CN116565075A - Preparation method of deep ultraviolet light-emitting diode and deep ultraviolet light-emitting diode - Google Patents
Preparation method of deep ultraviolet light-emitting diode and deep ultraviolet light-emitting diode Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 49
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- 238000005530 etching Methods 0.000 claims abstract description 46
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- 239000002096 quantum dot Substances 0.000 claims abstract description 32
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000003491 array Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010410 layer Substances 0.000 description 159
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- 229910002704 AlGaN Inorganic materials 0.000 description 9
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/0004—Devices characterised by their operation
- H01L33/0008—Devices characterised by their operation having p-n or hi-lo junctions
- H01L33/0012—Devices characterised by their operation having p-n or hi-lo junctions p-i-n devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0093—Wafer bonding; Removal of the growth substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
- H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a preparation method of a deep ultraviolet light emitting diode and the deep ultraviolet light emitting diode, wherein the preparation method comprises the following steps: firstly transferring a bi-pass anodized aluminum template to the surface of one side, far away from a substrate, of a deep ultraviolet light-emitting diode epitaxial structure, secondly forming an anti-etching layer on the bi-pass anodized aluminum template, then stripping the bi-pass anodized aluminum template, etching the deep ultraviolet light-emitting diode epitaxial structure by taking the anti-etching layer as a mask, enabling a luminescent material layer in the deep ultraviolet light-emitting diode epitaxial structure to form a quantum dot array, and finally removing the anti-etching layer; according to the invention, the luminous material layer in the deep ultraviolet light-emitting diode epitaxial structure is prepared into the quantum dot array by adopting the bi-pass anodic aluminum oxide template, so that the deep ultraviolet light-emitting diode can greatly improve the light output power.
Description
Technical Field
The invention relates to the field of semiconductor photoelectricity, in particular to a preparation method of a deep ultraviolet light emitting diode and the deep ultraviolet light emitting diode.
Background
In the deep ultraviolet light emitting diode, alGaN is a direct band gap wide forbidden band semiconductor material, the forbidden band width of the AlGaN can be changed by changing the doping amount of Al element (GaN with the forbidden band width of 3.4eV is continuously adjustable to AlN with the forbidden band width of 6.2 eV), so that light emission in a spectrum range of 365nm to 200nm is realized, and the AlGaN has excellent performances of stable physicochemical properties, high temperature resistance, radiation resistance and the like, and is the best candidate material for preparing a semiconductor deep ultraviolet light source device at present. Moreover, compared with the traditional mercury lamp, the AlGaN-based deep ultraviolet light emitting diode has the advantages of small volume, low power consumption, environmental protection, safety, high integration level and the like, and is expected to be breakthrough progress and huge application in the next years, and more attention and importance are paid in recent years.
However, the current deep ultraviolet light emitting diode based on AlGaN material still has low light emitting efficiency, because AlGaN material is wurtzite structure, the vertical lattice of the structure along the c direction has spontaneous polarization and piezoelectric polarization, and the polarization forms a large polarized electric field inside the material. The electric field generated by polarization can separate the wave functions of electrons and holes, and reduce the overlapping rate of the wave functions, thereby reducing the luminous efficiency of the ultraviolet light-emitting diode. The piezoelectric polarization of the AlGaN material is related to the internal stress of the film, and when the material is stressed, the c/a value (the ratio of the vertical lattice constant to the lattice constant of the bottom surface) changes, so that the polarization intensity inside the material is affected.
Therefore, a method for manufacturing a deep ultraviolet light emitting diode and a deep ultraviolet light emitting diode are needed to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a preparation method of a deep ultraviolet light-emitting diode and the deep ultraviolet light-emitting diode, which are used for solving the technical problem that the light-emitting efficiency of the deep ultraviolet light-emitting diode in the prior art is low.
In order to solve the technical problems, the invention firstly provides a preparation method of a deep ultraviolet light emitting diode, which comprises the following steps:
s10, transferring a double-pass anodic aluminum oxide template to the surface of one side, far away from the substrate, of a deep ultraviolet light-emitting diode epitaxial structure;
s20, forming an etching-resistant layer on the double-pass anodic aluminum oxide template;
s30, stripping the double-pass anodized aluminum template;
s40, etching the deep ultraviolet light-emitting diode epitaxial structure by taking the etching-resistant layer as a mask, so that a luminescent material layer in the deep ultraviolet light-emitting diode epitaxial structure forms a quantum dot array 101;
s50, removing the anti-etching layer.
In the method for manufacturing the deep ultraviolet light emitting diode provided by the embodiment of the invention, in step S10, the deep ultraviolet light emitting diode epitaxial structure comprises a substrate, an intrinsic layer, an electron injection layer, a quantum well active layer, an electron blocking layer and a hole injection layer which are stacked from bottom to top.
In the preparation method of the deep ultraviolet light emitting diode provided by the embodiment of the invention, in the step S10, the thickness range of the double-pass anodized aluminum template is 10-500 nm, and the aperture range of the double-pass anodized aluminum template is 2-50 nm.
In the method for manufacturing a deep ultraviolet light emitting diode provided by the embodiment of the invention, in step S20, the material of the etching resistant layer includes at least one of gold, nickel, silicon oxide or silicon nitride.
In the method for manufacturing the deep ultraviolet light emitting diode provided by the embodiment of the invention, in step S30, the double-pass anodized aluminum template is peeled off by a high-temperature adhesive tape or an electroplating adhesive tape.
In the method for manufacturing a deep ultraviolet light emitting diode provided by the embodiment of the invention, in step S40, the light emitting material layer includes an electron injection layer, a quantum well active layer, an electron blocking layer and a hole injection layer.
In the method for manufacturing a deep ultraviolet light emitting diode provided by the embodiment of the present invention, step S50 further includes: and soaking the epitaxial structure of the deep ultraviolet light-emitting diode by using a strong alkaline solution.
In the method for manufacturing a deep ultraviolet light emitting diode provided by the embodiment of the present invention, step S50 further includes: an N-type electrode is disposed on the electron injection layer, and a P-type electrode is disposed on the hole injection layer.
Correspondingly, the invention also provides a deep ultraviolet light-emitting diode which is prepared by the preparation method of any one of the deep ultraviolet light-emitting diodes, wherein the deep ultraviolet light-emitting diode comprises a substrate, an intrinsic layer, an electron injection layer, a quantum well active layer, an electron blocking layer and a hole injection layer which are laminated from bottom to top;
the electron injection layer, the quantum well active layer, the electron blocking layer and the hole injection layer are all quantum dot arrays 101.
In the deep ultraviolet light emitting diode provided by the embodiment of the invention, the particle size range of the quantum dots in the quantum dot array 101 is 2-50 nm.
The beneficial effects of the invention are as follows: different from the prior art, the invention provides a preparation method of a deep ultraviolet light emitting diode and the deep ultraviolet light emitting diode, wherein the preparation method comprises the following steps: firstly transferring a bi-pass anodized aluminum template to the surface of one side, far away from a substrate, of a deep ultraviolet light-emitting diode epitaxial structure, secondly forming an anti-etching layer on the bi-pass anodized aluminum template, then stripping the bi-pass anodized aluminum template, etching the deep ultraviolet light-emitting diode epitaxial structure by taking the anti-etching layer as a mask, enabling a luminescent material layer in the deep ultraviolet light-emitting diode epitaxial structure to form a quantum dot array, and finally removing the anti-etching layer; according to the invention, the luminous material layer in the deep ultraviolet light-emitting diode epitaxial structure is prepared into the quantum dot array by adopting the bi-pass anodic aluminum oxide template, so that on one hand, the stress of a deep ultraviolet active region is released by etching, the polarization intensity is reduced, the quantum confinement Stark effect is remarkably relieved, and the radiation recombination efficiency of the deep ultraviolet light-emitting diode is improved; on the other hand, the luminescent material layer of the quantum dot array structure can limit the movement of carriers in three spatial dimensions, so that the carrier injection efficiency of the deep ultraviolet light-emitting diode is improved; in addition, the quantum dot structure also improves the light extraction efficiency of the deep ultraviolet light emitting diode in an active region, and the three comprehensively realize the larger improvement of the light output power of the deep ultraviolet light emitting diode.
Drawings
FIG. 1 is a flowchart of a method for manufacturing a deep ultraviolet light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of each step in a preparation method of a deep ultraviolet light emitting diode according to an embodiment of the present invention;
FIG. 3 is a schematic cross-sectional view of a deep ultraviolet LED according to an embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of a deep ultraviolet light emitting diode (sample B) according to an embodiment of the present invention after a bi-pass anodized aluminum template is transferred during the preparation process;
fig. 5 is a graph showing the variation of light output power with current for two different configurations of deep ultraviolet leds.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Referring to fig. 1 to 3, fig. 1 is a flowchart illustrating a method for manufacturing a deep ultraviolet light emitting diode according to an embodiment of the present invention; fig. 2 is a schematic structural diagram of each step in a preparation method of a deep ultraviolet light emitting diode according to an embodiment of the present invention; fig. 3 is a schematic cross-sectional structure of a deep ultraviolet light emitting diode according to an embodiment of the present invention.
Specifically, the luminescent material layer 13 in the deep ultraviolet light emitting diode epitaxial structure 100 is prepared into the quantum dot array 101 by adopting the bi-pass anodic aluminum oxide template 200, on one hand, the stress of a deep ultraviolet active region is released by etching, the polarization intensity is reduced, the Stark effect of quantum restriction is obviously relieved, thereby improving the radiation recombination efficiency of the deep ultraviolet light emitting diode, on the other hand, the luminescent material layer 13 in the quantum dot array 101 structure can restrict the movement of carriers in three spatial dimensions, thereby improving the carrier injection efficiency of the deep ultraviolet light emitting diode, and in addition, the quantum dot structure also improves the light extraction efficiency of the deep ultraviolet light emitting diode in the active region, so that the three comprehensively realize the great improvement of the light output power of the deep ultraviolet light emitting diode.
The technical solutions of the present application will now be described with reference to specific embodiments.
Referring to fig. 1, fig. 1 is a flowchart of a method for manufacturing a deep ultraviolet light emitting diode according to an embodiment of the present invention; the preparation method of the deep ultraviolet light-emitting diode comprises the following steps:
s10, the bi-pass anodized aluminum template 200 is transferred onto a surface of the deep ultraviolet led epitaxial structure 100 on a side far from the substrate 11.
Specifically, step S10 further includes:
s101, growing a deep ultraviolet light emitting diode epitaxial structure 100 by adopting a metal-organic chemical vapor deposition (MOCVD) technology, as shown in 2a of FIG. 2 and FIG. 3; the deep ultraviolet light emitting diode epitaxial structure 100 includes a substrate 11, an intrinsic layer 12, an electron injection layer 131, a quantum well active layer 132, an electron blocking layer 133, and a hole injection layer 134, which are stacked from bottom to top.
Specifically, the substrate 11 is a sapphire material; sapphire materials have many advantages: firstly, the production technology of the sapphire material is mature, and the quality of the device is good; secondly, the sapphire has good stability and can be applied to a high-temperature growth process; finally, the sapphire has high mechanical strength and is easy to process and clean. Therefore, most processes typically use sapphire as the substrate 11.
Specifically, the intrinsic layer 12 includes a low temperature buffer layer disposed on the substrate 11 and an aluminum nitride intrinsic layer disposed on the low temperature buffer layer; the low-temperature buffer layer is made of aluminum nitride, the growth temperature of the low-temperature buffer layer is in the range of 400-800, and the thickness of the low-temperature buffer layer is in the range of 10-50 nm; the intrinsic layer of aluminum nitride is aluminum nitride, the growth temperature is in the range of 1200-1400 nm, and the thickness is in the range of 500-4000 nm.
Specifically, the material of the electron injection layer 131 is N-type doped aluminum nitrideGallium material with SiH dopant 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the composition of aluminum element in the electron injection layer 131 ranges from 20% to 90%, the thickness of the electron injection layer 131 ranges from 500nm to 4000nm, and the growth temperature of the electron injection layer 131 ranges from 900 to 1200.
Specifically, the quantum well active layer 132 is disposed on the electron injection layer 131, and the growth temperature of the quantum well active layer 132 ranges from 900 to 1200.
Specifically, the quantum well active layer 132 is an AlGaN multi-layer periodic structure which is periodically arranged, each periodic structure includes a barrier layer and a potential well layer, each potential well layer is inserted between two adjacent barrier layers, the materials of the barrier layer and the potential well layer are aluminum gallium nitride, and the barrier layer and the potential well layer are different only in the content of aluminum components;
further, the number of cycles of the entire quantum well active layer 132 is 1 or more and 10 or less; the thickness range of the potential well layer is 0.5 nm-15 nm, and the mass percentage range of the aluminum component in the potential well layer is 15% -70%; the thickness of the barrier layer ranges from 1nm to 20nm, and the mass percentage of the aluminum component in the barrier layer ranges from 30% to 95%.
In the embodiment of the present invention, the barrier layer in the quantum well active layer 132 adopts SiH 4 As an N-type dopant, the growth pressure is 20-100torr.
Specifically, the electron blocking layer 133 is disposed on the quantum well active layer 132, and a growth temperature of the electron blocking layer 133 ranges from 700 to 1100; the electron blocking layer 133 is a single-layer AlGaN structure, and the electron blocking layer 133 is a P-type doped semiconductor material, which uses magnesium dicyclopentadiene as a P-type dopant.
Further, the percentage of aluminum element in the electron blocking layer 133 ranges from 45% to 100%, and the thickness of the electron blocking layer 133 ranges from 1nm to 100nm.
Specifically, the hole injection layer 134 is disposed on the electron blocking layer 133, and the growth temperature of the hole injection layer 134 ranges from 700 to 1100; the material of the hole injection layer 134 is P-type doped aluminum gallium nitride material, the percentage of the aluminum component content in the hole injection layer 134 ranges from 20% to 60%, the thickness of the hole injection layer 134 ranges from 1nm to 100nm, and the hole injection layer 134 adopts magnesium cyclopentadienyl as a dopant.
In the embodiment of the present invention, the electron injection layer 131, the quantum well active layer 132, the electron blocking layer 133 and the hole injection layer 134 form the light emitting material layer 13 of the deep ultraviolet light emitting diode epitaxial structure 100, electrons are input into the quantum well active layer 132 through the electron injection layer 131, and holes are input into the quantum well active layer 132 through the hole injection layer 134, so that electrons and holes are recombined in the quantum well active layer 132 to emit light.
S102, the bi-pass anodized aluminum template 200 is transferred onto a surface of the deep ultraviolet led epitaxial structure 100 on a side far from the substrate 11.
Specifically, step S102 further includes:
first, the deep ultraviolet light emitting diode epitaxial structure 100 is subjected to a hydrophilic treatment using a piranha etching solution, and then the ultra-thin double-pass anodized aluminum template 200 is transferred onto a surface of the deep ultraviolet light emitting diode epitaxial structure 100 away from the substrate 11 (i.e., the double-pass anodized aluminum template 200 is in contact with the hole injection layer 134) in an acetone solution, as shown in fig. 2 b.
Specifically, the bi-pass anodized aluminum template 200 is a transparent template having a nano-pore size, uniform pore size and highly ordered distribution, and can synthesize nano-materials having various structures (tubes, rods, wires, etc.) and good dispersibility. The strength of the two-pass anodized aluminum template 200 depends on the porosity and template thickness, generally the lower the porosity, the higher the strength; the thickness of the template is increased, and the strength is increased.
Specifically, the thickness range of the double-pass anodized aluminum template 200 provided by the invention is 10-500 nm, and the aperture range is 5-100 nm.
Specifically, the deep ultraviolet light emitting diode epitaxial structure 100 is subjected to hydrophilic treatment by using the piranha etching solution, so that the bi-pass anodized aluminum template 200 can be better attached to the deep ultraviolet light emitting diode epitaxial structure 100.
S20, an etching resist 300 is formed on the bi-pass anodized aluminum template 200.
Specifically, S20 further includes:
and depositing an anti-etching layer 300 on the surface of the double-pass anodized aluminum template 200 by adopting technologies such as chemical vapor deposition, electron beam evaporation or magnetron sputtering, and the like, wherein the anti-etching layer 300 completely fills a plurality of nano holes in the double-pass anodized aluminum template 200.
Specifically, the material of the etching resist layer 300 includes at least one of gold, nickel, silicon oxide, or silicon nitride; the thickness of the etch resistant layer 300 is 1 to 10 times the pore size of a single nanopore in the ultra-thin bi-pass anodized aluminum template 200.
S30, stripping the double-pass anodized aluminum template 200.
Specifically, S30 further includes:
removing the double-pass anodized aluminum template 200 on the surface of the deep ultraviolet light-emitting diode epitaxial structure 100 by adopting a high-temperature adhesive tape or an electroplating adhesive tape; wherein a portion of the etch resist 300 located on the surface of the bi-pass anodized aluminum template 200 is removed following the bi-pass anodized aluminum template 200, only the etch resist 300 located in the plurality of nano-holes of the bi-pass anodized aluminum template 200 remains, as shown in fig. 2 c.
And S40, etching the deep ultraviolet light emitting diode epitaxial structure 100 by taking the etching resistance layer 300 as a mask, so that the light emitting material layer 13 in the deep ultraviolet light emitting diode epitaxial structure 100 forms the quantum dot array 101.
Specifically, S40 further includes:
the deep ultraviolet light emitting diode epitaxial structure 100 is etched by using the anti-etching layer 300 as a mask and adopting an Inductively Coupled Plasma (ICP) process, so that the light emitting material layer 13 in the deep ultraviolet light emitting diode epitaxial structure 100 forms the quantum dot array 101. Even though the electron injection layer 131, the quantum well active layer 132, the electron blocking layer 133, and the hole injection layer 134 all form the quantum dot array 101, as shown in 2d of fig. 2.
Specifically, the deep ultraviolet light emitting diode epitaxial structure 100 is etched using an Inductively Coupled Plasma (ICP) process to an etch depth of 20-2000nm.
And S50, removing the anti-etching layer 300.
Specifically, S50 further includes:
when the material of the etching resist layer 300 is silicon or silicon dioxide, removing the etching resist layer 300 by using hydrofluoric acid solution; when the material of the etching resist layer 300 is a metal material, the etching resist layer 300 is removed using an aqua regia solution, as shown in fig. 2 e.
In the embodiment of the invention, when the deep ultraviolet light emitting diode epitaxial structure 100 is etched by adopting an Inductively Coupled Plasma (ICP) process, the surface of the deep ultraviolet light emitting diode epitaxial structure 100 generates lattice defects due to ion bombardment in the plasma etching process, thereby forming a deep energy level center and generating compensation and composite effects. The combination of ion tunneling energy and rapid defect diffusion results in deep ultraviolet light emitting diode epitaxial structure 100 emission etching damage; wherein, the damage layer caused by etching can reach 100nm at most.
Therefore, after the step of removing the anti-etching layer 300 is completed, the deep ultraviolet light emitting diode epitaxial structure 100 needs to be soaked in a strong alkaline solution (such as KOH solution) in order to remove the damage caused by the plasma etching. This is mainly due to the fact that KOH reacts with defects at the lattice interface, thereby compensating for etching damage.
In the embodiment of the present invention, after the step of soaking the deep ultraviolet light emitting diode epitaxial structure 100 in the strong alkaline solution, the SOG solution (spin-on glass) is further required to be rotationally coated on the outer surface of the deep ultraviolet light emitting diode epitaxial structure 100, so that the outer surface of the deep ultraviolet light emitting diode epitaxial structure 100 can be locally flattened; on the other hand, the SOG solution may also serve as a bonding material for bonding the electrode material.
Specifically, the SOG solution consists of silanol and methyl polymer dissolved in an alcohol/acetone solvent.
In the embodiment of the present invention, after the step of rotationally coating the SOG solution on the outer surface of the deep ultraviolet light emitting diode epitaxial structure 100 is completed, the N-type electrode 14 and the P-type electrode 15 are prepared on the surface of the deep ultraviolet light emitting diode epitaxial structure 100 by using a conventional light emitting diode preparation process, as shown in fig. 2 f.
Specifically, a portion of the quantum dot array 101 of the deep ultraviolet light emitting diode epitaxial structure 100 corresponding to the N-type region is removed by an etching process, so that the N-type electrode 14 is prepared on the electron injection layer 131; thereafter, the P-type electrode 15 is prepared on the hole injection layer 134.
Further, a step structure is formed between the electron injection layer 131 and the quantum well active layer 132, the area of the electron injection layer 131 is larger than that of the quantum well active layer 132, the P-type electrode 15 is disposed on the hole injection layer 134, and the N-type electrode 14 is disposed at the step structure of the electron injection layer 131.
In the embodiment of the invention, the depth of the SOG solution for soaking the outer surface of the deep ultraviolet light emitting diode epitaxial structure 100 is 10-30nm lower than the etching depth of the deep ultraviolet light emitting diode epitaxial structure 100; this is to expose the P-type region at the top of the deep uv led epitaxial structure 100to prepare the P-type electrode 15; because SOG solutions are non-conductive.
Accordingly, referring to fig. 2 and 4, the present invention further provides a deep ultraviolet light emitting diode, which is prepared by the method for preparing a deep ultraviolet light emitting diode according to any one of the above, wherein the deep ultraviolet light emitting diode comprises a substrate 11, an intrinsic layer 12, an electron injection layer 131, a quantum well active layer 132, an electron blocking layer 133 and a hole injection layer 134 which are stacked from bottom to top;
the electron injection layer 131, the quantum well active layer 132, the electron blocking layer 133, and the hole injection layer 134 are all quantum dot arrays 101.
Specifically, the particle size of the quantum dots in the quantum dot array 101 ranges from 2 to 50nm (the particle size of the quantum dots in the quantum dot array 101 is the same as the pore size of the double-pass anodized aluminum template 200).
In the embodiment of the invention, after the preparation of the deep ultraviolet light emitting diode is completed, the two deep ultraviolet light emitting diodes are compared with the deep ultraviolet light emitting diode in the prior art, and under the action of different driving currents (mA), the light output powers (mW) corresponding to the two deep ultraviolet light emitting diodes are respectively tested.
Comparative example (sample a):
the deep ultraviolet light emitting diode provided in the comparative example was prepared by a conventional process, and the film structure thereof from the substrate 11 to the hole injection layer 134 was substantially the same in structure and materials, as follows:
a substrate 11 made of sapphire;
an intrinsic layer 12 made of aluminum nitride and having a thickness of 2000nm;
the electron injection layer 131 is made of Si-doped aluminum gallium nitride material, wherein the Al component in the electron injection layer 131 accounts for 50% of the mass of the electron injection layer 131, and the thickness of the electron injection layer is 2500nm;
in the quantum well active layer 132, the number of cycles is 5, the thickness of the barrier layer is 10nm, the content of Al component in the barrier layer is 0.55, the content of Al component in the potential well layer is 0.4, and the thickness of the potential well layer is 5nm;
the electron blocking layer 133 is a single-layer AlGaN structure, has a thickness of 50nm, and has an Al component content of 0.6;
the material of the hole injection layer 134 is P-type doped aluminum gallium nitride material, the content of aluminum component in the hole injection layer 134 is 0.4, the thickness is 50nm, and magnesium oxide is adopted as P-type dopant.
Further, the N-type electrodes 14 of the same material are disposed on the electron injection layer 131 and the P-type electrodes of the same material are disposed on the hole injection layer 134 by a conventional method, so as to form a complete epitaxial chip structure, and the specific process is not described herein. Wherein the N-type electrode 14 and the P-type electrode are both made of multi-layer composite metal materials.
Inventive example (sample B):
the embodiment of the invention is prepared by adopting the preparation method of the deep ultraviolet light-emitting diode, wherein the thickness of the ultrathin double-pass anodic aluminum oxide template 200 used in the process of preparing the sample B is 100nm, and the pore size is 20nm. The material of the evaporated anti-etching layer 300 is gold, and the thickness is 80nm; the depth of the plasma etch was 500nm. The materials of the other film layers of the embodiment of the present invention are the same as those of the other film layers of the comparative example.
Referring to fig. 4, fig. 4 is a scanning electron microscope image of a deep ultraviolet light emitting diode (sample B) according to an embodiment of the present invention after a bi-pass anodized aluminum template 200 is transferred during the preparation process; as can be seen from fig. 4, after the bi-pass anodized aluminum template 200 is transferred, the quantum dot array 101 is formed on the surface of the deep ultraviolet led epitaxial structure 100 provided by the present invention.
Referring to fig. 5, fig. 5 is a graph showing the variation of the light output power of the two different structures of the deep ultraviolet light emitting diode 100 with current; under the action of different driving currents (mA), the graphs of the light output power (mW) of the two deep ultraviolet light emitting diodes with the driving currents are tested respectively, as shown in fig. 5.
Specifically, as can be seen from fig. 5, chip tests were performed on the conventional deep ultraviolet light emitting diode (sample a of the comparative example) and the deep ultraviolet light emitting diode of the present invention (sample B of the present example), respectively; wherein, when the injection current is 100mA, the light output power of the traditional deep ultraviolet light emitting diode is 18.0mW; the light output power of the deep ultraviolet light emitting diode in the embodiment of the invention is 32.0mW; compared with the comparative example, the light output power corresponding to the deep ultraviolet light emitting diode is improved by 77.8% when the injection current is 100 mA.
This is because the light emitting material layer 13 in the deep ultraviolet light emitting diode is designed as the quantum dot array 101, so that the stress of the deep ultraviolet quantum well region can be released, the quantum confinement stark effect is reduced, and the confinement effect of carriers is also improved. Thereby realizing the great improvement of the light output power of the deep ultraviolet light-emitting diode.
In summary, the present invention provides a preparation method of a deep ultraviolet light emitting diode and the deep ultraviolet light emitting diode, which are different from the prior art, wherein the preparation method comprises: firstly, transferring the double-pass anodized aluminum template 200 onto one side surface of the deep ultraviolet light-emitting diode epitaxial structure 100 far away from the substrate 11, then forming an anti-etching layer 300 on the double-pass anodized aluminum template 200, then stripping the double-pass anodized aluminum template 200, then etching the deep ultraviolet light-emitting diode epitaxial structure 100 by taking the anti-etching layer 300 as a mask, forming a quantum dot array 101 by using a luminescent material layer 13 in the deep ultraviolet light-emitting diode epitaxial structure 100, and finally removing the anti-etching layer 300; according to the invention, the luminous material layer 13 in the deep ultraviolet light emitting diode epitaxial structure 100 is prepared into the quantum dot array 101 by adopting the double-pass anodic aluminum oxide template 200, so that on one hand, the stress of a deep ultraviolet active region is released by etching, the polarization intensity is reduced, the quantum confinement Stark effect is remarkably relieved, and the radiation recombination efficiency of the deep ultraviolet light emitting diode is improved; on the other hand, the luminescent material layer 13 of the quantum dot array 101 structure can limit the movement of carriers in three spatial dimensions, so that the carrier injection efficiency of the deep ultraviolet light emitting diode is improved; in addition, the quantum dot structure also improves the light extraction efficiency of the deep ultraviolet light emitting diode in an active region, and the three comprehensively realize the larger improvement of the light output power of the deep ultraviolet light emitting diode.
It should be noted that, the foregoing embodiments all belong to the same inventive concept, and the descriptions of the embodiments have emphasis, and where the descriptions of the individual embodiments are not exhaustive, reference may be made to the descriptions of the other embodiments.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, which is therefore intended to be covered by the appended claims.
Claims (10)
1. A method for preparing a deep ultraviolet light emitting diode, the method comprising:
s10, transferring a double-pass anodic aluminum oxide template to the surface of one side, far away from the substrate, of a deep ultraviolet light-emitting diode epitaxial structure;
s20, forming an etching-resistant layer on the double-pass anodic aluminum oxide template;
s30, stripping the double-pass anodized aluminum template;
s40, etching the deep ultraviolet light-emitting diode epitaxial structure by taking the etching resistant layer as a mask, so that a luminescent material layer in the deep ultraviolet light-emitting diode epitaxial structure forms a quantum dot array 101;
s50, removing the anti-etching layer.
2. The method according to claim 1, wherein in the step S10, the deep ultraviolet light emitting diode epitaxial structure includes a substrate, an intrinsic layer, an electron injection layer, a quantum well active layer, an electron blocking layer and a hole injection layer stacked from bottom to top.
3. The method according to claim 1, wherein in the step S10, the thickness of the bi-pass anodized aluminum template ranges from 10nm to 500nm, and the pore size of the bi-pass anodized aluminum template ranges from 2 nm to 50nm.
4. The method according to claim 1, wherein in the step S20, the material of the etching resist layer includes at least one of gold, nickel, silicon oxide or silicon nitride.
5. The method of manufacturing a deep ultraviolet light emitting diode according to claim 1, wherein in the step S30, the bi-pass anodized aluminum stencil is peeled off by a high temperature tape or a plating tape.
6. The method according to claim 2, wherein in the step S40, the light emitting material layer includes the electron injection layer, the quantum well active layer, the electron blocking layer, and the hole injection layer.
7. The method of manufacturing a deep ultraviolet light emitting diode according to claim 6, wherein the step S50 further comprises: and soaking the deep ultraviolet light-emitting diode epitaxial structure by adopting a strong alkaline solution.
8. The method for manufacturing a deep ultraviolet light emitting diode according to claim 7, wherein the step S50 further comprises: an N-type electrode is disposed on the electron injection layer, and a P-type electrode is disposed on the hole injection layer.
9. A deep ultraviolet light emitting diode prepared by the preparation method of the deep ultraviolet light emitting diode according to any one of claims 1 to 8, wherein the deep ultraviolet light emitting diode comprises a substrate, an intrinsic layer, an electron injection layer, a quantum well active layer, an electron blocking layer and a hole injection layer which are stacked from bottom to top;
the electron injection layer, the quantum well active layer, the electron blocking layer and the hole injection layer are all quantum dot arrays.
10. The deep ultraviolet light-emitting diode according to claim 9, wherein the particle size of the quantum dots in the quantum dot array is in the range of 2-50 nm.
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