CN116682916B - Multi-quantum well layer, preparation method thereof, epitaxial wafer and light-emitting diode - Google Patents
Multi-quantum well layer, preparation method thereof, epitaxial wafer and light-emitting diode Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a multiple quantum well layer and a preparation method thereof, an epitaxial wafer and a light-emitting diode, wherein the multiple quantum well layer comprises a quantum well layer, a cap layer and a quantum barrier layer which are periodically stacked; the quantum well layer is an AlScN layer, the cap layer is an AlSiN layer, and the quantum barrier layer is an AlN layer. The invention solves the problems of low light extraction efficiency of the LED and low luminous efficiency of the LED caused by low electron hole radiation recombination efficiency in the multi-quantum well in the prior art.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a multiple quantum well layer, a preparation method thereof, an epitaxial wafer and a light-emitting diode.
Background
In the past ten years, the AlGaN material has been paid attention to because of the great application potential in ultraviolet Light electric devices, and ultraviolet LEDs (Light-Emitting diodes, LEDs for short) have the characteristics of high photon energy, short wavelength, small volume, low power consumption, long service life, environmental friendliness and the like, and have wide application in the fields of high-color-rendering-index white Light illumination, high-density optical data storage, sensors, lithography, air purification, environmental protection and the like.
Many technical difficulties faced by the development of AlGaN-based ultraviolet LEDs, such as the small effective mass of the electrons themselves, and high mobility, result in many electrons that easily spill over to the P-layer through the quantum well; for AlGaN materials with high Al components, the defect density is higher, the crystal quality of an epitaxial layer is poor, and compared with GaN materials, the AlGaN materials with high Al components are more difficult to dope in N type or P type, especially the doping of P type AlGaN is more troublesome, the activation efficiency of a dopant Mg is low, the hole is insufficient, and the radiation recombination efficiency is reduced; in addition, the quantum efficiency in the AlGaN-based ultraviolet LED is relatively lower than that of a blue-green light emitting diode, although the preparation of the deep ultraviolet LED can be realized by adjusting the Al component of the AlGaN material of the light emitting layer, as the Al component is gradually increased, the alloy scattering is also enhanced, so that the light emitting efficiency is relatively lower, and the performance of the ultraviolet light emitting diode is severely limited. In order to improve the quantum efficiency of ultraviolet LEDs, it is necessary to prepare highly conductive p-type and n-type AlGaN materials and epitaxial layer structures of high crystal quality. Therefore, how to increase the luminous efficiency of the ultraviolet light emitting diode is a hot spot of industry research.
At present, the internal quantum efficiency of an AlGaN-based ultraviolet LED is relatively lower than that of a blue-green light emitting diode, because the blue-green light LED epitaxial structure is composed of InGaN/GaN, the ultraviolet LED epitaxial layer is composed of GaN/AlGaN, the ultraviolet light absorption is serious, and alloy scattering is also enhanced along with the gradual increase of Al components, the light emitting mode of the ultraviolet LED is changed from a transverse magnetic field mode to a transverse electric field mode, namely, the longitudinal light emitting is changed into the transverse light emitting mode, so that the light extraction efficiency of the ultraviolet LED is reduced; in addition, the electron hole radiation recombination efficiency in the ultraviolet LED quantum well is low, and finally the LED luminous efficiency is low.
Disclosure of Invention
Based on the above, the invention aims to provide a multiple quantum well layer, a preparation method thereof, an epitaxial wafer and a light-emitting diode, and aims to solve the problems that the light extraction efficiency of the LED in the prior art is reduced, and the electron hole radiation recombination efficiency in the quantum well is low, so that the light-emitting efficiency is low.
The embodiment of the invention is realized as follows:
on one hand, the embodiment of the invention provides a multiple quantum well layer, which is characterized by comprising a quantum well layer, a cap layer and a quantum barrier layer which are periodically stacked;
the quantum well layer is an AlScN layer, the cap layer is an AlSiN layer, and the quantum barrier layer is an AlN layer.
In addition, according to the multiple quantum well layer proposed above, at least the following additional technical features may be provided:
further, in a single period, the thickness of the quantum well layer is 2nm-4nm, the thickness of the cap layer is 0.5 nm-1 nm, and the thickness of the quantum barrier layer is 8nm-15 nm.
Further, the Si doping concentration of the cap layer is 0.5X10 in a single period 18 cm -3 -2×10 18 cm -3 。
Further, the Al component of the quantum well layer is 65% -85%, and the Sc component is 15% -35%.
Further, the growth period of the quantum well layer, the cap layer and the quantum barrier layer is 5-12.
In another aspect, an embodiment of the present invention provides a method for preparing a multiple quantum well layer, which is used for preparing the multiple quantum well layer described in any one of the foregoing, the method including:
introducing a source and a carrier gas required for growth;
sequentially growing a quantum well layer, a cap layer and a quantum barrier layer according to a preset period to form a multi-quantum well layer;
the quantum well layer is an AlScN layer, the cap layer is an AlSiN layer, and the quantum barrier layer is an AlN layer.
Further, in the preparation method of the multiple quantum well layer, the growth temperature of the quantum well layer, the cap layer and the quantum barrier layer is 1000-1200 ℃.
Further, in the preparation method of the multiple quantum well layer, the growth pressure of the quantum well layer is 30 Torr-75 Torr, and the growth pressures of the cap layer and the quantum barrier layer are both 30 Torr-75 Torr.
In still another aspect, an embodiment of the present invention provides an epitaxial wafer, including the multiple quantum well layer described in any one of the foregoing, where the epitaxial wafer further includes a substrate, a buffer layer, an undoped AlGaN layer, an N-type doped AlGaN layer, an electron blocking layer, a P-type doped AlGaN layer, and a contact layer;
the buffer layer, the undoped AlGaN layer, the N-type doped AlGaN layer, the multiple quantum well layer, the electron blocking layer, the P-type doped AlGaN layer and the contact layer are sequentially laminated on the substrate.
In still another aspect, an embodiment of the present invention provides a light emitting diode including the epitaxial wafer described above.
Compared with the prior art, the embodiment of the invention has at least the following beneficial effects:
the AlScN/AlSiN/AlN periodic structure is used as a multi-quantum well structure, wherein an AlScN layer is a quantum well layer, an AlSiN layer is a cap layer, and an AlN layer is a quantum barrier layer. Because GaN/AlGaN (or AlGaN/AlGaN) absorbs ultraviolet light in a traditional ultraviolet LED quantum well and polarization effect between well barriers causes low electron hole radiation recombination efficiency, so that the luminous efficiency of the ultraviolet LED is reduced, alN absorbs ultraviolet light very little, sc is introduced into the AlN quantum well, piezoelectric polarization charge density is increased, unbalanced holes are caused to be injected into the quantum well, the radiation recombination efficiency of electron holes is improved, the luminous efficiency of the ultraviolet LED is finally improved, in order to avoid the situation that the AlScN surface is rough when Sc is introduced into the AlN, an AlSiN cap layer is added between an AlScN well layer and an AlN barrier layer, the interface roughness of the well barrier can be reduced, and finally the luminous efficiency of the LED is improved.
Drawings
Fig. 1 is a schematic structural diagram of an epitaxial wafer according to an embodiment of the present invention;
FIG. 2 is a flow chart of a method for fabricating a multi-quantum well layer according to an embodiment of the invention;
the invention will be further described in the following detailed description in conjunction with the above-described figures.
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.
Aiming at the problems that the existing LED is low in luminous efficiency due to the fact that the light extraction efficiency is reduced and the electron hole radiation recombination efficiency in a quantum well is low, the embodiment of the invention provides a multi-quantum well layer, a preparation method thereof, an epitaxial wafer and a light-emitting diode, wherein:
referring to fig. 1, a schematic structure of an epitaxial wafer according to an embodiment of the present invention is shown, where the epitaxial wafer includes:
a substrate 1, a buffer layer 2, an undoped AlGaN layer 3, an N-type doped AlGaN layer 4, a multiple quantum well layer 5, an electron blocking layer 6, a P-type doped AlGaN layer 7, and a contact layer 8, which are sequentially stacked on the substrate 1.
The multiple quantum well layer 5 includes a quantum well layer 51, a cap layer 52, and a quantum barrier layer 53, which are periodically stacked.
Specifically, the quantum well layer 51 is an AlScN layer, the cap layer 52 is an AlSiN layer, and the quantum barrier layer 53 is an AlN layer.
It will be appreciated that a periodic AlScN/AlSiN/AlN is used as the multiple quantum well structure, where AlScN is the quantum well layer 51, alSiN is the cap layer 52, and AlN is the quantum barrier layer 53. Because GaN/AlGaN (or AlGaN/AlGaN) absorbs ultraviolet light in a traditional ultraviolet LED quantum well and polarization effect between well barriers causes low electron hole radiation recombination efficiency, so that the luminous efficiency of the ultraviolet LED is reduced, alN absorbs ultraviolet light very little, sc is introduced into the AlN quantum well, piezoelectric polarization charge density is increased, unbalanced holes are caused to be injected into the quantum well, the radiation recombination efficiency of electron holes is improved, the luminous efficiency of the ultraviolet LED is finally improved, in order to avoid the situation that the AlScN surface is rough when Sc is introduced into the AlN, an AlSiN cap layer is added between an AlScN well layer and an AlN barrier layer, the interface roughness of the well barrier can be reduced, and finally the luminous efficiency of the LED is improved.
Further, the thickness of the quantum well layer 51 is 2nm-4nm, the thickness of the cap layer 52 is 0.5 nm-1 nm, and the thickness of the quantum barrier layer 53 is 8nm-15nm, so that the crystal quality of the multi-quantum well layer 5 is ensured; the Si doping concentration of the cap layer 52 is 0.5X10 18 cm -3 -2×10 18 cm -3 Reducing the roughness of the well barrier interface; the Al component of the quantum well layer 51 is 65% -85%, the Sc component is 15% -35%, the piezoelectric polarization charge density is increased, unbalanced holes are caused to be injected into the quantum well, and the radiation recombination efficiency of electron holes is improved; the growth period of the quantum well layer 51, the cap layer 52 and the quantum barrier layer 53 is 5-12, so that the crystal quality of the multi-quantum well layer 5 is ensured.
The structure of the epitaxial wafer except for the other layers of the multiple quantum well layer 5 and the corresponding growth process in the embodiment of the present invention are as follows:
wherein, the substrate 1 is mainly made of sapphire Al 2 O 3 A substrate;
wherein the buffer layer 2 is an AlN layer, the thickness can be 15nm-50nm, the buffer layer is grown on the substrate 1 by PVD, the growth temperature is 400-650 ℃, the sputtering power is 2000-4000W, and the pressure is 1-10 torr;
in addition, the buffer layer 2 can be subjected to in-situ annealing treatment in the hydrogen atmosphere in MOCVD, the temperature is 1000-1200 ℃, the pressure range is 150Torr-500Torr, the time is 5-10 minutes, wherein after annealing is finished, the temperature is adjusted to 1050-1200 ℃, the undoped AlGaN layer 3 with the thickness of 1.0-3.0 micrometers is grown, the growth pressure is 50Torr-100Torr, and the Al component is 30-80%;
wherein, after the undoped AlGaN layer 3 is grown, a layer of Si doped is grownThe thickness of the doped N-type doped AlGaN layer 4 is 1.0-3.0 micrometers, the growth temperature is 1100-1200 ℃, the pressure is 100 Torr-300 Torr, and the Si doping concentration is 1 multiplied by 10 19 cm -3 ~1×10 20 cm -3 ；
Wherein, after the growth of the N-type doped AlGaN layer 4 is finished, a multi-quantum well layer 5 is grown;
the electron blocking layer 6 of the AlGaN layer grows after the growth of the multiple quantum well layer 5 is finished, the growth temperature is 1000-1100 ℃, the growth pressure is 50-100 Torr, the growth thickness is 20-100 nm, and the Al component is 20-80%;
wherein, after the electron blocking layer 6 grows, a P-type doped AlGaN layer 7 is grown, the thickness is 30 nm-200 nm, the growth temperature is 1050-1150 ℃, the growth pressure is 50Torr-100Torr, and the doping concentration of Mg is 1 multiplied by 10 19 cm -3 ~1×10 20 cm -3 ；
Growing a contact layer 8 of the AlGaN layer on the P-type doped AlGaN layer 7, wherein the thickness is 10 nm-50nm, the growth temperature is 1000-1100 ℃, the growth pressure is 50Torr-100Torr, and the Al component is less than or equal to 30%;
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 minutes, and cooling to room temperature to finish epitaxial growth.
Wherein trimethylaluminum (TMAl), trimethylgallium or triethylgallium (TMGa or TEGa), triethylboron (TEB) are used as precursors of group iii sources, ammonia is used as precursors of group v sources, silane is used as precursors of N-type dopants, magnesium-cyclopentadienyl is used as precursors of P-type dopants, and nitrogen and hydrogen are used as carrier gases.
Referring to fig. 2, on the other hand, the method for preparing a multiple quantum well layer according to the embodiment of the present invention is used for preparing the multiple quantum well layer, and the method includes steps S10 to S11.
Step S10, supplying source and carrier gas required for growth.
Wherein Trimethylaluminum (TMAL) is an aluminum source, trimethylgallium or triethylgallium (TMGa or TEGa) is a gallium source, NH 3 Silane and magnesium-dicyclopentadiene as precursors of group III and V sources, respectivelyThe precursor of scandium (Sc) is tricyclopentadienyl scandium (Cp) 3 Sc），N 2 And H 2 As a carrier gas.
And S11, sequentially growing a quantum well layer, a cap layer and a quantum barrier layer according to a preset period to form a multi-quantum well layer.
The quantum well layer is an AlScN layer, the cap layer is an AlSiN layer, and the quantum barrier layer is an AlN layer.
Specifically, the growth temperature of the quantum well layer, the cap layer and the quantum barrier layer is 1000-1200 ℃, the growth pressure of the quantum well layer is 30 Torr-75 Torr, and the growth pressure of the cap layer and the quantum barrier layer is 30 Torr-75 Torr.
On the other hand, the light emitting diode provided by the embodiment of the invention comprises the epitaxial wafer.
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. 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.
Example 1
The first embodiment of the invention provides a preparation method of an epitaxial wafer, which comprises the following steps:
providing a substrate;
sequentially growing a buffer layer, an undoped AlGaN layer, an N-type doped AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type doped AlGaN layer and a contact layer;
the growing the multi-quantum well layer comprises sequentially growing the quantum well layer, the cap layer and the quantum barrier layer according to a preset period to form the multi-quantum well layer.
Wherein the quantum well layer is AlScN layer, the cap layer is AlSiN layer, the quantum barrier layer is AlN layer, the growth pressure of the multiple quantum well layer is 30torr, sc component in the quantum well layer is 30%, and Si doping concentration of the cap layer is 1×10 18 cm -3 。
Example two
The second embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the first embodiment in that:
the growth pressure of the multi-quantum well layer is 40torr.
Example III
The third embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the first embodiment in that:
the growth pressure of the multi-quantum well layer is 50torr.
Example IV
The fourth embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the first embodiment in that:
the growth pressure of the multi-quantum well layer is 60 torr.
Example five
The fifth embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the first embodiment in that:
the growth pressure of the multi-quantum well layer is 40torr, and the Sc component in the quantum well layer is 15%.
Example six
The sixth embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the method for preparing an epitaxial wafer in the first embodiment in that:
the growth pressure of the multi-quantum well layer is 40torr, and the Sc component in the quantum well layer is 20%.
Example seven
The seventh embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the first embodiment in that:
the growth pressure of the multi-quantum well layer is 40torr, and the Sc component in the quantum well layer is 35%.
Example eight
The eighth embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the method for preparing an epitaxial wafer in the first embodiment in that:
the growth pressure of the multi-quantum well layer is 40torr, and the Si doping concentration of the cap layer is 0.6X10 18 cm -3 。
Example nine
The eighth embodiment of the present invention also provides a method for preparing an epitaxial wafer, which is different from the method for preparing an epitaxial wafer in the first embodiment in that:
the growth pressure of the multi-quantum well layer is 40torr, and the Si doping concentration of the cap layer is 0.8X10 18 cm -3 。
For comparison with the above-described embodiments of the present invention, the following comparative examples are also presented.
Comparative example one
The first comparative example of the present invention also proposes an epitaxial wafer manufacturing method, which differs from the epitaxial wafer manufacturing method of the first example in that:
the multi-quantum well structure is an existing multi-quantum well structure, and no cap layer is arranged.
Please refer to the following table one, which shows parameters corresponding to the above embodiments one to nine and the comparative example one of the present invention.
List one
In practical application, the corresponding epitaxial wafers are prepared by adopting the preparation methods and parameters corresponding to the first embodiment to the ninth embodiment and the first comparative embodiment of the present invention, and performance tests are performed on the epitaxial wafers prepared in each embodiment and the epitaxial wafers prepared in the comparative embodiment, respectively, and the test data are shown in the following table two.
In order to ensure the reliability of the verification result, the first to ninth embodiments of the present invention and the first comparative example should have the same parameters except for the above parameters, for example, the manufacturing process and parameters of each layer of the epitaxial wafer should be kept consistent.
Watch II
As is apparent from the data in the first and second tables, the periodic AlScN/AlSiN/AlN is used as the multi-quantum well structure, wherein the AlScN layer is a quantum well layer, the AlSiN layer is a cap layer, and the AlN layer is a quantum barrier layer. Because GaN/AlGaN (or AlGaN/AlGaN) absorbs ultraviolet light in a traditional ultraviolet LED quantum well and polarization effect between well barriers causes low electron hole radiation recombination efficiency, so that the luminous efficiency of the ultraviolet LED is reduced, alN absorbs ultraviolet light very little, sc is introduced into the AlN quantum well, piezoelectric polarization charge density is increased, unbalanced holes are caused to be injected into the quantum well, the radiation recombination efficiency of electron holes is improved, the luminous efficiency of the ultraviolet LED is finally improved, in order to avoid the situation that the AlScN surface is rough when Sc is introduced into the AlN, an AlSiN cap layer is added between an AlScN well layer and an AlN barrier layer, the interface roughness of the well barrier can be reduced, and finally the luminous efficiency of the LED is improved.
In addition, as is obvious from the fifth to seventh embodiments, the light-emitting efficiency of the LED is obviously improved by the suitable Sc component, that is, the introduction of Sc into the quantum well of AlN increases the piezoelectric polarization charge density, which causes unbalanced hole injection into the quantum well, improves the radiative recombination efficiency of electron holes, and finally improves the light-emitting efficiency of the ultraviolet LED.
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 multi-quantum well layer is characterized by comprising a quantum well layer, a cap layer and a quantum barrier layer which are periodically stacked;
wherein the quantum well layer is AlScN layer, the cap layer is AlSiN layer, the quantum barrier layer is AlN layer, and the Si doping concentration of the cap layer is 0.5X10 18 cm -3 -2×10 18 cm -3 The quantum well layer comprises 65% -85% of Al and 15% -35% of Sc.
2. The multiple quantum well layer of claim 1, wherein the quantum well layer has a thickness of 2nm to 4nm, the cap layer has a thickness of 0.5nm to 1nm, and the quantum barrier layer has a thickness of 8nm to 15nm in a single period.
3. The multiple quantum well layer according to any one of claims 1to 2, wherein a growth period of the quantum well layer, the cap layer, and the quantum barrier layer is 5to 12.
4. A method for producing the multiple quantum well layer, characterized by being used for producing the multiple quantum well layer of any one of claims 1to 3, comprising:
introducing a source and a carrier gas required for growth;
sequentially growing a quantum well layer, a cap layer and a quantum barrier layer according to a preset period to form a multi-quantum well layer;
the quantum well layer is an AlScN layer, the cap layer is an AlSiN layer, and the quantum barrier layer is an AlN layer.
5. The method of claim 4, wherein the growth temperature of the quantum well layer, the cap layer and the quantum barrier layer is 1000 ℃ to 1200 ℃.
6. The method of producing a multiple quantum well layer according to claim 4 or 5, wherein the growth pressure of the quantum well layer is 30to 75Torr, and the growth pressures of the cap layer and the quantum barrier layer are both 30to 75Torr.
7. An epitaxial wafer, characterized in that the epitaxial wafer comprises the multi-quantum well layer of any one of claims 1to 3, and further comprises a substrate, a buffer layer, an undoped AlGaN layer, an N-type doped AlGaN layer, an electron blocking layer, a P-type doped AlGaN layer and a contact layer;
the buffer layer, the undoped AlGaN layer, the N-type doped AlGaN layer, the multiple quantum well layer, the electron blocking layer, the P-type doped AlGaN layer and the contact layer are sequentially laminated on the substrate.
8. A light-emitting diode comprising the epitaxial wafer of claim 7.
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