CN117174793B - Blue-green light LED epitaxial wafer, preparation method thereof and LED chip - Google Patents
Blue-green light LED epitaxial wafer, preparation method thereof and LED chip Download PDFInfo
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Abstract
The invention provides a blue-green light LED epitaxial wafer and a preparation method thereof, and an LED chip.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a blue-green light LED epitaxial wafer, a preparation method thereof and an LED chip.
Background
GaN materials have been widely used in high frequency, high temperature, high voltage electronic device fields, light Emitting Diodes (LEDs), and semiconductor Lasers (LD), etc., because of their low heat generation efficiency, radiation resistance, high breakdown voltage, high electron saturation drift velocity, and small dielectric constant, and have become a hot spot for current research.
The LED epitaxial growth process faces a plurality of technical difficulties, such as smaller effective mass of electrons and higher mobility, so that electrons can easily overflow to the P layer through the quantum well; for example, the doping of P-type GaN is difficult, the activation efficiency of the dopant Mg is low, which results in insufficient holes, and the mobility of holes is very low, which results in the reduction of the efficiency of radiative recombination of electron holes, and the activation efficiency, mobility and epitaxial layer crystal quality of holes are further reduced with the increase of Al components, which results in the reduction of the luminous efficiency of the LED; in addition, polarization electric fields exist between the well barriers due to lattice mismatch, so that the energy bands of the well barriers are inclined, the interfaces of the well barriers are unclear, and electron holes in the quantum well are unevenly distributed, so that the overlapping rate of electron-hole wave functions in the quantum well is reduced, finally, the radiation recombination efficiency is reduced, and the performance and the application of the light-emitting diode are severely limited. In order to improve the luminous efficiency of the LED, it is necessary to prepare an epitaxial layer structure with high radiation recombination efficiency and high crystal quality.
At present, a multi-quantum well layer in a blue-green LED epitaxial structure obtained by an MOCVD (Metal-organic Chemical Vapor Deposition, metal organic chemical vapor deposition) method is generally composed of InGaN/GaN, wherein InGaN is used as a well layer, gaN is used as a barrier layer, a larger polarized electric field exists between InGaN and GaN due to lattice mismatch, so that energy bands between the well barriers are inclined, electron holes in a quantum well are unevenly distributed, and scattering is serious when the electron holes move; the barrier height of the GaN barrier layer is limited, and electrons in the quantum well easily overflow the barrier layer to the p-type layer; in addition, the In component In the InGaN layer is very sensitive to the growth temperature, the In component In the quantum well needs to be improved by a method of reducing the growth temperature In order to grow a quantum well with a deeper energy band, but the crystal quality of the quantum well is reduced due to low growth temperature, and defects are increased; the growth temperature of the quantum well is increased, so that the crystal quality can be improved, but In components are easily separated out, the interface of a well barrier is not clear, the energy band of the quantum well is made shallow, the limiting capacity for carriers is reduced, electrons are more easily overflowed to a p-type layer, and the radiation recombination efficiency of electron holes is severely reduced.
Disclosure of Invention
Based on the structure, the invention aims to provide a blue-green light LED epitaxial wafer, a preparation method thereof and an LED chip, and aims to introduce a novel multi-quantum well layer structure into the blue-green light LED epitaxial wafer so as to improve the radiation recombination efficiency of electron holes in the multi-quantum well layer of the blue-green light LED epitaxial wafer.
According to the embodiment of the invention, the blue-green LED epitaxial wafer comprises a multi-quantum well layer, wherein the multi-quantum well layer comprises a quantum well layer and a quantum barrier layer which are periodically and alternately grown, the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, the thickness of the quantum well layer is smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the temperature during growth of the first quantum barrier layer is smaller than that during growth of the second quantum barrier layer, and the temperature during growth of the second quantum barrier layer is 100-130 ℃ higher than that during growth of the first quantum barrier layer.
Further, the blue-green light LED epitaxial wafer further comprises a substrate, an AlN buffer layer, an undoped GaN layer, an N-type doped GaN layer, an electron blocking layer, a P-type doped GaN layer and a contact layer;
and depositing the AlN buffer layer, the undoped GaN layer, the N-type doped GaN layer, the multiple quantum well layer, the electron blocking layer, the P-type doped GaN layer and the contact layer on the substrate in sequence along the epitaxial growth direction.
Further, the thickness of the quantum well layer is 2 nm-5 nm, and the thickness of the quantum barrier layer is 10 nm-20 nm.
Further, the thickness of the first quantum barrier layer is 1 nm-3 nm.
Further, the thickness of the second quantum barrier layer is 8 nm-19 nm.
Further, the temperature of the first quantum barrier layer is 800-900 ℃.
Further, the temperature of the second quantum barrier layer is 950-1000 ℃.
Further, the temperature of the quantum well layer is 800-900 ℃.
According to the preparation method of the blue-green LED epitaxial wafer, which is provided by the embodiment of the invention, the preparation method is used for preparing the blue-green LED epitaxial wafer, and comprises the following steps:
periodically and alternately growing a quantum well layer and a quantum barrier layer along an epitaxial growth direction, wherein the quantum well layer is a GaSb layer, and the quantum barrier layer is a GaN layer, wherein the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, the thickness of the quantum well layer is controlled to be smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is controlled to be smaller than that of the second quantum barrier layer, the temperature during growth of the first quantum barrier layer is controlled to be smaller than that during growth of the second quantum barrier layer, and the temperature during growth of the second quantum barrier layer is controlled to be 100-130 ℃ higher than that during growth of the first quantum barrier layer.
According to an embodiment of the invention, an LED chip comprises the blue-green light LED epitaxial wafer.
The beneficial effects of the invention are as follows:
the multi-quantum well layer structure is arranged to be a GaSb/GaN structure, wherein the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises the first quantum barrier layer and the second quantum barrier layer which are sequentially deposited, the forbidden band width of the GaSb quantum well layer is 0.73 and eV, a quantum well with a deeper energy band can be formed, the electron overflow is favorably limited, the sensitivity of the GaSb quantum well layer to the temperature is far lower than that of the InGaN quantum well layer, a quantum well layer with good crystal quality and a deep energy band can be formed, and particularly, the stress generated by lattice mismatch of GaSb and GaN can be released by the first quantum barrier layer through reducing the growth temperature, so that the energy band curvature between the well barriers is reduced, the well interface is clear and steep, the overlapping rate of electron-hole wave functions in the quantum well is increased, and finally the radiation recombination efficiency of electron holes is increased.
Drawings
Fig. 1 is a schematic structural diagram of a blue-green LED epitaxial wafer according to an embodiment of the present invention;
fig. 2 is a flowchart of a preparation method of a blue-green LED epitaxial wafer according to an embodiment of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Several embodiments of the invention are presented in the figures. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "mounted" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, a schematic structural diagram of a blue-green LED epitaxial wafer according to an embodiment of the present invention is provided, where the blue-green LED epitaxial wafer includes a substrate 1, and an AlN buffer layer 2, an undoped GaN layer 3, an N-type doped GaN layer 4, a multiple quantum well layer 5, an electron blocking layer 6, a P-type doped GaN layer 7, and a contact layer 8 sequentially disposed on the substrate 1.
In the present embodiment, the substrate 1 is a sapphire substrate, specifically, the thickness of the AlN buffer layer 2 is 15nm to 50nm, and the thickness of the AlN buffer layer is, for example, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, or the like, but not limited thereto; the undoped GaN layer 3 has a thickness of 1 μm to 3 μm, and the undoped GaN layer 3 has a thickness of 1 μm,1.5 μm, 2 μm, 2.5 μm, 3 μm, or the like, but is not limited thereto; the dopant of the N-type doped GaN layer 4 is Si, and the doping concentration of the N-type doped GaN layer 4 can be 1E19atoms/cm 3 ~1E20 atoms/cm 3 The thickness of the N-type doped GaN layer 4 is 1 μm to 3 μm, and exemplary N-type doped GaN layers 4 are 1 μm, 1.5 μm, 2 μm, 2.5 μm, or 3 μm, etc., but are not limited thereto; the multi-quantum well layer 5 comprises a quantum well layer and a quantum barrier layer which are periodically and alternately grown, the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, wherein the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, the first quantum barrier layer and the second quantum barrier layer are both GaN layers, the thickness of the quantum well layer is smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the energy band of the quantum barrier layer is larger than that of the quantum well layer, the quantum barrier layer is used for blocking electrons overflowing to the p-type GaN layer, the thickness of the quantum barrier layer is larger than that of the quantum well layer, the effect of blocking electrons overflowing is better, in addition, the growth temperature of the first quantum barrier layer is reduced for releasing stress between the quantum well layer and the second quantum barrier layer, the polarization effect between the well barriers is reduced, the luminous efficiency of the quantum well is improved, and the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the crystal quality is worse than that of the second quantum barrier layer, the whole luminous efficiency of the LED is improved.
The growth period of the quantum well layer and the quantum barrier layer in the active layer is 6-12, specifically, the thickness of the quantum well layer is 2-5 nm, and the thickness of the quantum well layer is 2nm, 2.5 nm, 3nm, 3.5 nm, 4nm, 4.5nm or 5nm, etc., but is not limited thereto; the thickness of the quantum barrier layer is 10nm to 20nm, and exemplary, but not limited thereto, the thickness of the quantum barrier layer is 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, or the like; the thickness of the first quantum barrier layer is 1nm to 3nm, and exemplary, but not limited thereto, the thickness of the first quantum barrier layer is 1nm, 2nm, 3nm, or the like; the second quantum barrier layer has a thickness of 8nm to 19nm, and illustratively the second quantum barrier layer has a thickness of 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, or19nm, etc., but is not limited thereto; the thickness of the electron blocking layer 6 is 20 nm-100 nm, the electron blocking layer 6 is made of AlGaN material, the Al composition is 0.1-0.5, and the thickness of the electron blocking layer 6 is exemplified by, but not limited to, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc.; the doping agent of the P-type doped GaN layer 7 is Mg, and the doping concentration of the Mg is 1E19atoms/cm 3 ~1E20 atoms/cm 3 The thickness of the P-type doped GaN layer 7 is 10nm to 50nm, and exemplary thicknesses of the P-type doped GaN layer 7 are 10nm, 20nm, 30nm, 40nm or 50nm, etc., but are not limited thereto; the contact layer 8 is a P-type GaN contact layer, the doping agent of the P-type GaN contact layer is Mg, and the doping concentration of the Mg is 1E19atoms/cm 3 ~1E20 atoms/cm 3 The thickness of the P-type GaN contact layer is 10nm to 50nm, and exemplary P-type GaN contact layers are 10nm, 20nm, 30nm, 40nm or 50nm, etc., but are not limited thereto.
In the process of growing the multiple quantum well layer 5, the temperature at which the first quantum barrier layer is grown is controlled to be lower than the temperature at which the second quantum barrier layer is grown, and the purpose of this is to release stress generated by lattice mismatch between GaSb and GaN, specifically, the temperature at which the first quantum barrier layer is grown is 800 to 900 ℃, the temperature at which the second quantum barrier layer is grown is 950 to 1000 ℃, and the temperature at which the quantum well layer is grown is 800 to 900 ℃.
Correspondingly, referring to fig. 2, the embodiment of the invention further provides a preparation method of the blue-green LED epitaxial wafer, which is used for preparing the blue-green LED epitaxial wafer, and specifically comprises the following steps:
s100: providing a substrate;
wherein, sapphire Al with (0001) crystal orientation is adopted 2 O 3 Is a substrate.
S200: sequentially depositing an AlN buffer layer, an undoped GaN layer, an N-type doped GaN layer, a multiple quantum well layer, an electron blocking layer, a P-type doped GaN layer and a contact layer on a substrate along the epitaxial growth direction;
specifically, S200 includes:
s201: growing an AlN buffer layer on the sapphire substrate;
specifically, an AlN buffer layer is deposited by adopting a PVD (Physical Vapor Deposition ) method, wherein in the process of growing the AlN buffer layer, the growth temperature is controlled to be 400-650 ℃, the sputtering power is 2000-4000W, the pressure is 1-10 torr, and finally the AlN buffer layer with the thickness of 15-50 nm is deposited.
And then carrying out in-situ annealing treatment in MOCVD (Metal-organic Chemical Vapor Deposition, metal organic chemical vapor deposition) equipment under the hydrogen atmosphere, wherein the temperature is 1000-1200 ℃, the pressure is 150-500 torr, and the time is 5 min-10 min.
S202: growing an undoped GaN layer on the AlN buffer layer;
and growing an undoped GaN layer in MOCVD equipment, specifically, controlling the growth temperature to 1050-1200 ℃ and the pressure to 100-500 torr in the process of growing the undoped GaN layer, and finally depositing the undoped GaN layer with the thickness of 1-3 mu m.
S203: growing an N-type doped GaN layer on the undoped GaN layer;
specifically, an N-type doped GaN layer is grown in MOCVD equipment, wherein the doping agent of the N-type doped GaN layer is Si, and the doping concentration of the N-type doped GaN layer is 1E19atoms/cm 3 ~1E20 atoms/cm 3 And controlling the temperature in the MOCVD reaction chamber to be 1100-1200 ℃ and the pressure to be 100-300 torr, and finally depositing an N-type doped GaN layer with the thickness of 1-3 mu m.
S204: growing a multi-quantum well layer on the N-doped GaN layer;
specifically, growing a multiple quantum well layer in MOCVD equipment, wherein the multiple quantum well layer comprises a quantum well layer and a quantum barrier layer which are periodically and alternately grown, the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, it can be understood that the first quantum barrier layer and the second quantum barrier layer are both GaN layers, the thickness of the quantum well layer is smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the growth period of the quantum well layer and the quantum barrier layer in the active layer is 6-12, and the requirement is that the thickness of the quantum well layer in a single period is controlled to be 2-5 nm, the growth temperature is 800-900 ℃, and the pressure is 100-200 torr;
the thickness of the quantum barrier layer in a single period is 10-20 nm, wherein the quantum barrier layer is divided into a first quantum barrier layer and a second quantum barrier layer;
the thickness of the first quantum barrier layer is 1-3 nm, the growth temperature is 800-900 ℃, and the pressure is 200-300 torr;
the thickness of the second quantum barrier layer is 8-19 nm, the growth temperature is 950-1000 ℃, and the pressure is 100-300 torr.
S205: growing an electron blocking layer on the multiple quantum well layer;
specifically, an AlGaN electron blocking layer grows in MOCVD equipment, the thickness of the deposited electron blocking layer is controlled to be 20 nm-100 nm, the Al component is controlled to be 0.1-0.5, wherein the temperature in the MOCVD equipment is controlled to be 1000-1100 ℃, and the pressure is controlled to be 50-100 torr.
S206: growing a P-type doped GaN layer on the electron blocking layer;
specifically, growing a P-type doped GaN layer in MOCVD equipment, and controlling the thickness of the deposited P-type doped GaN layer to be 30-200 nm, wherein the doping agent of the P-type doped GaN layer is Mg, and the doping concentration of the Mg is 1E19atoms/cm 3 ~1E20 atoms/cm 3 The temperature in the MOCVD equipment is controlled to be 950-1050 ℃ and the air pressure is controlled to be 100-600 torr.
S207: growing a contact layer on the P-type doped GaN layer;
specifically, growing a P-type contact layer in MOCVD equipment, and controlling the thickness of the deposited P-type contact layer to be 10 nm-50 nm, wherein the doping agent of the P-type contact layer is Mg, and the doping concentration of the Mg is 1E19atoms/cm 3 ~1E20 atoms/cm 3 The temperature in the MOCVD equipment is controlled to be 1000-1100 ℃ and the air pressure is controlled to be 100-300 torr.
And after the epitaxial structure is grown, reducing the temperature of the reaction cavity, annealing in a nitrogen atmosphere at 650-850 ℃ for 5-15 min, and cooling to room temperature to finish epitaxial growth.
Trimethylaluminum (TMAL), trimethylindium (TMIn), trimethylgallium or triethylgallium (TMGa or TEGa) as a precursor of a group III source, ammonia (NH) 3 ) And stibine (SbH) 3 ) As a precursor to the group v source, silane (SiH 4 ) And magnesium dicyclopentadiene (Cp) 2 Mg) are used as precursors for the N-type dopant and the P-type dopant, respectively, and nitrogen and hydrogen are used as carrier gases.
The invention is further illustrated by the following examples:
example 1
The embodiment 1 of the invention provides a blue-green LED epitaxial wafer, which comprises a substrate, an AlN buffer layer, an undoped GaN layer, an N-type doped GaN layer, a multiple quantum well layer, an electron blocking layer, a P-type doped GaN layer and a contact layer, wherein the AlN buffer layer, the undoped GaN layer, the N-type doped GaN layer, the multiple quantum well layer, the electron blocking layer, the P-type doped GaN layer and the contact layer are sequentially arranged on the substrate.
In this embodiment, the substrate is a sapphire substrate, and specifically, the thickness of the AlN buffer layer is 20nm; the undoped GaN layer has a thickness of 2.5 μm; the doping agent of the N-type doped GaN layer is Si, and the doping concentration of the N-type doped GaN layer can be 9E19atoms/cm 3 The thickness of the N-type doped GaN layer is 2.8 mu m; the multi-quantum well layer comprises a quantum well layer and a quantum barrier layer which are periodically and alternately grown, the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, it can be understood that the first quantum barrier layer and the second quantum barrier layer are both GaN layers, the thickness of the quantum well layer is smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the growth period of the quantum well layer and the quantum barrier layer in the active layer is 10, and specifically, the thickness of the quantum well layer is 2nm; the thickness of the quantum barrier layer is 11nm; the thickness of the first quantum barrier layer is 1nm; the thickness of the second quantum barrier layer is 10nm; the thickness of the electron blocking layer is 50nm, the electron blocking layer is made of AlGaN material, and the Al component is 0.4; the doping agent of the P-type doped GaN layer is Mg, and the doping concentration of the Mg is 9E19atoms/cm 3 The thickness of the P-type doped GaN layer is 50nm; the contact layer is a P-type GaN contact layer, the doping agent of the P-type GaN contact layer is Mg, and the doping concentration of the Mg is 1E20 atoms/cm 3 The thickness of the P-type GaN contact layer is 20nm.
The preparation method of the blue-green LED epitaxial wafer in the embodiment comprises the following steps:
(1) Providing a sapphire substrate;
wherein, sapphire Al with (0001) crystal orientation is adopted 2 O 3 Is a substrate.
(2) Growing an AlN buffer layer on the sapphire substrate;
specifically, an AlN buffer layer is deposited by adopting a PVD (Physical Vapor Deposition ) method, wherein in the process of growing the AlN buffer layer, the growth temperature is controlled to be 600 ℃, the sputtering power is 3500W, the pressure is 4torr, and finally the AlN buffer layer with the thickness of 20nm is deposited.
Then in-situ annealing treatment is carried out in MOCVD (Metal-organic Chemical Vapor Deposition, metal organic chemical vapor deposition) equipment under hydrogen atmosphere at 1000 ℃ under 300torr for 8min.
(3) Growing an undoped GaN layer on the AlN buffer layer;
wherein, the undoped GaN layer is grown in MOCVD equipment, specifically, in the process of growing the undoped GaN layer, the growth temperature is controlled to be 1140 ℃, the pressure is controlled to be 150torr, and finally the undoped GaN layer with the thickness of 2.5 μm is deposited.
(4) Growing an N-type doped GaN layer on the undoped GaN layer;
specifically, an N-type doped GaN layer is grown in MOCVD equipment, wherein the doping agent of the N-type doped GaN layer is Si, and the doping concentration of the N-type doped GaN layer is 9E19atoms/cm 3 The temperature in the MOCVD reaction chamber is controlled to be 1150 ℃, the pressure is controlled to be 150torr, and finally the N-type doped GaN layer with the thickness of 2.8 mu m is deposited.
(5) Growing a multi-quantum well layer on the N-doped GaN layer;
specifically, growing a multiple quantum well layer in MOCVD equipment, wherein the multiple quantum well layer comprises a quantum well layer and a quantum barrier layer which are periodically and alternately grown, the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, it can be understood that the first quantum barrier layer and the second quantum barrier layer are both GaN layers, the thickness of the quantum well layer is smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the growth period of the quantum well layer and the quantum barrier layer in the active layer is 10, and the growth temperature is 850 ℃ and the pressure is 100torr in a single period;
the thickness of the first quantum barrier layer is 1nm, the growth temperature is 850 ℃, and the pressure is 300torr;
the thickness of the second quantum barrier layer is 10nm, the growth temperature is 950 ℃, and the pressure is 200torr.
(6) Growing an electron blocking layer on the multiple quantum well layer;
specifically, an AlGaN electron blocking layer is grown in MOCVD equipment, the thickness of the deposited electron blocking layer is controlled to be 50nm, and the Al component is controlled to be 0.4, wherein the temperature in the MOCVD equipment is controlled to be 1100 ℃, and the pressure is controlled to be 70torr.
(7) Growing a P-type doped GaN layer on the electron blocking layer;
specifically, growing a P-type doped GaN layer in MOCVD equipment, and controlling the thickness of the deposited P-type doped GaN layer to be 50nm, wherein the doping agent of the P-type doped GaN layer is Mg, and the doping concentration of the Mg is 9E19atoms/cm 3 The temperature in the MOCVD equipment is controlled to 980 ℃ and the air pressure is controlled to 600torr.
(8) Growing a contact layer on the P-type doped GaN layer;
specifically, growing a P-type contact layer in MOCVD equipment, and controlling the thickness of the deposited P-type contact layer to be 20nm, wherein the doping agent of the P-type contact layer is Mg, and the doping concentration of the Mg is 1E20 atoms/cm 3 The temperature in the MOCVD apparatus was controlled to 1020℃and the gas pressure to 200torr.
And after the epitaxial structure is grown, reducing the temperature of the reaction cavity, annealing in a nitrogen atmosphere at 800 ℃ for 10min, and cooling to room temperature to finish epitaxial growth.
In this example, trimethylaluminum (TMAL), trimethylindium (TMIn), trimethylgallium or triethylgallium (TMGa or TEGa) was used as a precursor of the group III source, ammonia (NH) 3 ) And stibine (SbH) 3 ) As a precursor to the group v source, silane (SiH 4 ) And magnesium dicyclopentadiene (Cp) 2 Mg) as precursors for N-type and P-type dopants, respectively, nitrogenAnd hydrogen as a carrier gas.
Example 2
Embodiment 2 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the quantum well layer thickness is controlled to be 3nm in a single period.
Example 3
Embodiment 3 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the quantum well layer thickness is controlled to be 4nm in a single period.
Example 4
Embodiment 4 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the quantum well layer thickness is controlled to be 5nm in a single period.
Example 5
Embodiment 5 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the thickness of the quantum well layer in a single period is controlled to be 4nm, and the thickness of the first quantum barrier layer in a single period is controlled to be 2nm.
Example 6
The embodiment 6 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the thickness of the quantum well layer in a single period is controlled to be 4nm, and the thickness of the first quantum barrier layer in the single period is controlled to be 3nm.
Example 7
Embodiment 7 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the thickness of the quantum well layer in a single period is controlled to be 4nm, the thickness of the first quantum barrier layer in a single period is controlled to be 2nm, and the thickness of the second quantum barrier layer in a single period is controlled to be 12nm.
Example 8
The embodiment 8 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the thickness of a quantum well layer in a single period is controlled to be 4nm, the thickness of a first quantum barrier layer in the single period is controlled to be 2nm, and the thickness of a second quantum barrier layer in the single period is controlled to be 14nm.
Example 9
Embodiment 9 of the present invention also provides a blue-green light LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the growth temperature of the quantum well layer in a single period is controlled to 800 ℃, the thickness of the quantum well layer in the single period is controlled to 4nm, the thickness of the first quantum barrier layer in the single period is controlled to 2nm, and the thickness of the second quantum barrier layer in the single period is controlled to 14nm.
Example 10
The embodiment 10 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the growth temperature of a quantum well layer in a single period is controlled to 900 ℃, the thickness of the quantum well layer in the single period is controlled to 4nm, the thickness of a first quantum barrier layer in the single period is controlled to 2nm, and the thickness of a second quantum barrier layer in the single period is controlled to 12nm.
Example 11
The embodiment 11 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the growth temperature of a first quantum barrier layer in a single period is controlled to be 800 ℃, the thickness of a quantum well layer in the single period is controlled to be 4nm, the thickness of the first quantum barrier layer in the single period is controlled to be 2nm, and the thickness of a second quantum barrier layer in the single period is controlled to be 12nm.
Example 12
The embodiment 12 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the growth temperature of a first quantum barrier layer in a single period is controlled to 900 ℃, the thickness of a quantum well layer in the single period is controlled to 4nm, the thickness of the first quantum barrier layer in the single period is controlled to 2nm, and the thickness of a second quantum barrier layer in the single period is controlled to 12nm.
Example 13
The embodiment 13 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the growth temperature of a first quantum barrier layer in a single period is controlled to be 800 ℃, the thickness of a quantum well layer in the single period is controlled to be 4nm, the thickness of the first quantum barrier layer in the single period is controlled to be 2nm, and the thickness of a second quantum barrier layer in the single period is controlled to be 12nm.
Example 14
Embodiment 14 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the growth temperature of the first quantum barrier layer in a single period is controlled to 800 ℃, the thickness of the quantum well layer in the single period is controlled to 4nm, the thickness of the first quantum barrier layer in the single period is controlled to 2nm, the thickness of the second quantum barrier layer in the single period is controlled to 12nm, and the growth temperature of the second quantum barrier layer in the single period is controlled to 980 ℃.
Example 15
Embodiment 15 of the present invention also provides a blue-green LED epitaxial wafer and a method for preparing the same, which are different from embodiment 1 in that the growth temperature of the first quantum barrier layer in a single period is controlled to 800 ℃, the thickness of the quantum well layer in the single period is controlled to 4nm, the thickness of the first quantum barrier layer in the single period is controlled to 2nm, the thickness of the second quantum barrier layer in the single period is controlled to 12nm, and the growth temperature of the second quantum barrier layer in the single period is controlled to 1000 ℃.
Example 16
The embodiment 16 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the thickness of a quantum well layer in a single period is controlled to be 4nm, the thickness of a first quantum barrier layer in the single period is controlled to be 2nm, the thickness of a second quantum barrier layer in the single period is controlled to be 12nm, and the growth temperature of the second quantum barrier layer in the single period is controlled to be 980 ℃.
Example 17
The embodiment 17 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the thickness of a quantum well layer in a single period is controlled to be 4nm, the thickness of a first quantum barrier layer in the single period is controlled to be 2nm, the thickness of a second quantum barrier layer in the single period is controlled to be 12nm, and the growth temperature of the second quantum barrier layer in the single period is controlled to be 1000 ℃.
Example 18
The embodiment 18 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the thickness of a quantum well layer in a single period is controlled to be 4nm, the growth temperature of a second quantum barrier layer in the single period is controlled to be 900 ℃, the thickness of a first quantum barrier layer in the single period is controlled to be 2nm, the thickness of the second quantum barrier layer in the single period is controlled to be 12nm, and the growth temperature of the second quantum barrier layer in the single period is controlled to be 980 ℃.
Example 19
The embodiment 19 of the invention also provides a blue-green LED epitaxial wafer and a preparation method thereof, which are different from the embodiment 1 in that the thickness of a quantum well layer in a single period is controlled to be 4nm, the growth temperature of a second quantum barrier layer in the single period is controlled to be 900 ℃, the thickness of a first quantum barrier layer in the single period is controlled to be 2nm, the thickness of the second quantum barrier layer in the single period is controlled to be 12nm, and the growth temperature of the second quantum barrier layer in the single period is controlled to be 1000 ℃.
The LED chips prepared from the blue-green LED epitaxial wafers of examples 1to 19 and the LED chip having a multiple quantum well layer structure of InGaN/GaN in the prior art were tested under the same conditions (test current 120 mA), and specific results were as follows:
as can be seen from the table, the LED chip prepared by the blue-green LED epitaxial wafer obtained by the method in the embodiment of the invention has the advantage that the luminous brightness is effectively improved compared with the LED chip prepared by the traditional method of the comparative example under the same test condition, wherein the luminous brightness of the LED chip prepared by the blue-green LED epitaxial wafer obtained by the method in the embodiment 16 of the invention is the maximum and is 123.3mW, and the fact that the effect is optimal when the temperature of the second quantum barrier layer is 100-130 ℃ higher than the temperature of the first quantum barrier layer.
The embodiment of the invention also provides an LED chip, which comprises the blue-green light LED epitaxial wafer.
In summary, according to the blue-green light LED epitaxial wafer, the preparation method and the LED chip provided by the embodiment of the invention, the multi-quantum well layer structure is a GaSb/GaN structure, wherein the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, the forbidden band width of the GaSb quantum well layer is 0.73 and eV, a quantum well with a deeper energy band can be formed, the electron overflow is favorably limited, the sensitivity of the GaSb quantum well layer to the temperature is far lower than that of the InGaN quantum well layer, a quantum well layer with good crystal quality and a deep energy band can be formed, and particularly, the first quantum barrier layer can release stress generated by lattice mismatch between GaSb and GaN due to the fact that the growth temperature is reduced, so that the energy band bending between the well barriers is clear and steep, the overlapping rate of electron-hole wave functions in the quantum well is increased, and finally the radiation recombination efficiency of electron holes is increased.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The blue-green light LED epitaxial wafer is characterized by comprising a multi-quantum well layer, wherein the multi-quantum well layer comprises a quantum well layer and a quantum barrier layer which are periodically and alternately grown, the quantum well layer is a GaSb layer, the quantum barrier layer is a GaN layer, the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, the thickness of the quantum well layer is smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is smaller than that of the second quantum barrier layer, the temperature during growth of the first quantum barrier layer is smaller than that during growth of the second quantum barrier layer, and the temperature during growth of the second quantum barrier layer is 100-130 ℃ higher than that during growth of the first quantum barrier layer;
the temperature of the first quantum barrier layer is 800-900 ℃ and the temperature of the second quantum barrier layer is 950-1000 ℃.
2. The blue-green LED epitaxial wafer of claim 1, further comprising a substrate, an AlN buffer layer, an undoped GaN layer, an N-type doped GaN layer, an electron blocking layer, a P-type doped GaN layer, and a contact layer;
and depositing the AlN buffer layer, the undoped GaN layer, the N-type doped GaN layer, the multiple quantum well layer, the electron blocking layer, the P-type doped GaN layer and the contact layer on the substrate in sequence along the epitaxial growth direction.
3. The blue-green LED epitaxial wafer according to claim 1 or 2, wherein the quantum well layer has a thickness of 2nm to 5nm and the quantum barrier layer has a thickness of 10nm to 20nm.
4. The blue-green LED epitaxial wafer of claim 3, wherein the first quantum barrier layer has a thickness of 1nm to 3nm.
5. The blue-green LED epitaxial wafer of claim 3, wherein the second quantum barrier layer has a thickness of 8nm to 19nm.
6. The blue-green LED epitaxial wafer according to claim 1 or 2, wherein the temperature at which the quantum well layer is grown is 800 ℃ to 900 ℃.
7. A method for preparing a blue-green LED epitaxial wafer, which is used for preparing the blue-green LED epitaxial wafer according to any one of claims 1to 6, the method comprising:
periodically and alternately growing a quantum well layer and a quantum barrier layer along an epitaxial growth direction, wherein the quantum well layer is a GaSb layer, and the quantum barrier layer is a GaN layer, wherein the quantum barrier layer comprises a first quantum barrier layer and a second quantum barrier layer which are sequentially deposited, the thickness of the quantum well layer is controlled to be smaller than that of the quantum barrier layer, the thickness of the first quantum barrier layer is controlled to be smaller than that of the second quantum barrier layer, the temperature during growth of the first quantum barrier layer is controlled to be smaller than that during growth of the second quantum barrier layer, and the temperature during growth of the second quantum barrier layer is controlled to be 100-130 ℃ higher than that during growth of the first quantum barrier layer.
8. An LED chip comprising the blue-green LED epitaxial wafer according to any one of claims 1to 6.
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