Therefore, a new defect may be introduced into the stress release layer due to too much radiation dose of silver ions, which affects the overall crystal quality of the epitaxial wafer and reduces the light emitting efficiency of the LED.
Preferably, when the ions irradiating the surface of the stress relieving layer include silver ions, the radiation energy of the silver ions may be 150MeV to 250 MeV.
If the radiation energy of the silver ions is less than 150MeV, oxygen ions may not effectively act on the stress release layer due to too low radiation energy of the silver ions, and thus the resistivity of the stress release layer is not changed, and finally the light emitting efficiency and the forward voltage of the LED are not changed; if the radiation energy of the silver ions is more than 250MeV, adverse effects may be caused due to too high radiation energy of the silver ions, reducing the luminous efficiency of the LED.
Wherein the radiation dose of the ions is the total number of ions radiated per unit area of the ion radiation surface, and the radiation energy of the ions is the product of the electron charge and the potential difference. Specifically, the radiation dose of the oxygen ions is the total number of the oxygen ions radiated per unit area of the surface of the stress release layer, and the radiation energy of the oxygen ions is the product of the electron charge of the oxygen ions and the potential difference; the radiation dose of the silver ions is the total number of the silver ions radiated per unit area of the surface of the stress release layer, and the radiation energy of the silver ions is the product of the electronic charge of the silver ions and the potential difference.
Alternatively, the temperature of the vacuum environment may be 20 ℃ to 100 ℃.
If the temperature of the vacuum environment is less than 20 ℃, the ion radiation stress release layer may be affected because the temperature of the vacuum environment is too low to cause ion inactivity; if the temperature of the vacuum environment is higher than 100 ℃, ions may be over-activated due to the high temperature of the vacuum environment, causing adverse effects.
Step 103: and annealing the stress release layer. This step 103 is an optional step.
And eliminating the crystal lattice damage through annealing treatment.
Optionally, the temperature of the annealing treatment can be 700-850 ℃, and the realization effect is better.
Optionally, the time of the annealing treatment can be 20min to 50min, so that the realization effect is better.
Step 104: and sequentially growing an active layer and a P-type semiconductor layer on the stress release layer by adopting a chemical vapor deposition technology.
Specifically, this step 104 may include:
controlling the pressure to be 100-500 torr (preferably 300torr), and growing an active layer on the stress release layer, wherein the active layer comprises a plurality of quantum wells and a plurality of quantum barriers which are alternately grown; the number of quantum wells is the same as that of quantum barriers, and the number of quantum barriers is 5-15 (preferably 10); the thickness of the quantum well is 2.5 nm-3.5 nm (preferably 3nm), the growth temperature of the quantum well is 720 ℃ -829 ℃ (preferably 770 ℃); the thickness of the quantum barrier is 9 nm-20 nm (preferably 15nm), the growth temperature of the quantum barrier is 850 ℃ -959 ℃ (preferably 900 ℃);
controlling the temperature to 850-1080 deg.C (preferably 960 deg.C) and the pressure to 100-300 torr (preferably 200torr), and growing a P-type semiconductor layer with a thickness of 100-800 nm (preferably 450nm) on the active layer, wherein the P-type semiconductor layer has a doping concentration of 1018cm-3~1019cm-3(preferably 5 x 10)18cm-3)。
Specifically, indium gallium nitride may be used as the material of the quantum well, and gallium nitride may be used as the material of the quantum barrier. The P-type semiconductor layer can be made of P-type doped gallium nitride.
Optionally, before growing the P-type semiconductor layer on the active layer, the manufacturing method may further include:
the temperature is controlled to be 1000 ℃ to 1100 ℃ (preferably 1050 ℃), the pressure is controlled to be 100torr to 500torr (preferably 300torr), and the electron blocking layer with the thickness of 50nm to 150nm (preferably 100nm) is grown on the active layer.
Accordingly, a P-type semiconductor layer is grown on the electron blocking layer.
Specifically, the material of the electron blocking layer may be P-type doped aluminum gallium nitride (AlGaN), preferably P-type doped AlyGa1-yAnd N is more than 0.1 and less than 0.5, so that electrons are prevented from jumping into the P-type semiconductor layer to be subjected to non-radiative recombination with holes, and the luminous efficiency of the LED is further influenced.
Optionally, after step 104, the manufacturing method may further include:
the temperature is controlled to be 850 to 1050 ℃ (preferably 950 ℃), the pressure is controlled to be 100to 300torr (preferably 200torr), and the P-type contact layer with the thickness of 5 to 300nm (preferably 150nm) is grown on the P-type semiconductor layer.
Specifically, the P-type contact layer may be made of P-type doped indium gallium nitride, so as to form a good ohmic contact with an electrode or a transparent conductive film in a chip process.
Optionally, after the end of the epitaxial growth, the manufacturing method may further include:
the annealing treatment is carried out in a nitrogen atmosphere while controlling the temperature at 650 to 850 ℃ (preferably 750 ℃) for 5 to 15 minutes (preferably 10 minutes).
It should be noted that the temperature and the pressure controlled as described above are the temperature and the pressure in the reaction chamber, respectively. During implementation, trimethyl gallium or trimethyl ethyl is used as a gallium source, high-purity nitrogen is used as a nitrogen source, trimethyl indium is used as an indium source, trimethyl aluminum is used as an aluminum source, silane is used as an N-type dopant, and magnesium diclocide is used as a P-type dopant.
The embodiment of the invention provides another manufacturing method of a light emitting diode epitaxial wafer, which is a specific implementation of the manufacturing method shown in fig. 1, and the manufacturing method comprises the following steps:
step 201: a buffer layer with a thickness of 25nm was grown on the substrate at a controlled temperature of 500 ℃ and a pressure of 500 torr.
Step 202: the buffer layer was annealed in situ at 1100 deg.C under 500torr for 8 minutes.
Step 203: controlling the temperature at 1100 deg.C and the pressure at 300torr, and growing an N-type semiconductor layer with a thickness of 3 μm on the buffer layer, wherein the doping concentration of N-type dopant in the N-type semiconductor layer is 5 × 1018cm-3
Step 204: and controlling the temperature to be 950 ℃ and the pressure to be 300torr, and growing a stress release layer with the thickness of 275nm on the N-type semiconductor layer, wherein the stress release layer comprises 6 first sublayers with the thickness of 2nm and 6 second sublayers with the thickness of 30nm which are alternately grown.
Step 205: irradiating the surface of the stress release layer with accelerated oxygen ions at a radiation dose of 5 × 10 in a vacuum environment at 60 deg.C11ions/cm2The radiation energy of the oxygen ions was 100 MeV.
Step 206: controlling the pressure to be 300torr, and growing an active layer on the stress release layer, wherein the active layer comprises 10 quantum wells and 10 quantum barriers which are alternately grown; the thickness of the quantum well is 3nm, and the growth temperature of the quantum well is 770 ℃; the thickness of the quantum barrier is 15nm, and the growth temperature of the quantum barrier is 900 ℃.
Step 207: controlling the temperature to 960 deg.C and the pressure to 200torr, growing a P-type semiconductor layer with a thickness of 450nm on the active layer, wherein the doping concentration of the P-type dopant in the P-type semiconductor layer is 5 × 1018cm-3
Compared with the chip without ion radiation, the forward voltage of the chip is reduced by 1-2%, and the luminous energy efficiency is improved by 1-2%.
The embodiment of the invention provides another manufacturing method of a light emitting diode epitaxial wafer, which is another specific implementation of the manufacturing method shown in fig. 1, and the manufacturing method includes:
step 301: a buffer layer with a thickness of 25nm was grown on the substrate at a controlled temperature of 500 ℃ and a pressure of 500 torr.
Step 302: the buffer layer was annealed in situ at 1100 deg.C under 500torr for 8 minutes.
Step 303: controlling the temperature at 1100 deg.C and the pressure at 300torr, and growing an N-type semiconductor layer with a thickness of 3 μm on the buffer layer, wherein the doping concentration of N-type dopant in the N-type semiconductor layer is 5 × 1018cm-3
Step 304: and controlling the temperature to be 950 ℃ and the pressure to be 300torr, and growing a stress release layer with the thickness of 275nm on the N-type semiconductor layer, wherein the stress release layer comprises 6 first sublayers with the thickness of 2nm and 6 second sublayers with the thickness of 30nm which are alternately grown.
Step 305: irradiating the surface of the stress release layer with accelerated silver ions at a radiation dose of 5 × 10 in a vacuum environment at 60 deg.C11ions/cm2The radiation energy of the oxygen ions was 200 MeV.
Step 306: controlling the pressure to be 300torr, and growing an active layer on the stress release layer, wherein the active layer comprises 10 quantum wells and 10 quantum barriers which are alternately grown; the thickness of the quantum well is 3nm, and the growth temperature of the quantum well is 770 ℃; the thickness of the quantum barrier is 15nm, and the growth temperature of the quantum barrier is 900 ℃.
Step 307: the temperature is controlled to be 960 ℃, the pressure is 200torr, in the presence ofGrowing a P-type semiconductor layer with a thickness of 450nm on the source layer, wherein the doping concentration of a P-type dopant in the P-type semiconductor layer is 5 x 1018cm-3
Compared with the chip without ion radiation, the forward voltage of the chip is reduced by 1.5-3%, and the luminous energy efficiency is improved by 1-2%.
The embodiment of the invention provides another manufacturing method of a light emitting diode epitaxial wafer, which is another specific implementation of the manufacturing method shown in fig. 1, and the manufacturing method includes:
step 401: a buffer layer with a thickness of 25nm was grown on the substrate at a controlled temperature of 500 ℃ and a pressure of 500 torr.
Step 402: the buffer layer was annealed in situ at 1100 deg.C under 500torr for 8 minutes.
Step 403: controlling the temperature at 1100 deg.C and the pressure at 300torr, and growing an N-type semiconductor layer with a thickness of 3 μm on the buffer layer, wherein the doping concentration of N-type dopant in the N-type semiconductor layer is 5 × 1018cm-3
Step 404: and controlling the temperature to be 950 ℃ and the pressure to be 300torr, and growing a stress release layer with the thickness of 275nm on the N-type semiconductor layer, wherein the stress release layer comprises 6 first sublayers with the thickness of 2nm and 6 second sublayers with the thickness of 30nm which are alternately grown.
Step 405: irradiating the surface of the stress release layer with accelerated oxygen ions and silver ions at a radiation dose of 5 × 1011ions/cm2The radiation energy of oxygen ions is 100MeV, and the radiation dose of silver ions is 5 x 1011ions/cm2The radiation energy of the oxygen ions was 200 MeV.
Step 406: controlling the pressure to be 300torr, and growing an active layer on the stress release layer, wherein the active layer comprises 10 quantum wells and 10 quantum barriers which are alternately grown; the thickness of the quantum well is 3nm, and the growth temperature of the quantum well is 770 ℃; the thickness of the quantum barrier is 15nm, and the growth temperature of the quantum barrier is 900 ℃.
Step 407: controlling the temperature at 960 deg.C and the pressure200torr, growing a P-type semiconductor layer with a thickness of 450nm on the active layer, wherein the doping concentration of a P-type dopant in the P-type semiconductor layer is 5 x 1018cm-3
Compared with the chip without ion radiation, the forward voltage of the chip is reduced by 1.5-3%, and the luminous efficiency is improved by 2-3%.
An embodiment of the present invention provides an led epitaxial wafer, and fig. 2 is a schematic structural diagram of an led epitaxial wafer according to an embodiment of the present invention, and referring to fig. 2, the led epitaxial wafer includes a substrate 10, a buffer layer 20, an N-type semiconductor layer 30, a stress release layer 40, an active layer 50, and a P-type semiconductor layer 60, and the buffer layer 20, the N-type semiconductor layer 30, the stress release layer 40, the active layer 50, and the P-type semiconductor layer 60 are sequentially stacked on the substrate 10.
In the present embodiment, the surface of the stress relaxation layer 40 is the ion-irradiated surface.
Alternatively, the ions of the radiation stress relieving layer may include at least one of oxygen ions and silver ions.
Preferably, when the ions of the radiation stress relieving layer may include oxygen ions, the radiation dose of the oxygen ions may be 1011ions/cm2~1012ions/cm2
Preferably, when the ions of the radiation stress relieving layer may include silver ions, the radiation dose of the silver ions may be 1010ions/cm2~1013ions/cm2
Specifically, sapphire may be used as the material of the substrate 10. The buffer layer 20 may be made of gallium nitride (GaN). The material of the N-type semiconductor layer 30 may be N-type doped gallium nitride. The stress release layer 40 may include a plurality of first sublayers and a plurality of second sublayers, which are alternately stacked; the material of the first sub-layer can adopt indium gallium nitride, and the molar content of the indium component in the first sub-layer is less than or equal to 0.05; the material of the second sub-layer can adopt aluminum gallium nitride, and the molar content of the aluminum component in the second sub-layer can be less than or equal to 0.2. The active layer 50 may include a plurality of quantum wells and a plurality of quantum barriers, which are alternately stacked; the quantum well may be indium gallium nitride (InGaN), and the quantum barrier may be gallium nitride (gan). The P-type semiconductor layer 60 may be made of P-type doped gallium nitride.
More specifically, the thickness of the buffer layer 20 may be 15nm to 35nm (preferably 25 nm). The thickness of the N-type semiconductor layer 30 may be 1 μm to 5 μm (preferably 3 μm), and the doping concentration of the N-type dopant in the N-type semiconductor layer 30 may be 1018cm-3~1019cm-3(preferably 5 x 10)18cm-3). The number of the first sublayers is the same as that of the second sublayers, and the number of the second sublayers can be 3-9; the thickness of the first sub-layer is 1 nm-3 nm, and the thickness of the second sub-layer is 20 nm-40 nm. The number of quantum wells is the same as that of quantum barriers, and the number of quantum barriers can be 5-15 (preferably 10); the thickness of the quantum well may be 2.5nm to 3.5nm (preferably 3nm), and the thickness of the quantum barrier may be 9nm to 20nm (preferably 15 nm). The thickness of the P-type semiconductor layer 60 may be 100nm to 800nm (preferably 450nm), and the doping concentration of the P-type dopant in the P-type semiconductor layer 50 may be 1018cm-3~1019cm-3(preferably 5 x 10)18cm-3)。
Optionally, as shown in fig. 2, the light emitting diode epitaxial wafer may further include an undoped gallium nitride layer 70 disposed between the buffer layer 20 and the N-type semiconductor layer 30 to alleviate lattice mismatch between the substrate and the N-type semiconductor layer.
Specifically, the thickness of the undoped gallium nitride layer 70 may be 1 μm to 5 μm (preferably 3 μm).
Optionally, as shown in fig. 2, the light emitting diode epitaxial wafer may further include an electron blocking layer 80, and the electron blocking layer 80 is disposed between the active layer 50 and the P-type semiconductor layer 60 to prevent electrons from jumping into the P-type semiconductor layer to combine with holes in a non-radiative manner, thereby affecting the light emitting efficiency of the LED.
Specifically, the electron blocking layer 80 may be made of P-type doped aluminum gallium nitride (AlGaN), preferably P-type doped AlyGa1-yN,Y is more than 0.1 and less than 0.5; the thickness of the electron blocking layer 80 may be 50nm to 150nm (preferably 100 nm).
Optionally, as shown in fig. 2, the light emitting diode epitaxial wafer may further include a P-type contact layer 90, and the P-type contact layer 90 is disposed on the P-type semiconductor layer 60 to form a good ohmic contact with an electrode or a transparent conductive film in a chip process.
Specifically, the P-type contact layer 90 may be made of P-type doped indium gallium nitride; the thickness of the P-type contact layer 90 may be 5nm to 300nm (preferably 150 nm).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A manufacturing method of a light emitting diode epitaxial wafer is characterized by comprising the following steps:
growing a buffer layer, an N-type semiconductor layer and a stress release layer on a substrate in sequence by adopting a chemical vapor deposition technology;
irradiating accelerated ions on the surface of the stress release layer in a vacuum environment to reduce the resistivity of the stress release layer, wherein the ions comprise at least one of oxygen ions and silver ions;
and sequentially growing an active layer and a P-type semiconductor layer on the stress release layer by adopting a chemical vapor deposition technology.
2. The method of claim 1, wherein when the ions comprise oxygen ions, the radiation dose of the oxygen ions is 1011ions/cm2~1012ions/cm2
3. The method of claim 2, wherein when the ions include oxygen ions, the radiation energy of the oxygen ions is 50MeV to 150 MeV.
4. The method of claim 1, wherein when the ions comprise silver ions, the radiation dose of the silver ions is 1010ions/cm2~1013ions/cm2
5. The method of claim 4, wherein when the ions include silver ions, the radiation energy of the silver ions is 150MeV to 250 MeV.
6. The method according to any one of claims 1 to 5, wherein the temperature of the vacuum environment is 20 ℃ to 100 ℃.
7. The production method according to any one of claims 1 to 5, further comprising:
and after the surface of the stress release layer is subjected to ion irradiation, annealing treatment is carried out on the stress release layer.
8. The light-emitting diode epitaxial wafer comprises a substrate, a buffer layer, an N-type semiconductor layer, a stress release layer, an active layer and a P-type semiconductor layer, wherein the buffer layer, the N-type semiconductor layer, the stress release layer, the active layer and the P-type semiconductor layer are sequentially stacked on the substrate.
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