CN113257969A - Nonpolar AlGaN-based ultraviolet LED epitaxial wafer and preparation method thereof - Google Patents
Nonpolar AlGaN-based ultraviolet LED epitaxial wafer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nonpolar AlGaN-based ultraviolet LED epitaxial wafer and a preparation method thereof, wherein the structure of the epitaxial wafer comprises the following components: the high-temperature AlGaN/GaN high-temperature-resistant high-temperature AlN layer grown on the high-temperature AlN layer, the high-temperature non-doped a-surface AlGaN layer grown on the low-temperature a-surface AlGaN layer, the n-type doped a-surface AlGaN layer grown on the high-temperature non-doped a-surface AlGaN layer, the a-surface AlGaN multi-quantum well layer grown on the n-type doped a-surface AlGaN layer, the electron blocking layer grown on the a-surface AlGaN multi-quantum well layer, the p-type doped AlGaN layer grown on the electron blocking layer, and the p-type doped GaN layer grown on the p-type doped AlGaN layer. The nonpolar AlGaN-based ultraviolet LED epitaxial wafer on the silicon carbide substrate has low defect density, good crystallization quality and good electrical and optical properties, can effectively reduce dislocation formation, improves the radiation recombination efficiency of current carriers, and prepares the ultraviolet LED with high heat conductivity, high electric conductivity and high luminous performance.
Description
Technical Field
The invention relates to the technical field of semiconductor devices, in particular to a non-polar ultraviolet LED epitaxial wafer and a preparation method thereof.
Background
The ultraviolet light has wide application prospect in the fields of national defense technology, information technology, bio-pharmaceuticals, environmental monitoring, public health, sterilization, disinfection and the like. The traditional ultraviolet light sources adopted at present are gas lasers and mercury lamps, but have the defects of large volume, high energy consumption, pollution and the like. An AlGaN-based compound semiconductor ultraviolet Light Emitting Diode (LED) is a solid ultraviolet light source and has the advantages of small volume, high efficiency, long service life, environmental friendliness, low energy consumption, no pollution and the like. The AlGaN material is an irreplaceable material system for preparing the high-performance ultraviolet LED, has great requirements in civil and military aspects, such as medical and health fields of curing, cancer detection, skin disease treatment and the like, and has the advantages of no mercury pollution, adjustable wavelength, small volume, good integration, low energy consumption, long service life and the like.
Most of the conventional AlGaN-based ultraviolet LED structures are grown on a c-plane sapphire substrate. However, since AlGaN materials that are epitaxial on c-plane sapphire are generally c-plane and c-plane nitride materials are polar materials, AlGaN-based ultraviolet LEDs have extremely strong polarization fields. The polarizing electric field results from spontaneous polarization and piezoelectric polarization along the c-axis direction. Due to the polarization, the energy band of a multi-quantum well region of the ultraviolet LED is seriously bent, the wave functions of electrons and holes are separated in space, and the separation causes the effective recombination probability of the electron holes in an active region to be reduced, so that the luminous efficiency of the AlGaN-based LED is influenced. Meanwhile, the carrier transport is blocked by the polarized electric field, and finally, the carrier distribution is not uniform. Therefore, it is required to suppress polarization effects inside the material to improve the light emitting performance of the device.
Therefore, various performances of the AlGaN-based ultraviolet LED epitaxial wafer need to be improved.
Disclosure of Invention
In view of the problems in the background art, the present disclosure is directed to a non-polar AlGaN-based ultraviolet LED epitaxial wafer and a method for manufacturing the same.
In order to achieve the above object, the present disclosure provides a nonpolar AlGaN based ultraviolet LED epitaxial wafer and a preparation method thereof, wherein the epitaxial wafer structure includes: the high-temperature AlGaN/GaN high-temperature-resistant high-temperature AlN layer grown on the high-temperature AlN layer, the high-temperature non-doped a-surface AlGaN layer grown on the low-temperature a-surface AlGaN layer, the n-type doped a-surface AlGaN layer grown on the high-temperature non-doped a-surface AlGaN layer, the a-surface AlGaN multi-quantum well layer grown on the n-type doped a-surface AlGaN layer, the electron blocking layer grown on the a-surface AlGaN multi-quantum well layer, the p-type doped AlGaN layer grown on the electron blocking layer, and the p-type doped GaN layer grown on the p-type doped AlGaN layer.
In some embodiments, the low temperature AlN layer has a thickness of 5 to 100 nm.
In some embodiments, the high temperature AlN layer has a thickness of 200 to 500 nm.
In some embodiments, the thickness of the low-temperature a-plane AlGaN layer is 50-200 nm;
in some embodiments, the thickness of the high-temperature non-doped a-plane AlGaN layer is 500-1000 nm.
In some embodiments, the n-doped a-plane AlGaN layer has a thickness of 3 to 5 μm.
In some embodiments, the a-plane AlGaN multi-quantum well layer is composed of 7-10 periods of Al0.1Ga0.9N well layers and Al0.25Ga0.75N barrier layers.
In some embodiments, the thickness of the Al0.1Ga0.9N well layer is 2-3 nm;
in some embodiments, the thickness of the Al0.25Ga0.75N barrier layer is 7-10 nm.
In some embodiments, the electron blocking layer is an al0.2ga0.8n electron blocking layer;
in some embodiments, the electron blocking layer has a thickness of 20 to 50 nm.
In some embodiments, the p-doped AlGaN layer has a thickness of 300to 350 nm.
In some embodiments, the thickness of the p-type doped GaN layer is 300-350 nm.
In some embodiments, a method for preparing a nonpolar AlGaN-based ultraviolet LED epitaxial wafer includes:
step S1, selecting silicon carbide as a substrate;
step S2, growing a low-temperature AlN layer on the silicon carbide substrate;
step S3 growing a high-temperature AlN layer on the low-temperature AlN layer;
step S4 is to grow a low-temperature a-plane AlGaN layer on the high-temperature AlN layer
Step S5 of growing a high-temperature undoped a-plane AlGaN layer on the low-temperature a-plane AlGaN layer;
step S6 of growing an n-type doped a-plane AlGaN layer on the high-temperature undoped a-plane AlGaN layer;
step S7 of epitaxially growing an a-plane AlGaN multi-quantum well layer on the n-type doped a-plane AlGaN layer;
step S8 is to epitaxially grow an electronic barrier layer on the a-plane AlGaN multi-quantum well layer;
step S9 epitaxially growing a p-type doped AlGaN layer on the electron blocking layer;
step S10 epitaxially grows a p-type doped GaN layer on the p-type doped AlGaN layer.
The beneficial effects of this disclosure are as follows:
the nonpolar AlGaN-based ultraviolet LED epitaxial wafer on the silicon carbide substrate prepared by the method has the advantages of low defect density, good crystallization quality, good electrical and optical properties, capability of effectively reducing dislocation formation, improvement of radiation recombination efficiency of carriers, and capability of preparing an ultraviolet LED with high heat conduction, high electric conduction and high light-emitting property.
Drawings
Fig. 1 is a schematic structural diagram of a nonpolar AlGaN-based ultraviolet LED epitaxial wafer on a silicon carbide substrate according to an embodiment of the present invention;
fig. 2 is an electroluminescence spectrum of the nonpolar AlGaN-based ultraviolet LED epitaxial wafer prepared according to the embodiment of the present invention.
Detailed Description
The following describes in detail the nonpolar AlGaN-based ultraviolet LED epitaxial wafer and the preparation method according to the present invention.
First, a nonpolar AlGaN-based ultraviolet LED epitaxial wafer according to the first aspect of the present invention will be described.
The nonpolar AlGaN-based ultraviolet LED epitaxial wafer according to the first aspect of the present invention, as shown in fig. 1, includes: the low-temperature AlGaN layer 102 on the silicon carbide substrate 101 grows, the high-temperature AlN layer 103 grows on the low-temperature AlN layer 102, the low-temperature a-plane AlGaN layer 104 grows on the high-temperature AlN layer 103, the high-temperature non-doped a-plane AlGaN layer 105 grows on the low-temperature a-plane AlGaN layer 104, the n-type doped a-plane AlGaN layer 106 grows on the high-temperature non-doped a-plane AlGaN layer 105, the a-plane AlGaN multi-quantum well layer 107 grows on the n-type doped a-plane AlGaN layer 106, the electron blocking layer 108 grows on the a-plane AlGaN multi-quantum well layer 107, the p-type doped AlGaN layer 109 grows on the electron blocking layer 108, and the p-type doped GaN layer 110 grows on the p-type doped AlGaN layer 109.
The nonpolar AlGaN-based ultraviolet LED epitaxial wafer on the silicon carbide substrate provided by the embodiment of the invention grows on the silicon carbide substrate 101, and has low defect density, good crystallization quality and good electrical and optical properties. By growing the nonpolar AlGaN material (comprising the undoped a-surface AlGaN layer and the n-type doped a-surface AlGaN layer) and the multi-quantum well active layer on the silicon carbide substrate, the polar effect is effectively solved, and the luminous performance of the LED is effectively improved.
In some embodiments, a silicon carbide substrate 101 is selected. The silicon carbide can conduct electricity, the LED chip with the vertical structure can be prepared, the problem that the LED chip with the vertical structure cannot be prepared by adopting a sapphire substrate in the prior preparation method is solved, the two electrodes are distributed on the surface and the bottom of the chip, and the generated heat can be directly LED out through the electrodes, so that the service life of an epitaxial wafer can be prolonged; the silicon carbide substrate has good heat conductivity. In addition, the epitaxial structure can be used for directly preparing the nonpolar ultraviolet LED epitaxial wafer, so that the preparation of a nonpolar LED by adopting expensive self-supporting nonpolar GaN or self-supporting AlN substrate is avoided, and the production cost is low.
In the present example, for a polar group III nitride material, the growth direction is parallel to the polarization direction of the material, and a polarization electric field (up to the order of MV/cm) exists in the growth direction. The polarization electric field bends the energy band of the quantum well, which causes the wave functions of electrons and holes at the quantum well to be separated in space, reduces the recombination efficiency of the electrons and the holes, and finally seriously reduces the luminous efficiency of the device, namely the so-called Quantum Confinement Stark Effect (QCSE). And for non-polar III-nitride materials, the direction of the polarizing electric field is perpendicular to the growth direction of the material. The energy band of the non-polar group III nitride material is not bent by the presence of the polarizing electric field and the wave functions of electrons and holes are exactly spatially aligned, i.e., no QCSE is present. By utilizing the characteristic, the problem that the luminous efficiency of the ultraviolet LED is reduced due to QCSE can be solved fundamentally, and the problem that the efficiency of the ultraviolet LED is reduced along with the increase of the injection current is relieved to a great extent. On the other hand, due to its own characteristics, nonpolar group III nitride materials are more easily activated when p-type doping is performed than polar materials, and p-type materials with high hole concentration are more easily realized.
In some embodiments, a high temperature undoped a-plane AlGaN layer 105 is grown on the low temperature a-plane AlGaN layer 104. In the epitaxial growth technology of high-quality a-plane AlGaN, few AlGaN nucleation sites are generated at high temperature, so that two-dimensional layered growth is directly performed at high temperature, and the defect density in AlGaN is high; firstly, growing the low-temperature a-plane AlGaN, firstly growing the three-dimensional island-shaped AlGaN, then transversely growing and merging the three-dimensional island-shaped a-plane AlGaN under the high-temperature condition, continuing to grow two-dimensional layers, reducing the defect density in the AlGaN material, and finally obtaining the a-plane AlGaN layer with high crystal quality.
In some embodiments, the low temperature AlN layer 102 has a thickness of 5 to 100 nm.
In some embodiments, the high temperature AlN layer 103 has a thickness of 200 to 500 nm.
In some embodiments, the thickness of the low-temperature a-plane AlGaN layer 104 is 50-200 nm;
in some embodiments, the high temperature undoped a-plane AlGaN layer 105 has a thickness of 500 to 1000 nm.
In some embodiments, the n-doped a-plane AlGaN layer 106 has a thickness of 3 to 5 μm. Specifically, the n-type doped a-plane AlGaN layer 106 is doped with Si, and the doping concentration of Si may be 1 × 1017cm-1×1020cm-3。
In some embodiments, the a-plane AlGaN MQW layer 107 is composed of 7-10 periods of Al0.1Ga0.9N well layers and Al0.25Ga0.75N barrier layers. The period here means that one layer of Al0.1Ga0.9N well layer and one layer of Al0.25Ga0.75N barrier layer are alternately arranged to form one period, and 7-10 periods are arranged in total.
In some embodiments, the thickness of the Al0.1Ga0.9N well layer is 2-3 nm;
in some embodiments, the thickness of the Al0.25Ga0.75N barrier layer is 7-10 nm.
In some embodiments, the electron blocking layer 108 is an al0.2ga0.8n electron blocking layer;
in some embodiments, the electron blocking layer 108 has a thickness of 20 to 50 nm. In order to avoid that the injected electrons cannot be efficiently radiatively recombined in the active region, the electron blocking layer is provided in the embodiment of the present invention.
In some embodiments, the thickness of the p-doped AlGaN layer 109 is 300to 350 nm.
In some embodiments, the thickness of the p-type doped GaN layer 110 is 300-350 nm.
The electroluminescence spectrum of the nonpolar AlGaN-based ultraviolet LED epitaxial wafer finally prepared in the embodiment of the present invention is shown in fig. 2.
Next, a method for producing the nonpolar AlGaN-based ultraviolet LED epitaxial wafer according to the second aspect of the present application will be described.
The preparation method of the nonpolar AlGaN-based ultraviolet LED epitaxial wafer according to the second aspect comprises the following steps:
step S1, selecting silicon carbide as a substrate;
step S2, growing a low-temperature AlN layer on the silicon carbide substrate;
step S3 growing a high-temperature AlN layer on the low-temperature AlN layer;
step S4 growing a low-temperature a-plane AlGaN layer on the high-temperature AlN layer;
step S5 of growing a high-temperature undoped a-plane AlGaN layer on the low-temperature a-plane AlGaN layer;
step S6 of growing an n-type doped a-plane AlGaN layer on the high-temperature undoped a-plane AlGaN layer;
step S7 of epitaxially growing an a-plane AlGaN multi-quantum well layer on the n-type doped a-plane AlGaN layer;
step S8 is to epitaxially grow an electronic barrier layer on the a-plane AlGaN multi-quantum well layer;
step S9 epitaxially growing a p-type doped AlGaN layer on the electron blocking layer;
step S10 epitaxially grows a p-type doped GaN layer on the p-type doped AlGaN layer.
In some embodiments, in step S2, a low-temperature AlN layer is grown on the silicon carbide substrate by metal organic chemical vapor deposition, under the following process conditions: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1050-1200 ℃, the beam ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S3, a metal organic chemical vapor deposition method is used to grow a high temperature AlN layer on the low temperature AlN layer, and the process conditions are as follows: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S4, a low-temperature a-plane AlGaN layer is grown on the high-temperature AlN layer by using a metal organic chemical vapor deposition method under the following process conditions: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1050-1200 ℃, the beam ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S5, a high-temperature undoped a-plane AlGaN layer is grown on the low-temperature a-plane AlGaN layer by using a metal organic chemical vapor deposition method under the following process conditions: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S6, an n-type doped a-plane AlGaN layer is grown on the high-temperature undoped a-plane AlGaN layer by metal organic chemical vapor deposition under the following process conditions: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h; the n-type doped AlGaN layer is doped with Si with the doping concentration of 1 multiplied by 1017～1×1020cm-3。
In some embodiments, in step S7, Al is grown on the n-type doped a-plane AlGaN layer for 7-10 periods by metal organic chemical vapor deposition0.1Ga0.9N well layer/Al0.25Ga0.75N base layers, the process conditions are as follows: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S8, Al is grown on the a-plane AlGaN multi-quantum well layer using a metal organic chemical vapor deposition method0.2Ga0.8The process conditions of the N electron blocking layer are as follows: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S9, a p-type doped AlGaN layer is grown on the electron blocking layer by metal organic chemical vapor deposition under the following process conditions: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
In some embodiments, in step S10, a p-type doped GaN layer is grown on the p-type doped AlGaN layer by metal organic chemical vapor deposition under the following process conditions: the pressure of the reaction chamber is 50-300 torr, the temperature of the silicon carbide substrate is 1200-1360 ℃, the beam current ratio V/III is 3000-5000, and the growth rate is 2-4 mu m/h.
The epitaxial structure of the embodiment of the invention fundamentally eliminates the strong polarization problem in the c-plane polar AlGaN-based material, eliminates the self-polarization in the LED, ensures that electrons and holes in an active region are easier to generate radiative recombination, improves the quantum efficiency in the ultraviolet LED, and improves the luminescence of the ultraviolet LED; the ultraviolet LED epitaxial wafer provided by the embodiment of the invention can effectively reduce the formation of dislocation, improve the radiation recombination efficiency of carriers, and can be used for preparing an ultraviolet LED with high heat conductivity, high electric conductivity and high light-emitting property; the preparation process of the embodiment of the invention is simple, has repeatability and can realize large-scale production and application.
The above-disclosed features are not intended to limit the scope of practice of the present disclosure, and therefore, all equivalent variations that are described in the claims of the present disclosure are intended to be included within the scope of the claims of the present disclosure.
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