CN111725372B - Submicron vertical deep ultraviolet LED based on surface plasmon enhancement and preparation method thereof - Google Patents
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Abstract
The invention discloses a submicron vertical deep ultraviolet LED based on surface plasmon enhancement and a preparation method thereof, wherein the submicron vertical deep ultraviolet LED comprises a p-type electrode layer, a p-type conductive silicon substrate, a metal bonding layer, a p-type reflecting electrode layer, a p-GaN layer, an MQWs layer, an n-AlGaN layer and an n-type electrode which are sequentially arranged, the n-type electrode is arranged to be a net structure, the n-AlGaN layer is positioned in the net structure of the n-type electrode and is filled with a plasmon modification layer, and the whole thickness of a deep ultraviolet LED device is not more than 200 mu m. The submicron vertical structure deep ultraviolet LED reduces the waveguide mode limiting effect caused by internal total reflection by reducing the whole thickness of a device, and further enhances the light emitting efficiency of the deep ultraviolet LED by combining surface plasmon modification on an n-AlGaN surface, so that the electro-optic conversion efficiency is improved.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to an information material, a semiconductor device, visible light communication, illumination, display and medical sterilization, and relates to a submicron vertical structure deep ultraviolet LED based on surface plasmon enhancement and a preparation method thereof.
Background
The forbidden band width of the III nitride material is from 0.64eV to 6.14eV, almost all spectrums from ultraviolet to infrared bands are covered, and corresponding light-emitting wavelengths can be obtained by doping different elements. At present, the electro-optic conversion efficiency of commercial red and blue LEDs is over 60 percent, and a ternary compound of AlGaN is obtained by introducing Al doping to obtain an ultraviolet device in the range of 210-400nm, wherein the electro-optic conversion efficiency is much lower than that of blue light, particularly deep ultraviolet light in a UVC wave band. The deep ultraviolet light can be used in the fields of medical sterilization, disinfection and the like, and in recent years, the research of the deep ultraviolet light in the field of scattering communication is very hot. However, due to the problem of low electro-optic conversion efficiency of the deep ultraviolet LED, the power of the deep ultraviolet LED device has a large difference compared with the power of the traditional deep ultraviolet light source mercury lamp, and the deep ultraviolet LED device cannot comprehensively replace the mercury lamp in a short time.
One of the important reasons for the low electro-optic conversion efficiency of the deep ultraviolet LED device is that the refractive index difference between the AlGaN material and air is large, so that most of the deep ultraviolet light excited by the quantum well is trapped inside the device by the mode effect of the waveguide due to internal total reflection, and is transmitted and absorbed by multiple reflection.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a submicron vertical structure deep ultraviolet LED based on surface plasmon enhancement and a preparation method thereof.
The technical scheme adopted by the invention is as follows: the submicron vertical deep ultraviolet LED based on surface plasmon enhancement comprises a p-type electrode layer, a p-type conductive silicon substrate, a metal bonding layer, a p-type reflecting electrode layer, a p-GaN layer, an MQWs layer, an n-AlGaN layer and an n-type electrode which are sequentially arranged, wherein the n-type electrode is of a net structure, the n-AlGaN layer is positioned in the net structure of the n-type electrode and is filled with a plasmon modification layer, and the whole thickness of a deep ultraviolet LED device is not more than 200 mu m.
Furthermore, the metal bonding layer is made of an Au/Sn alloy layer, the p-type reflecting electrode layer is made of Ni/Al/Ti/Au, the Ni/Al/Ti/Au multilayer metal with high deep ultraviolet reflectivity greatly contributes to the improvement of the reflectivity of the LED device, and the n-type electrode is made of Ni/Au, so that the reflection efficiency of the manufactured LED device can be further improved.
Furthermore, the n-AlGaN layer is made by thinning through dry etching, and the integral thickness of the structure formed by the p-GaN layer, the MQWs layer and the n-AlGaN layer is ensured to be less than 1 mu m.
Further, the plasmon modification layer is made of an Al particle layer grown by magnetron sputtering.
The preparation method of the submicron vertical deep ultraviolet LED based on surface plasmon enhancement comprises the following steps:
step 1), selecting materials and preprocessing, selecting and cleaning a deep ultraviolet LED wafer which is provided with a p-GaN layer, an MQWs layer, an n-AlGaN layer, a buffer layer and a sapphire substrate in sequence, preparing a p-type reflecting electrode layer on the p-GaN layer of the deep ultraviolet LED wafer by adopting electron beam evaporation, and then carrying out rapid annealing to form ohmic contact;
step 2), performing metal bonding, namely respectively preparing metal layers on a p-type conductive silicon substrate and a p-type reflecting electrode layer of the deep ultraviolet LED wafer by thermal evaporation, and then performing metal bonding on the prepared metal layers to prepare metal bonding layers;
step 3), removing the sapphire substrate and the buffer layer of the wafer prepared in the step 2) by mechanical grinding;
step 4), thinning the n-AlGaN layer by adopting inductive coupling plasma etching;
step 5), uniformly spin-coating a layer of photoresist on the thinned n-AlGaN layer, defining a window area of the n-type electrode by photoetching, preparing the n-type electrode by adopting electron beam evaporation, and then cleaning and removing the residual photoresist to finish the preparation of the n-type electrode;
step 6), sputtering a layer of Al particles on the surface of the n-AlGaN layer by adopting a magnetron sputtering process to finish the preparation of the plasmon modification layer;
step 7), spin-coating a layer of photoresist on the n-type electrode and the plasmon polariton modification layer of the LED obtained in the step 6) for protection, then thinning the conductive silicon substrate of the LED to a thickness not more than 200 microns by adopting a mechanical thinning and polishing process, and cleaning the protective photoresist after thinning is finished;
and 8), preparing a p-type electrode layer on the thinned conductive silicon substrate by adopting electron beam evaporation, and scribing to obtain the surface plasmon enhancement-based deep ultraviolet LED device with the submicron vertical structure.
Compared with the prior art, the invention has the beneficial effects that:
1) the epitaxial layer is transferred to the silicon substrate through the metal bonding layer, so that the LED heat dissipation effect is better.
2) And by adopting a vertical structure, the current injection efficiency is high, and the problem of device thermal death caused by current crowding is favorably solved.
3) And the n-AlGaN layer is thinned, so that the structural thickness of the LED device is greatly reduced to be not more than 200 mu m, the waveguide mode effect of the device is reduced, and the light extraction efficiency is improved.
4) And the light emitting efficiency of the device is improved by adopting the p-type reflective metal electrode.
5) And a surface plasmon modification layer is prepared on the n-AlGaN layer, so that the light extraction efficiency of the device is enhanced.
According to the deep ultraviolet LED device with the submicron vertical structure, the n-AlGaN layer is thinned, so that the waveguide mode limiting effect of the device is reduced or even eliminated, and the light emitting efficiency of the device is improved. Meanwhile, the thickness of the n-AlGaN layer is very thin, the principle of surface plasmon enhancement is actually a near-field effect of an electric field, and free electrons carried on the surface of modified metal particles resonate with the applied electric field, so that higher energy is localized in a range close to the particles in the metal particles, the amplitude of a nonlinear effect generated in the region is enhanced, the recombination speed of carriers is accelerated, and the effect of enhancing luminescence is achieved. Therefore, if the thickness of the n-GaN is not less than a certain amount, the plasmon enhancement effect cannot be generated, so that the sub-micron deep ultraviolet LED device with the vertical structure can further improve the light extraction efficiency of the device by utilizing the near field enhancement effect of the surface plasmon, thereby improving the electro-optic conversion efficiency of the device.
Drawings
FIG. 1 is a schematic structural diagram of a sub-micron vertical structure deep ultraviolet LED device based on surface plasmon enhancement;
FIG. 2 is a top view of a sub-micron vertical structure deep ultraviolet LED device based on surface plasmon enhancement according to the present invention;
FIG. 3 is a schematic cross-sectional structure of a carrier, i.e., a sapphire substrate wafer, of a sub-micron vertical structure deep ultraviolet LED device based on surface plasmon enhancement according to the present invention;
FIG. 4 is a flow chart of the manufacturing process of the sub-micron vertical structure deep ultraviolet LED device based on surface plasmon enhancement.
The figure shows that: a 1-p type electrode layer; a 2-p type conductive silicon substrate; 3-a metal bonding layer; a 4-p type reflective electrode layer; a 5-p-GaN layer; a 6-MQWs layer; a 7-n-AlGaN layer; an 8-n type electrode; 9-a plasmon modification layer; 10-a buffer layer; 11-sapphire substrate.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the combination or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, are not to be construed as limiting the present invention. In addition, in the description process of the embodiment of the present invention, the positional relationships of the devices such as "upper", "lower", "front", "rear", "left", "right", and the like in all the drawings are based on fig. 1.
As shown in fig. 1, the submicron vertical deep ultraviolet LED based on surface plasmon enhancement comprises a p-type electrode layer 1, a p-type conductive silicon substrate 2, a metal bonding layer 3, a p-type reflective electrode layer 4, a p-GaN layer 5, an MQWs layer 6, an n-AlGaN layer 7 and an n-type electrode 8 which are sequentially arranged, wherein the n-type electrode 8 is arranged in a mesh structure, the n-AlGaN layer 7 is arranged in the mesh structure of the n-type electrode 8 and filled with a plasmon modification layer 9, and the whole thickness of the deep ultraviolet LED device is not more than 200 μm. The advantage that n type electrode 8 sets up to network structure is that make plasmon modification layer 9 can directly adopt magnetron sputtering growth to make the Al particle layer to in the mesh or the mesh of network structure of n type electrode 8 is directly filled with plasmon modification layer 9, and then make contributions for strengthening perpendicular deep ultraviolet LED's of submicron reflection efficiency. The submicron vertical deep ultraviolet LED is thin in overall thickness, and the light-emitting efficiency of the device can be further improved by utilizing the near field enhancement effect of surface plasmons, so that the electro-optic conversion efficiency of the device is improved; the n-AlGaN layer 7 is thinned, so that the waveguide mode limiting effect caused by internal total reflection is reduced, and the two methods are combined to further enhance the light-emitting efficiency of the deep ultraviolet LED, so that the purpose of improving the electro-optic conversion efficiency is achieved.
The preferable embodiment of the submicron vertical deep ultraviolet LED is that the metal bonding layer 3 is an Au/Sn alloy layer, the p-type reflecting electrode layer 4 is a multilayer metal with high Ni/Al/Ti/Au reflectivity to deep ultraviolet light, the reflectivity of the LED device is greatly improved, and the n-type electrode 8 is Ni/Au, so that the reflection efficiency of the manufactured LED device can be further improved.
The better implementation mode of the submicron vertical deep ultraviolet LED is that the n-AlGaN layer 7 is made by thinning through dry etching, and meanwhile, the integral thickness of a structure formed by the p-GaN layer 5, the MQWs layer 6 and the n-AlGaN layer 7 is ensured to be less than 1 mu m, so that the purpose of design is to ensure that the plasmon modification layer 9 and the n-AlGaN layer 7 can be well combined finally, and the electro-optic conversion efficiency of the submicron vertical deep ultraviolet LED is improved.
The better implementation mode of the submicron vertical deep ultraviolet LED is that the plasmon modification layer 9 is made of an Al particle layer grown by magnetron sputtering, and the process of the Al particle layer grown by magnetron sputtering has the advantages of simple equipment, easiness in control, large coating area, strong adhesive force and the like, and is a better choice for making the plasmon modification layer 9.
As shown in fig. 4, the preparation method of the submicron vertical deep ultraviolet LED based on surface plasmon enhancement mainly includes the following steps:
step 1), selecting materials and preprocessing, selecting and cleaning a deep ultraviolet LED wafer which is sequentially provided with a p-GaN layer 5, an MQWs layer 6, an n-AlGaN layer 7, a buffer layer 10 and a sapphire substrate 11, preparing a p-type reflecting electrode layer 4 on the p-GaN layer 5 of the deep ultraviolet LED wafer by adopting electron beam evaporation, and then carrying out rapid annealing to form ohmic contact. Fig. 2 is a schematic cross-sectional view of a selected duv LED wafer, and fig. 3 is a top view of the selected duv LED wafer. Electron Beam Evaporation (Electron Beam Evaporation) is one type of physical vapor deposition. Different from the traditional evaporation method, the electron beam evaporation can accurately realize the bombardment of the target material in the crucible by using high-energy electrons by using the cooperation of an electromagnetic field, so that the target material is melted and then deposited on a substrate, and a high-purity and high-precision film can be plated by using the electron beam evaporation, so that the quality of the p-type reflecting electrode layer 4 is ensured;
step 2), metal bonding, namely respectively preparing metal layers on a p-type conductive silicon substrate 2 and a p-type reflecting electrode layer 4 of a deep ultraviolet LED wafer by adopting thermal evaporation, and then carrying out metal bonding on the prepared metal layers to prepare a metal bonding layer 3, wherein the thermal evaporation refers to a process of placing a substrate or a workpiece to be coated in a vacuum chamber, heating a coating material to evaporate and gasify the coating material to deposit the coating material on the surface of the substrate or the workpiece and form a film or a coating, and is also called vacuum evaporation coating, which is called evaporation coating or vapor deposition for short;
step 3), removing the sapphire substrate 11 and the buffer layer 10 of the wafer prepared in the step 2) by mechanical grinding;
step 4), thinning the n-AlGaN layer 7 by adopting inductive coupling plasma etching;
step 5), uniformly spin-coating a layer of photoresist on the thinned n-AlGaN layer 7, aiming at protecting the lower material (such as an etching or ion implantation barrier layer), defining a window area of an n-type electrode 8 by photoetching, preparing the n-type electrode 8 by adopting electron beam evaporation, and then cleaning and removing the residual photoresist to finish the preparation of the n-type electrode 8;
step 6), sputtering a layer of Al particles on the surface of the n-AlGaN layer 7 by adopting a magnetron sputtering process to complete the preparation of the plasmon modification layer 9;
step 7), spin-coating a layer of photoresist on the n-type electrode 8 and the plasmon modification layer 9 of the LED obtained in the step 6) for protection, then thinning the conductive silicon substrate 2 of the LED to a thickness not more than 200 μm by adopting a mechanical thinning and polishing process, and cleaning the protective photoresist after thinning;
and 8), preparing a p-type electrode layer 1 on the thinned conductive silicon substrate 2 by adopting electron beam evaporation, and scribing to obtain the surface plasmon enhancement-based submicron vertical structure deep ultraviolet LED device.
The noun explains: the MQWs layer 6 is a multi-quantum trap layer, the n-AlGaN layer is made of n-type aluminum gallium nitride, and the p-GaN layer is made of gallium nitride.
The embodiments of the present invention are disclosed as the preferred embodiments, but not limited thereto, and those skilled in the art can easily understand the spirit of the present invention and make various extensions and changes without departing from the spirit of the present invention.
Claims (3)
1. Submicron perpendicular deep ultraviolet LED based on surface plasmon enhancement, its characterized in that: the deep ultraviolet LED device comprises a p-type electrode layer (1), a p-type conductive silicon substrate (2), a metal bonding layer (3), a p-type reflecting electrode layer (4), a p-GaN layer (5), an MQWs layer (6), an n-AlGaN layer (7) and an n-type electrode (8) which are sequentially arranged, wherein the n-type electrode (8) is arranged to be a net structure, the net structure of the n-type electrode (8) in which the n-AlGaN layer (7) is positioned is filled with a plasmon modification layer (9), and the whole thickness of the deep ultraviolet LED device is not more than 200 mu m;
the submicron vertical deep ultraviolet LED comprises the following steps:
step 1), selecting materials and preprocessing, selecting and cleaning a deep ultraviolet LED wafer which is provided with a p-GaN layer (5), an MQWs layer (6), an n-AlGaN layer (7), a buffer layer (10) and a sapphire substrate (11) in sequence, preparing a p-type reflecting electrode layer (4) on the p-GaN layer (5) of the deep ultraviolet LED wafer by adopting electron beam evaporation, and then carrying out rapid annealing to form ohmic contact;
step 2), performing metal bonding, namely respectively preparing metal layers on a p-type conductive silicon substrate (2) and a p-type reflecting electrode layer (4) of the deep ultraviolet LED wafer by thermal evaporation, and then performing metal bonding on the prepared metal layers to prepare a metal bonding layer (3);
step 3), removing the sapphire substrate (11) and the buffer layer (10) of the wafer prepared in the step 2) by mechanical grinding;
step 4), thinning the n-AlGaN layer (7) by adopting inductive coupling plasma etching;
step 5), uniformly spin-coating a layer of photoresist on the thinned n-AlGaN layer (7), defining a window area of the n-type electrode (8) by photoetching, preparing the n-type electrode (8) by adopting electron beam evaporation, and then cleaning and removing the residual photoresist to finish the preparation of the n-type electrode (8);
step 6), sputtering a layer of Al particles on the surface of the n-AlGaN layer (7) by adopting a magnetron sputtering process to finish the preparation of the plasmon modification layer (9);
step 7), spin-coating a layer of photoresist on the n-type electrode (8) and the plasmon modification layer (9) of the LED obtained in the step 6) for protection, then thinning the conductive silicon substrate (2) of the LED to a thickness not more than 200 microns by adopting a mechanical thinning and polishing process, and cleaning the protective photoresist after thinning;
step 8), preparing a p-type electrode layer (1) on the thinned conductive silicon substrate (2) by adopting electron beam evaporation, and scribing to obtain the surface plasmon enhancement-based submicron vertical structure deep ultraviolet LED device; the n-AlGaN layer (7) is made by thinning through dry etching, and meanwhile, the whole thickness of a structure formed by the p-GaN layer (5), the MQWs layer (6) and the n-AlGaN layer (7) is ensured to be less than 1 mu m.
2. The sub-micron deep vertical ultraviolet LED based on surface plasmon enhancement of claim 1, wherein: the metal bonding layer (3) is made of an Au/Sn alloy layer, the p-type reflecting electrode layer (4) is made of Ni/Al/Ti/Au, and the n-type electrode (8) is made of Ni/Au.
3. The sub-micron deep vertical ultraviolet LED based on surface plasmon enhancement of claim 1, wherein: the plasmon modification layer (9) is made of an Al particle layer grown by magnetron sputtering.
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