CN113540310A - Inverted deep ultraviolet LED chip and manufacturing method thereof - Google Patents
Inverted deep ultraviolet LED chip and manufacturing method thereof Download PDFInfo
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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
- H01L33/44—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 coatings, e.g. passivation layer or anti-reflective coating
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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
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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
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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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
- H01L33/02—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
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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
- H01L33/02—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
- H01L33/20—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 particular shape, e.g. curved or truncated substrate
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- H—ELECTRICITY
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- 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
Abstract
The invention discloses a flip deep ultraviolet LED chip and a manufacturing method thereof, wherein the flip deep ultraviolet LED chip comprises an anti-reflection layer, a sapphire substrate layer, an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer; the n-type AlGaN layer, the multi-layer quantum well active layer, the p-type AlGaN layer and the p-type GaN contact layer are sequentially stacked on one side of the sapphire substrate layer, and the anti-reflection layer is arranged on the other side of the sapphire substrate layer; and after the sapphire substrate layer is subjected to roughening etching on the side away from the n-type AlGaN layer, depositing the anti-reflection layer. According to the invention, the sapphire substrate layer is roughened at the side far away from the n-type AlGaN layer, and the anti-reflection layer is deposited, so that the photon escape probability is increased, the interface total reflection is reduced, and the light extraction efficiency of the chip is improved.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a flip deep ultraviolet LED chip and a manufacturing method thereof.
Background
Ultraviolet LED (UV-LED for short) is mainly applied to the aspects of biological medical treatment, anti-counterfeiting identification, purification field, computer data storage, military and the like. With the development of the technology, new application can continuously appear to replace the original technology and products, the ultraviolet LED has wide market application prospect, for example, an ultraviolet LED phototherapy instrument is a medical instrument which is popular in the future, but the technology is still in the growth period.
The semiconductor deep ultraviolet light source has great application value in the fields of illumination, sterilization, medical treatment, printing, biochemical detection, high-density information storage, secret communication and the like. The light-emitting wavelength of the deep ultraviolet LED taking the AlGaN material as the active region can cover an ultraviolet band of 210-365 nm, so that the AlGaN material is an ideal material for realizing a deep ultraviolet LED device product in the band, and has incomparable advantages compared with other traditional ultraviolet light sources.
At present, the sterilization performance of deep ultraviolet LEDs is concerned worldwide, the demand of flip-chip deep ultraviolet LED chips is suddenly increased, and UVC products in the market are expensive due to high technical barriers and tight supply chain resources. In order to maintain the interest of the supply chain, reduce the price of the unit optical power, and exert the value of technical improvement, the improvement of the light emitting efficiency of the chip is the main research subject at present.
For a traditional deep ultraviolet LED chip, a P-type GaN layer in an epitaxial structure has strong absorption on UVC wave band 260-285 nm, namely the UVC chip can hardly emit light at one side of an epitaxial surface, and the light emitted at the side can cause serious photon loss, so that the UVC chip is generally required to be manufactured into a flip chip and made of sapphire Al2O3The substrate surface performs light extraction. Due to sapphire Al2O3The refractive index of (2) is 1.7, the light is emitted into the air, the refractive index of the air is 1, and the light emission limitation is realized in two aspects: firstly, at a sapphire light-emitting interface, light outside a full emission angle is totally reflected back to the inside of the chip and is conducted towards the deposition direction of an epitaxial surface, and the light is absorbed when contacting a P-type GaN layer; second, light within the total reflection angle due to the presence of sapphire Al2O3The interface between (n ═ 1.7) and air (n ═ 1) causes interface reflection, accompanied by half-wave loss. Due to the above limitation factors, the light-emitting effect of the conventional deep ultraviolet LED chip is restricted, and a new solution is required to solve the above existing problems.
Disclosure of Invention
The invention aims to provide a flip deep ultraviolet LED chip and a manufacturing method thereof, and aims to solve the problem that the existing flip deep ultraviolet LED chip is poor in light emitting effect due to interface reflection at a substrate-air interface.
In order to solve the above technical problem, a first solution provided by the present invention is: a flip deep ultraviolet LED chip comprises an anti-reflection layer, a sapphire substrate layer, an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer; an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer are sequentially stacked on one side of a sapphire substrate layer, and an anti-reflection layer is arranged on the other side of the sapphire substrate layer; and after the sapphire substrate layer is subjected to roughening etching on the side away from the n-type AlGaN layer, an anti-reflection layer is deposited.
The specific steps of coarsening and etching comprise: evaporating a metal layer on one side of the sapphire substrate layer, which is far away from the n-type AlGaN layer; annealing the metal layer at 900-1000 ℃ for 1-2 min, wherein the heating rate is 15-25 ℃, and obtaining a self-assembled metal layer; and etching the sapphire substrate layer deposited with the self-assembly metal layer, and removing the self-assembly metal layer by using a solution after etching is finished to obtain the roughened substrate surface.
The method comprises the following steps of etching the sapphire substrate layer deposited with the self-assembly metal layer: adopting plasma etching process to etch with BCl3And etching the area, which is not covered by the self-assembly metal layer, on the surface of the sapphire substrate layer for etching gas.
Preferably, the solution for removing the self-assembly metal layer comprises concentrated sulfuric acid, hydrogen peroxide and water which are mixed according to the volume ratio of 5:1: 1.
Preferably, the thickness of the metal layer is 5-20 nm.
Preferably, the metal layer is a nickel metal layer.
Preferably, the material of the anti-reflection layer is SiO2The thickness is (2n +1) a, wherein n is an integer greater than 1, and a is greater than or equal to 44.2nm and less than or equal to 48.5 nm.
Preferably, the material of the anti-reflection layer is MgF2The thickness is (2n +1) b, wherein n is an integer greater than 1, and b is more than or equal to 47.1nm and less than or equal to 51.6 nm.
In order to solve the above technical problem, a second solution provided by the present invention is: a manufacturing method of a flip deep ultraviolet LED chip is used for manufacturing the flip deep ultraviolet LED chip in the first solution, and comprises the following specific steps: sequentially depositing an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer on one side of a sapphire substrate layer; evaporating a metal layer on one side of the sapphire substrate layer, which is far away from the n-type AlGaN layer; annealing the metal layer at 900-1000 ℃ for 1-2 min, wherein the heating rate is 15-25 ℃, and obtaining a self-assembled metal layer; etching the sapphire substrate layer deposited with the self-assembly metal layer, and removing the self-assembly metal layer by using a solution after etching is finished to obtain a roughened substrate surface; and depositing an anti-reflection layer on the roughened substrate surface to obtain the flip deep ultraviolet LED chip.
Preferably, the material of the anti-reflection layer is SiO2Or MgF2。
The invention has the beneficial effects that: compared with the prior art, the flip deep ultraviolet LED chip and the manufacturing method thereof provided by the invention have the advantages that the sapphire substrate layer is roughened at the side far away from the n-type AlGaN layer, and the anti-reflection layer is deposited, so that the photon escape probability is increased, the total reflection of the interface is reduced, and the light extraction efficiency of the chip is improved.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of a flip-chip deep ultraviolet LED chip in the present invention;
FIG. 2 is a diagram of a manufacturing process of an embodiment of a flip-chip deep ultraviolet LED chip in the present invention;
in the figure: the solar cell comprises a 1-antireflection layer, a 2-sapphire substrate layer, a 21-coarsened substrate surface, a 3-n type AlGaN layer, a 4-multilayer quantum well active layer, a 5-p type AlGaN layer, a 6-p type GaN contact layer, a 7-metal layer and an 8-self-assembly metal layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1, for a first solution of the present invention, a flip-chip deep ultraviolet LED chip is provided, which specifically includes an anti-reflection layer 1, a sapphire substrate layer 2, an n-type AlGaN layer 3, a multi-layer quantum well active layer 4, a p-type AlGaN layer 5, and a p-type GaN contact layer 6; an n-type AlGaN layer 3, a multi-layer quantum well active layer 4, a p-type AlGaN layer 5 and a p-type GaN contact layer 6 are sequentially stacked on one side of a sapphire substrate layer 2, and an anti-reflection layer 1 is arranged on the other side of the sapphire substrate layer 2; after the sapphire substrate layer 2 is subjected to roughening etching on the side far away from the n-type AlGaN layer 3, the antireflection layer 1 is deposited, and the light extraction efficiency of the chip is improved by roughening and depositing the antireflection layer.
Specifically, the step of roughening etching includes:
(1) and evaporating a metal layer 7 on the side of the sapphire substrate layer 2 far away from the n-type AlGaN layer 3. In the present embodiment, the thickness of the metal layer is preferably 5 to 20nm, and the metal layer is preferably a nickel metal layer.
(2) Annealing the metal layer for 1-2 min by adopting an RTA (room temperature annealing) rapid annealing furnace at 900-1000 ℃, wherein the heating rate is 15-25 ℃, and self-assembly spherical aggregation occurs on metal layer particles at the moment, so that a plurality of self-assembly metal layers in spherical distribution are obtained.
(3) And etching the sapphire substrate layer deposited with the self-assembly metal layer, and removing the self-assembly metal layer by using a solution after etching is finished to obtain the roughened substrate surface. In this step, a plasma etching process is adopted, and BCl is used3Etching the area, which is not covered by the self-assembly metal layer, on the surface of the sapphire substrate layer by using etching gas, and removing the self-assembly metal layer by using a solution after the etching is finished to obtain a roughened substrate surface, wherein the solution for removing the self-assembly metal layer is prepared by mixing concentrated sulfuric acid, hydrogen peroxide and water according to the volume ratio of 5:1: 1.
In this embodiment, regarding specific material selection and corresponding parameter setting of the anti-reflection layer, the following two setting methods are provided: first, the material of the anti-reflection layer is SiO2The refractive index n is 1.47, and the thickness is (2n +1) a, wherein n is an integer greater than 1, 44.2nm ≦ a ≦ 48.5nm, and the value of a is preferably 46.7 nm; secondly, the material of the anti-reflection layer is MgF2The refractive index n is 1.38 and the thickness is (2n +1) b, whereinn is an integer greater than 1, b is greater than or equal to 47.1nm and less than or equal to 51.6nm, and the value of b is preferably 49.8 nm. The thicknesses of the anti-reflection layers in the two setting modes need to be odd times of a quarter wavelength, and the materials and parameters of the anti-reflection layers can be adaptively adjusted according to actual requirements, which is not limited herein.
Referring to fig. 2, fig. 2 is a diagram of a manufacturing process of an embodiment of the flip-chip deep ultraviolet LED chip of the present invention. For the second solution provided by the present invention, a manufacturing method of a flip-chip deep ultraviolet LED chip is provided, and the manufacturing method is used for manufacturing the flip-chip deep ultraviolet LED chip in the first solution, and includes the following specific steps:
and S1, sequentially depositing an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer on one side of the sapphire substrate layer. As shown in fig. 2 (a), the refractive index n of the sapphire substrate layer 2 is 1.7, an MOCVD device is adopted, an n-type AlGaN layer 3, a multi-layer quantum well active layer 4, a p-type AlGaN layer 5 and a p-type GaN contact layer 6 are sequentially deposited on one side of the sapphire substrate layer 2, and a p electrode and an n electrode can be arranged on one side, away from the sapphire substrate layer 2, of the p-type GaN contact layer 6, so that a complete flip chip structure is formed.
And S2, evaporating a metal layer on the side of the sapphire substrate layer away from the n-type AlGaN layer. In this step, as shown in fig. 2 (b), a metal layer 7 is deposited on the sapphire substrate layer 2 away from the n-type AlGaN layer 3, and in this embodiment, a nickel metal layer is preferred for the formation of a subsequent self-assembled metal layer.
S3, annealing the metal layer at 900-1000 ℃ for 1-2 min at a temperature rise rate of 15-25 ℃ to obtain the self-assembled metal layer. As shown in fig. 2 (c), annealing the metal layer with an RTA rapid annealing furnace at 900-1000 ℃ for 1-2 min at a temperature rise rate of 15-25 ℃, preferably at a temperature rise rate of 20 ℃ for 2min, wherein the metal layer particles undergo self-assembly spheronization, so that the flat metal layer 7 is transformed into a plurality of self-assembly metal layers 8 distributed in a spheroid manner, and the self-assembly metal layers 8 can serve as templates in subsequent etching. Among them, nickel is preferable as a material of the metal layer because nickel is easily spherically polymerized at high temperature and is not easily dropped from the sapphire substrate layer, thereby improving the stability of the formed self-assembled metal layer and ensuring that the sapphire substrate can be well roughened later.
And S4, etching the sapphire substrate layer deposited with the self-assembly metal layer, and removing the self-assembly metal layer by using a solution after etching is finished to obtain a roughened substrate surface. This step is shown in FIG. 2 (d), and a plasma etching process is performed with BCl3Etching the area of the surface of the sapphire substrate layer 2 which is not covered by the self-assembly metal layer 8 under the conditions of proper cavity pressure and electrode power for etching gas, and removing the self-assembly metal layer 8 by using a solution after etching is finished to obtain a roughened substrate surface 21 with a concave-convex shape; due to the concave-convex shape structure of the roughened substrate surface 21, the surface area of the sapphire substrate layer is increased, the escape probability of photons in the flip chip is increased, and the total reflection limit of the interface is broken, so that the light extraction rate of the chip at the roughened substrate surface 21 is improved.
And S5, depositing an anti-reflection layer on the roughened substrate surface to obtain the flip-chip deep ultraviolet LED chip. As shown in fig. 2 (e), an anti-reflection layer 1 is deposited on a roughened substrate surface 21 having a concave-convex morphology, and at this time, the deposited anti-reflection layer 1 has a structure with concave-convex morphology on both surfaces, so that the surface area of the anti-reflection layer 1 is significantly increased, on one hand, the escape probability of photons at the interface between the anti-reflection layer and air is increased, and on the other hand, the total reflection limiting effect at the interface between the anti-reflection layer and air is significantly reduced, thereby solving the problem that the conventional flip chip generates cross-section reflection at the interface between the sapphire substrate and air and is accompanied by half-wave loss, and significantly improving the light extraction effect. In this embodiment, the material of the anti-reflection layer is preferably SiO2Or MgF2And the thickness of different materials needs to be correspondingly adjusted due to the difference of the refractive indexes, but no matter which material is selected, the thickness of the anti-reflection film needs to be odd times of a quarter wavelength, so that the anti-reflection effect on the light irradiated from the roughened substrate surface can be realized.
Further, the flip deep ultraviolet LED chip and the common flip deep ultraviolet LED chip in the prior art are subjected to a plurality of comparison tests on light extraction efficiency, and it can be found that the light extraction efficiency of the flip deep ultraviolet LED chip is improved by 10-15% compared with that of the common flip chip, and the scheme of the invention is proved to realize the improvement of the light extraction efficiency of the chip.
Compared with the prior art, the flip deep ultraviolet LED chip and the manufacturing method thereof provided by the invention have the advantages that the sapphire substrate layer is roughened at the side far away from the n-type AlGaN layer, and the anti-reflection layer is deposited, so that the photon escape probability is increased, the total reflection of the interface is reduced, and the light extraction efficiency of the chip is improved.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A flip deep ultraviolet LED chip is characterized by comprising an anti-reflection layer, a sapphire substrate layer, an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer;
the n-type AlGaN layer, the multi-layer quantum well active layer, the p-type AlGaN layer and the p-type GaN contact layer are sequentially stacked on one side of the sapphire substrate layer, and the anti-reflection layer is arranged on the other side of the sapphire substrate layer;
and after the sapphire substrate layer is subjected to roughening etching on the side away from the n-type AlGaN layer, depositing the anti-reflection layer.
2. The flip deep ultraviolet LED chip of claim 1, wherein the etching roughening step comprises:
evaporating a metal layer on one side of the sapphire substrate layer, which is far away from the n-type AlGaN layer;
annealing the metal layer at 900-1000 ℃ for 1-2 min, wherein the heating rate is 15-25 ℃, and obtaining a self-assembled metal layer;
and etching the sapphire substrate layer deposited with the self-assembly metal layer, and removing the self-assembly metal layer by using a solution after etching is finished to obtain a roughened substrate surface.
3. The flip deep ultraviolet LED chip of claim 2, wherein the step of etching the sapphire substrate layer deposited with the self-assembled metal layer specifically comprises: adopting plasma etching process to etch with BCl3And etching the area, which is not covered by the self-assembly metal layer, on the surface of the sapphire substrate layer for etching gas.
4. The flip-chip deep ultraviolet LED chip of claim 2, wherein the solution from which the self-assembled metal layer is removed is prepared by mixing concentrated sulfuric acid, hydrogen peroxide, and water in a volume ratio of 5:1: 1.
5. The flip-chip deep ultraviolet LED chip of claim 2, wherein the metal layer has a thickness of 5 to 20 nm.
6. The flip-chip deep ultraviolet LED chip of claim 2, wherein the metal layer is a nickel metal layer.
7. The flip-chip deep ultraviolet LED chip of claim 1, wherein the anti-reflection layer is made of SiO2The thickness is (2n +1) a, wherein n is an integer greater than 1, and a is greater than or equal to 44.2nm and less than or equal to 48.5 nm.
8. The flip-chip deep ultraviolet LED chip of claim 1, wherein the anti-reflective layer is MgF2The thickness is (2n +1) b, wherein n is an integer greater than 1, and b is more than or equal to 47.1nm and less than or equal to 51.6 nm.
9. The manufacturing method of the flip deep ultraviolet LED chip as claimed in any one of claims 1 to 8, comprising the following specific steps:
sequentially depositing an n-type AlGaN layer, a multi-layer quantum well active layer, a p-type AlGaN layer and a p-type GaN contact layer on one side of a sapphire substrate layer;
evaporating a metal layer on one side of the sapphire substrate layer, which is far away from the n-type AlGaN layer;
annealing the metal layer at 900-1000 ℃ for 1-2 min, wherein the heating rate is 15-25 ℃, and obtaining a self-assembled metal layer;
etching the sapphire substrate layer deposited with the self-assembly metal layer, and removing the self-assembly metal layer by using a solution after etching is finished to obtain a roughened substrate surface;
and depositing an anti-reflection layer on the roughened substrate surface to obtain the flip deep ultraviolet LED chip.
10. The method for manufacturing the flip-chip deep ultraviolet LED chip according to claim 9, wherein the anti-reflection layer is made of SiO2Or MgF2。
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| CN202110691398.8A CN113540310A (en) | 2021-06-22 | 2021-06-22 | Inverted deep ultraviolet LED chip and manufacturing method thereof |
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| CN114512581A (en) * | 2022-04-20 | 2022-05-17 | 至芯半导体(杭州)有限公司 | Deep ultraviolet UVC chip epitaxial structure and preparation method and application thereof |
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