CN113690325B - Solar cell and method for manufacturing same - Google Patents
Solar cell and method for manufacturing same Download PDFInfo
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- CN113690325B CN113690325B CN202110735496.7A CN202110735496A CN113690325B CN 113690325 B CN113690325 B CN 113690325B CN 202110735496 A CN202110735496 A CN 202110735496A CN 113690325 B CN113690325 B CN 113690325B
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- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 34
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims abstract description 18
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims description 74
- 229910052751 metal Inorganic materials 0.000 claims description 74
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 38
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/544—Solar cells from Group III-V materials
-
- 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 present disclosure provides a solar cell and a method of manufacturing the same, the solar cell including: the solar cell comprises a substrate, and a reflector layer, a p electrode layer, a p-type ohmic contact layer, a battery layer, an n-type AlGaInP layer, an n electrode layer and an anti-reflection layer which are sequentially laminated on the substrate; the battery layer comprises a GaInAs battery layer, a first tunneling junction, a GaInAsP battery layer, a second tunneling junction, a GaAs battery layer, a third tunneling junction, an AlGaAs battery layer, a fourth tunneling junction and an AlGaInP battery layer which are sequentially laminated on the p-type ohmic contact layer. The present disclosure can reduce the reflectance of the incident surface of the solar cell and allow more incident light to be absorbed and converted to improve the photoelectric conversion efficiency of the solar cell.
Description
Technical Field
The disclosure relates to the technical field of semiconductor photovoltaic devices, in particular to a solar cell and a manufacturing method thereof.
Background
A solar cell is a device that directly converts light energy into electric energy through a photoelectric effect or a photochemical effect. In the related art, a solar cell generally includes a plurality of subcells stacked, and a tunneling junction is disposed between two adjacent subcells. The p electrode and the n electrode are respectively arranged on the sub-cell positioned at the top and the sub-cell positioned at the bottom of the solar cell so as to supply power for the solar cell.
However, the photoelectric conversion efficiency of the solar cell in the related art is low, and the incident surface of the solar cell reflects much sunlight, but the sunlight incident into the solar cell cannot be completely absorbed and converted by the sub-cell, and the photoelectric conversion efficiency of the solar cell is also reduced.
Disclosure of Invention
The embodiment of the disclosure provides a solar cell and a manufacturing method thereof, which can reduce the reflectivity of an incident surface of the solar cell and enable more incident light to be absorbed and converted so as to improve the photoelectric conversion efficiency of the solar cell. The technical scheme is as follows:
embodiments of the present disclosure provide a solar cell including: the solar cell comprises a substrate, and a reflector layer, a p electrode layer, a p-type ohmic contact layer, a battery layer, an n-type AlGaInP layer, an n electrode layer and an anti-reflection layer which are sequentially laminated on the substrate; the battery layer comprises a GaInAs battery layer, a first tunneling junction, a GaInAsP battery layer, a second tunneling junction, a GaAs battery layer, a third tunneling junction, an AlGaAs battery layer, a fourth tunneling junction and an AlGaInP battery layer which are sequentially laminated on the p-type ohmic contact layer.
In one implementation of the embodiments of the present disclosure, the GaInAs battery layer, the GaInAsP battery layer, the GaAs battery layer, the GaInAsP battery layer, and the AlGaInP battery layer each include a back reflection layer, a base layer, an emitter layer, and a window layer that are stacked in order.
In another implementation of the disclosed embodiments, the mirror layer includes a first TiO layer sequentially laminated on the substrate 2 Layer and first MgF 2 A layer of the first MgF 2 The refractive index of the layer is 1.28-1.30, and the first TiO 2 The refractive index of the layer is 2.5-2.6.
In another implementation of an embodiment of the present disclosure, the mirror layer further includes an Au layer, the Au layer being located between the substrate and the first MgF2 layer.
In another implementation of the embodiments of the present disclosure, the anti-reflection layer includes a second TiO sequentially stacked on the n-type AlGaInP layer 2 Layer and third TiO 2 A layer of the third TiO 2 The surface of the layer remote from the substrate has a plurality of tapered protrusions.
In another implementation manner of the embodiment of the present disclosure, the anti-reflection layer further includes an HfO2 layer, an Al2O3 layer, and a second MgF2 layer sequentially stacked on the third TiO2 layer, and a refractive index of the HfO2 layer, a refractive index of the Al2O3 layer, and a refractive index of the second MgF2 layer sequentially become larger or smaller.
In another implementation manner of the embodiment of the disclosure, the n-electrode layer includes an n-type ohmic contact layer and a first metal protrusion, the n-type ohmic contact layer is located on a surface of the n-type AlGaInP layer, which is far away from the substrate, a first via hole penetrating through to the n-type ohmic contact layer is formed on the anti-reflection layer, and the first metal protrusion is located in the first via hole and extends out of the anti-reflection layer through the first via hole.
In another implementation manner of the embodiment of the disclosure, the second TiO2 layer has a groove exposing the p-type ohmic contact layer, and the HfO2 layer, the Al2O3 layer, and the second MgF2 layer cover surfaces of the second TiO2 layer and the groove; the p-electrode layer comprises a metal electrode layer and a second metal protrusion, the metal electrode layer is located between the reflector layer and the p-type ohmic contact layer, second through holes penetrating through the metal electrode layer are formed in the p-type ohmic contact layer, the HfO2 layer, the Al2O3 layer and the second MgF2 layer, and the second metal protrusion is located in the second through holes and extends into the groove through the second through holes.
In another implementation manner of the embodiment of the disclosure, the first metal protrusions are strip-shaped, the second metal protrusions are frame-shaped, and the second metal protrusions encircle the battery layer.
The embodiment of the disclosure provides a manufacturing method of a solar cell, which comprises the following steps: providing a substrate; sequentially growing an n-type AlGaInP layer, a battery layer and a p-type ohmic contact layer on the substrate, wherein the battery layer comprises an AlGaInP battery layer, a fourth tunneling junction, an AlGaAs battery layer, a third tunneling junction, a GaAs battery layer, a second tunneling junction, a GaInAsP battery layer, a first tunneling junction and a GaInAs battery layer which are sequentially laminated on the n-type AlGaInP layer; sequentially forming a p electrode layer and a reflecting mirror layer on the surface of the p-type ohmic contact layer; arranging a substrate on the surface of the reflector layer, and removing the substrate; and forming an anti-reflection layer on the surface of the n-type AlGaInP layer.
The technical scheme provided by the embodiment of the disclosure has the beneficial effects that at least:
in the solar cell provided by the embodiment of the disclosure, the cell layer is a stacked cell formed by five sub-cells, including a GaInAs cell layer, a GaInAsP cell layer, a GaAs cell layer, an AlGaAs cell layer and an AlGaAs cell layer, and in the direction from the light incident surface to the substrate of the solar cell, the forbidden band widths of the five cell layers are gradually reduced, that is, the energy band of the cell layer close to the light incident surface is highest and is sequentially reduced downwards, so as to form a gradual buffer layer, and thus photons with high energy are absorbed by the cell layer with high energy band above, while photons with low energy are absorbed by the cell layer with low energy band below through the cell layer above, thereby effectively improving the photoelectric conversion efficiency of the solar cell.
Meanwhile, an anti-reflection layer for increasing photon transmission is arranged above the battery layer, so that solar photon reflection is reduced, photons with different wave bands are more incident into the solar battery to be converted into photon-generated carriers, and photoelectric conversion efficiency is improved; and a reflecting mirror layer is arranged below the p electrode layer, and can reflect electrons transmitted from the battery layer back to the battery layer, namely photons which pass through each battery layer and are not absorbed are reflected back to the battery layer, so that the absorption of photons is increased, and the photoelectric conversion efficiency is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings required for the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present disclosure, and other drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
Fig. 1 is a schematic structural view of a solar cell according to an embodiment of the present disclosure;
fig. 2 is a schematic structural view of a battery layer according to an embodiment of the present disclosure;
FIG. 3 is a cross-sectional view of a solar cell provided by an embodiment of the present disclosure;
fig. 4 is a flowchart of a method of manufacturing a solar cell according to an embodiment of the present disclosure;
fig. 5 is a schematic view of a preparation state of a solar cell according to an embodiment of the present disclosure;
fig. 6 is a schematic view of a preparation state of a solar cell according to an embodiment of the present disclosure;
fig. 7 is a schematic view of a preparation state of a solar cell according to an embodiment of the present disclosure;
fig. 8 is a schematic view of a preparation state of a solar cell according to an embodiment of the present disclosure;
fig. 9 is a schematic view of a preparation state of a solar cell according to an embodiment of the disclosure.
The various labels in the figures are described below:
10-substrate, 11-metal bonding layer, 12-GaAs substrate, 13-n type GaAs buffer layer, 14-GaInP stop layer;
20-mirror layer, 201-first MgF 2 Layer, 202-first TiO 2 A layer, 203-Au layer;
30-p electrode layer, 301-metal electrode layer, 302-second metal bump;
40-p-type ohmic contact layer, 401-second via hole;
50-cell layer, 501-GaInAs cell layer, 502-first tunneling junction, 503-GaInAsP cell layer, 504-second tunneling junction, 505-GaAs cell layer, 506-third tunneling junction, 507-AlGaAs cell layer, 508-fourth tunneling junction, 509-AlGaInP cell layer, 511-back reflection layer, 512-base layer, 513-emitter layer, 514-window layer;
a 60-n type AlGaInP layer;
70-n electrode layer, 701-n type ohmic contact layer, 702-first metal bump, 703-branch bar;
80-antireflective layer, 801-second TiO 2 Layer, 802-third TiO 2 Layer 803-cone bump 804-HfO 2 Layer, 805-Al 2 O 3 Layer, 806-second MgF 2 Layer 807-first via;
a-groove.
Detailed Description
For the purposes of clarity, technical solutions and advantages of the present disclosure, the following further details the embodiments of the present disclosure with reference to the accompanying drawings.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The terms "first," "second," "third," and the like in the description and in the claims, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Likewise, the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one. The word "comprising" or "comprises", and the like, is intended to mean that elements or items that are present in front of "comprising" or "comprising" are included in the word "comprising" or "comprising", and equivalents thereof, without excluding other elements or items. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", "top", "bottom" and the like are used only to indicate relative positional relationships, which may be changed accordingly when the absolute position of the object to be described is changed.
Fig. 1 is a schematic structural diagram of a solar cell according to an embodiment of the present disclosure. As shown in fig. 1, the solar cell includes: a substrate 10, and a mirror layer 20, a p-electrode layer 30, a p-type ohmic contact layer 40, a battery layer 50, an n-type AlGaInP layer 60, an n-electrode layer 70, and an antireflection layer 80, which are sequentially stacked on the substrate 10.
As shown in fig. 1, the cell layer includes a GaInAs cell layer 501, a first tunneling junction 502, a GaInAsP cell layer 503, a second tunneling junction 504, a GaAs cell layer 505, a third tunneling junction 506, an AlGaAs cell layer 507, a fourth tunneling junction 508, and an AlGaInP cell layer 509, which are sequentially stacked on a p-type ohmic contact layer 40.
The gap width of the GaInAs cell layer 501 is 0.73eV, the gap width of the gainasp cell layer 503 is 1.11eV, the gap width of the gaas cell layer 505 is 1.40eV, the gap width of the algaas cell layer 507 is 1.71eV, and the gap width of the algainp cell layer 509 is 2.16eV.
In the solar cell provided in the embodiment of the present disclosure, the cell layer is a stacked cell formed by five sub-cells, including a GaInAs cell layer 501, a GaInAsP cell layer 503, a GaAs cell layer 505, an AlGaAs cell layer 507, and in the direction from the light incident surface of the solar cell to the substrate 10, the forbidden band widths of the five cell layers are gradually reduced, i.e., the energy bands of the cell layer close to the light incident surface are highest and sequentially reduced downward, so as to form a graded buffer layer, so that photons with high energy are absorbed by the cell layer with high energy band above, while photons with low energy are absorbed by the cell layer with low energy band below through the cell layer above, thereby effectively improving the photoelectric conversion efficiency of the solar cell.
Meanwhile, an anti-reflection layer 80 for increasing photon transmission is arranged above the cell layer, so that solar photon reflection is reduced, photons with different wave bands are more incident into the solar cell and are converted into photon-generated carriers, and photoelectric conversion efficiency is improved; and a reflecting mirror layer 20 is further disposed below the p-electrode layer 30, and the reflecting mirror layer 20 can reflect electrons transmitted from the cell layer back to the cell layer, i.e. photons passing through each cell layer and not being absorbed are reflected back to the cell layer, so as to increase photon absorption and improve photoelectric conversion efficiency.
Fig. 2 is a schematic structural view of a battery layer according to an embodiment of the present disclosure. As shown in fig. 2, the GaInAs cell layer 501, gaInAsP cell layer 503, gaAs cell layer 505, gaInAsP cell layer 503, and AlGaInP cell layer 509 each include a back reflection layer 511, a base layer 512, an emitter layer 513, and a window layer 514, which are stacked in this order.
The specific structure and the preparation materials of the back reflection layer 511, the base layer 512, the emitter layer 513 and the window layer 514 in the battery layer may refer to the related art, and embodiments of the present disclosure are not described.
Alternatively, as shown in FIG. 1, the mirror layer 20 includes a first TiO layer sequentially laminated on the substrate 10 2 Layer 202 and first MgF 2 Layer 201, first MgF 2 The refractive index of layer 201 is 1.28-1.30, the first TiO 2 The refractive index of layer 202 is 2.5-2.6.
Therefore, photons which are not absorbed can be reflected back to the inside of the cell by forming the high-low refractive index combined layer, so that the photon absorption efficiency is improved.
Illustratively, a first MgF 2 The refractive index of layer 201 is 1.29, first TiO 2 The refractive index of layer 202 is 2.5.
Optionally, a first MgF 2 The thickness of layer 201 is 20nm to 200nm. As an example, in embodiments of the present disclosure, the first MgF 2 The thickness of layer 201 is 50nm.
Optionally, the first TiO 2 Layer 202 has a thickness of 20nm to 200nm. As an example, in the embodiments of the present disclosure, the first TiO 2 Layer 20230nm.
Optionally, as shown in fig. 1, the mirror layer 20 further includes an Au layer 203, the Au layer 203 being located on the substrate 10 and the first MgF 2 Between layers 201. The Au layer 203 has good reflection performance, and can effectively reflect the solar photons transmitted to the Au layer 203 back to each cell layer, so as to improve the reflection effect of the mirror layer 20.
At the same time, through the first MgF 2 Layer 201, first TiO 2 The three film layers of the layer 202 and the Au layer 203 can form an omnidirectional reflector, so that photons which pass through the multi-layer battery layer and are not absorbed can be reflected into the battery, photon absorption is increased, and photoelectric conversion efficiency is improved.
Alternatively, as shown in FIG. 1, the anti-reflection layer 80 includes a second TiO layer sequentially laminated on the n-type AlGaInP layer 60 2 Layer 801 and third TiO 2 Layer 802, third TiO 2 The surface of the layer 802 remote from the substrate 10 has a plurality of tapered projections 803, the area of the cross section of the tapered projections 803 gradually decreasing in the direction away from the substrate 10.
By forming a second TiO on the n-type AlGaInP layer 60 2 Layer 801 and in a second TiO 2 A third TiO having a plurality of tapered projections 803 is formed on the layer 801 2 In the layer 802, since the side surface of the conical protrusion 803 is inclined, when sunlight reaches the side surface of the conical protrusion 803, if part of sunlight is reflected, the reflected sunlight still transmits towards the direction of other conical protrusions 803, so that the sunlight still can enter into TiO through the conical protrusion 803 2 A layer to be finally incident to the battery layer. Thus effectively solving the problem that the sunlight is blocked from entering the battery due to the reflection of the sunlight,photons in different wave bands are more incident into the solar cell and are converted into photon-generated carriers, so that the photoelectric conversion efficiency is improved.
At the same time, the formed surface is tapered third TiO 2 The layer 802 can play a role in absorption spectrum modulation of the externally grown battery layer by selecting different particle sizes and thicknesses, and has a good matching effect on spectrum absorption and current density limitation of the multi-junction GaAs battery.
Optionally, as shown in fig. 1, the anti-reflection layer 80 further includes a third TiO sequentially laminated thereon 2 HfO on layer 802 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Layer 806, hfO 2 Refractive index of layer 804, al 2 O 3 Refractive index of layer 805 and second MgF 2 The refractive index of layer 806 sequentially becomes larger or smaller.
Thus forming the third TiO 2 Layer 802, hfO 2 Layer 804, al 2 O 3 Layer 805, second MgF 2 The 4 continuous graded-index composite anti-reflection layers of the layer 806 reduce the reflection of solar photons, and photons with different wave bands are more incident into the battery device and are converted into photon-generated carriers, so that the photoelectric conversion efficiency is improved.
Wherein HfO is 2 Layer 804, al 2 O 3 Layer 805, second MgF 2 The thickness of layer 806 may be 50nm to 500nm; as an example, hfO 2 Layer 804, al 2 O 3 Layer 805, second MgF 2 Layer 806 may be 80nm.
Alternatively, as shown in fig. 1, the n-electrode layer 70 includes an n-type ohmic contact layer 701 and a first metal protrusion 702, the n-type ohmic contact layer 701 is located on a surface of the n-type AlGaInP remote from the substrate 10, a first via hole 807 penetrating through to the n-type ohmic contact layer 701 is provided on the anti-reflection layer 80, and the first metal protrusion 702 is located within the first via hole 807 and extends outside the anti-reflection layer 80 through the first via hole 807.
Wherein the n-type ohmic contact layer 701 may be an n-type GaAs layer. The first metal bump 702 may be Au, auGeNi, au, pt, au film layers sequentially stacked on the n-type ohmic contact layer 701, wherein each film layer has a thickness of 0.1 μm to 1 μm.
As shown in fig. 1, an n-type ohmic contact layer 701 and a second TiO 2 The layers 801 are each laminated on the n-type AlGaInP layer 60, i.e., the n-type ohmic contact layer 701 and the second TiO 2 Layer 801 is the same layer. Since the anti-reflection layer 80 includes the second TiO laminated in sequence 2 Layer 801, third TiO 2 Layer 802, hfO 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Layer 806, therefore, is subsequently laminated to a second TiO 2 The film layer on the layer 801 covers the n-type ohmic contact layer 701. In order to realize the solar cell power on, a first via hole 807 penetrating through to the n-type ohmic contact layer 701 is arranged on the anti-reflection layer 80, and a first metal protrusion 702 is arranged in the first via hole 807, so that the first metal protrusion 702 can extend out of the anti-reflection layer 80 through the first via hole 807 to be convenient for connection with a wire, and therefore the electric energy stored in the solar cell is transferred to an external electric device.
Fig. 3 is a cross-sectional view of a solar cell provided by an embodiment of the present disclosure. As shown in fig. 3, the first metal protrusion 702 may be in a bar shape, so that the first metal protrusion 702 is disposed in a bar shape not to block an excessively large area above the battery layer, so that most of external solar energy is incident to the battery layer through an area other than the first metal protrusion 702. And the tapered protrusion 803 is disposed at the portion outside the first metal protrusion 702, so that the solar reflectivity of the solar cell layer can be greatly reduced, more photons with different wavebands can be incident into the solar cell and converted into photon-generated carriers, and the photoelectric conversion efficiency is improved.
The broken line shown in fig. 3 is a sectional line of the section of fig. 1, and a state in which the tapered protrusion 803 shown in fig. 1 is located between two first metal protrusions 702 can be obtained according to the sectional line.
As shown in fig. 3, the side edge of the first metal protrusion 702 in the shape of a strip may further be provided with a plurality of branch strips 703 perpendicular to the first metal protrusion 702, which is beneficial to diversion of the photo-generated current distribution, so that the electric energy converted by the solar cell is easier to be converged to the first metal protrusion 702.
As shown in fig. 1, hfO 2 Layer 804, al 2 O 3 Layer 805 andtwo MgF 2 Layer 806 is laminated to a third TiO 2 After the surface of layer 802, hfO 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 The surface of layer 806 is also tapered. So that HfO 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Each film layer of the layer 806 can also improve the problem of blocking sunlight from entering the cell due to reflection of sunlight, and improve the photoelectric conversion efficiency.
Wherein, cover on the third TiO 2 HfO on layer 802 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 The surface of layer 806 is tapered; hfO (HfO) 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Layer 806 is on the surface of the third TiO 2 The surface outside layer 802 is planar.
It should be noted that only one array distribution in the third TiO is schematically shown in FIG. 1 2 Tapered projections 803 of the surface of layer 802. Tapered projections 803 are pyramid-shaped or cone-shaped. In other implementations, tapered protrusion 803 may also be a triangular-shaped rib in cross-section.
Optionally, as shown in FIG. 1, a second TiO 2 Layer 801 has grooves a, hfO exposing p-type ohmic contact layer 40 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Layer 806 is overlaid on a second TiO 2 The surface of layer 801 and groove A, the p-electrode layer 30 includes a metal electrode layer 301 and a second metal bump 302, the metal electrode layer 301 is located between the mirror layer 20 and the p-type ohmic contact layer 40, hfO 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 The second vias 401 penetrating through to the metal electrode layer 301 are disposed on the layers 806, and the second metal bumps 302 are located in the second vias 401 and extend into the grooves a through the second vias 401.
The metal electrode layer 301 may be Au, ti, pt, and Au film layers sequentially laminated on the mirror layer 20, and the Au, ti, pt, and Au film layers have thicknesses of 50nm, 100nm, and 50nm, respectively. The second metal bump 302 may be Ti, pd, pt, ag, pt and Au film layers laminated on the metal electrode layer 301, and each film layer in the second metal bump 302 may have a thickness of 0.1 μm to 1 μm.
As shown in FIG. 1, by forming a first TiO layer from a second TiO layer 2 The layer 801 etches down the recess a to reach the surface of the p-type ohmic contact layer 40 and to form a contact between the p-type ohmic contact layer 40 and the HfO 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 The layer 806 is provided with the second via 401, so that the second metal bump 302 can extend into the groove a through the second via 401, and thus the second metal bump 302 can be also disposed on the front surface of the solar cell, i.e. the side facing the solar energy and the light incident surface, so as to facilitate the electrical connection of the solar cell.
As shown in fig. 1, the second metal bump 302 protrudes from the p-type ohmic contact layer 40, hfO 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 After layer 806, the portion within recess a can be easily electrically connected to an external electrical device.
As shown in fig. 2, the second metal protrusion 302 is in a frame shape, and the second metal protrusion 302 surrounds the battery layer. By arranging the second metal protrusion 302 in a structure surrounding the battery layer, the distribution and diversion of the photo-generated current are facilitated, so that the electric energy converted by the solar cell is easier to be converged to the second metal protrusion 302.
Fig. 4 is a flowchart of a method for manufacturing a solar cell according to an embodiment of the present disclosure. As shown in fig. 4, the manufacturing method includes:
step S11: a substrate is provided.
Step S12: an n-type AlGaInP layer 60, a cell layer, and a p-type ohmic contact layer 40 are sequentially grown on the substrate.
The cell layer includes an AlGaInP cell layer 509, a fourth tunneling junction 508, an AlGaAs cell layer 507, a third tunneling junction 506, a GaAs cell layer 505, a second tunneling junction 504, a GaInAsP cell layer 503, a first tunneling junction 502, and a GaInAs cell layer 501 sequentially stacked on the n-type AlGaInP layer 60.
The gap width of the GaInAs cell layer 501 is 0.73eV, the gap width of the gainasp cell layer 503 is 1.11eV, the gap width of the gaas cell layer 505 is 1.40eV, the gap width of the algaas cell layer 507 is 1.71eV, and the gap width of the algainp cell layer 509 is 2.16eV.
Step S13: a p-electrode layer 30 and a mirror layer 20 are sequentially formed on the surface of the p-type ohmic contact layer 40.
Wherein the mirror layer 20 is used to reflect electrons transmitted from the cell layer back to the cell layer.
Step S14: the substrate 10 is provided on the surface of the mirror layer 20, and the substrate is removed.
Step S15: an anti-reflection layer 80 is formed on the surface of the n-type AlGaInP layer 60.
In the solar cell provided in the embodiment of the present disclosure, the cell layer is a stacked cell formed by five sub-cells, including a GaInAs cell layer 501, a GaInAsP cell layer 503, a GaAs cell layer 505, an AlGaAs cell layer 507, and an AlGaAs cell layer 507, in the direction from the light incident surface of the solar cell to the substrate 10, the forbidden band widths of the five cell layers gradually decrease, i.e., the energy band of the cell layer close to the light incident surface is highest and decreases in sequence, so as to form a graded buffer layer, so that photons with high energy are absorbed by the cell layer with high energy above, while photons with low energy are absorbed by the cell layer with low energy below through the cell layer above, thereby effectively improving the photoelectric conversion efficiency of the solar cell.
Meanwhile, an anti-reflection layer 80 for increasing photon transmission is arranged above the cell layer, so that solar photon reflection is reduced, photons with different wave bands are more incident into the solar cell and are converted into photon-generated carriers, and photoelectric conversion efficiency is improved; and a reflecting mirror layer 20 is further disposed below the p-electrode layer 30, and the reflecting mirror layer 20 can reflect electrons transmitted from the cell layer back to the cell layer, i.e. photons passing through each cell layer and not being absorbed are reflected back to the cell layer, so as to increase photon absorption and improve photoelectric conversion efficiency.
Fig. 5 is a schematic view of a preparation state of a solar cell according to an embodiment of the disclosure. As shown in fig. 5, in step S11, the substrate may be a GaAs substrate, and the substrate may be a flat substrate or a patterned substrate.
Wherein, the GaAs substrate 12 may be pretreated, the GaAs substrate 12 is placed in an MOCVD (Metal-organic Chemical Vapor Deposition, metal organic chemical vapor deposition) reaction chamber, and the GaAs substrate 12 is baked for 12 to 18 minutes. As an example, in the embodiment of the present disclosure, the GaAs substrate 12 is subjected to the baking process for 15 minutes.
Specifically, the baking temperature may be 1000 ℃ to 1200 ℃, and the pressure in the MOCVD reaction chamber during baking may be 100mbar to 200mbar.
Alternatively, the thickness of the GaAs substrate 12 may be 300 μm to 400 μm. As an example, the GaAs substrate 12 has a thickness of 350 μm.
As shown in fig. 5, after step S11, it may further include: an n-type GaAs buffer layer 13, a GaInP stop layer 14, and an n-type ohmic contact layer 701 are epitaxially grown in this order on the GaAs substrate 12.
Alternatively, the thickness of the n-type GaAs buffer layer 13 may be 10nm to 50nm, and as an example, the thickness of the n-type GaAs buffer layer 13 is 30nm.
Alternatively, the thickness of the GaInP cut-off layer 14 may be 60nm to 150nm, and as an example, the thickness of the GaInP cut-off layer 14 is 100nm.
Alternatively, the n-type ohmic contact layer 701 may be an n-type GaAs layer, and the thickness of the n-type ohmic contact layer 701 may be 50nm to 100nm, and as an example, the thickness of the n-type ohmic contact layer 701 is 80nm.
As shown in fig. 5, in step S12, an n-type AlGaInP layer 60, a cell layer, and a p-type ohmic contact layer 40 are sequentially formed on an n-type ohmic contact layer 701.
Among them, the thickness of the n-type AlGaInP layer 60 may be 0.1 μm to 1 μm, and as an example, the thickness of the n-type AlGaInP layer 60 is 0.5 μm.
As shown in fig. 5, the cell layers include a GaInAs cell layer 501, a first tunnel junction 502, a GaInAsP cell layer 503, a second tunnel junction 504, a GaAs cell layer 505, a third tunnel junction 506, an AlGaAs cell layer 507, a fourth tunnel junction 508, and an AlGaInP cell layer 509, which are sequentially stacked on an n-type AlGaInP layer 60.
Wherein the AlGaInP battery layer 509 has a thickness of 0.5 μm to 3 μm; the fourth tunneling junction 508 has a thickness of 30nm to 80nm; the AlGaAs battery layer 507 has a thickness of 0.5 μm to 3 μm; the thickness of the third tunneling junction 506 is 30nm to 80nm; the GaAs battery layer 505 has a thickness of 0.5 μm to 3 μm; the thickness of the second tunnel junction 504 is 30nm to 80nm; the GaInAsP cell layer 503 has a thickness of 0.5 μm to 3 μm and the first tunnel junction 502 has a thickness of 30nm to 80nm; the GaInAs battery layer 501 has a thickness of 0.5 μm to 3 μm.
Alternatively, the p-type ohmic contact layer 40 may be a p-type GaAs layer, and the thickness of the p-type ohmic contact layer 40 may be 100nm to 1000nm, and as an example, the thickness of the p-type ohmic contact layer 40 is 500nm.
The p-electrode layer 30 formed in step S13 is a formed metal electrode layer 301, and may specifically include:
after the growth of the n-type AlGaInP layer 60, the battery layer, and the p-type ohmic contact layer 40 in step S12 is completed, the surface of the p-type ohmic contact layer 40 of the epitaxial structure after the growth needs to be cleaned with acetone and isopropanol, a p-electrode pattern is defined on the surface by photolithography, and a Au, ti, pt, au film layer is evaporated, that is, the metal electrode layer 301 is formed.
Wherein, the thickness of the evaporated Au, ti, pt, au film layer is respectively 50nm, 100nm and 50nm.
Forming the mirror layer 20 in step S13 may include:
as shown in fig. 6, after the metal electrode layer 301 is formed by vapor deposition, the photoresist is removed first, and then the first MgF is sequentially vapor deposited on the surface of the metal electrode layer 301 facing away from the GaAs substrate 12 2 Layer 201, first TiO 2 Layer 202 and Au layer 203 to form mirror layer 20.
Then, the Au layer 203 is continuously evaporated with Ti, pt, au film layers so as to bond with the subsequent substrate 10.
Step S14 may include:
first, after polishing one surface of the Cu substrate 10 using CMP (Chemical Mechanical Polishing ), phosphoric acid is used: the mixed aqueous solution of hydrogen peroxide is soaked for 2min, the proportion of phosphoric acid, hydrogen peroxide and water is 8:3:4, and the temperature range of the solution is 40-45 ℃ so as to remove the metal cation pollution on the surface of the Cu substrate 10.
Then, as shown in fig. 7, ti, pt, au film layers are sequentially evaporated on the Cu substrate 10 so that the mirror layer 20 is bonded; next, the Cu substrate 10 is bondedThe metal film layer deposited on the upper surface is adhered to the metal film layer deposited on the reflector layer 20, and is placed at 300-350 ℃ under 9000Kg/cm 2 Up to 12000Kg/cm 2 Bonding is performed in the bonding cavity to form a metal bonding layer 11.
Finally, the GaAs substrate 12 on the bonded epitaxial structure is wet-removed with an alkaline solution, and the GaInP cut-off layer 14 is removed with an acidic solution.
The process of forming the second metal bump 302 of the p-electrode layer 30 and the first metal bump 702 of the n-electrode layer 70 may be further included after step S14:
first, as shown in fig. 8, a pattern of a p-electrode layer 30 is defined by using a photolithography technique, a dry etching process is performed to etch the p-electrode layer 301, a layer of negative photoresist is coated on the surface after photoresist removal and cleaning, a p-electrode pattern is defined, and a Ti, pd, pt, ag, pt, au film layer is deposited on the surface to form a second metal bump 302.
Wherein the deposited Ti, pd, pt, ag, pt, au film layer has a thickness of 0.1 μm1 μm.
Then, an n-electrode pattern is defined on the n-type ohmic contact layer 701 by photolithography, and a Au, auGeNi, au, pt, au film is deposited to form a first metal bump 702.
Wherein the deposited Au, auGeNi, au, pt, au film layer has a thickness of 0.1 μm to 1 μm.
Finally, annealing is performed at 300 ℃ to form good ohmic contact between the metal film layer and the n-type ohmic contact layer 701.
The process of forming the anti-reflection layer 80 in step S15 may include:
first, the region of the n-electrode layer 70 is protected by photolithography using NH 4 OH、H 22 The mixed solution removes the n-type ohmic contact layer 701 other than the n-electrode layer 70.
Then, as shown in FIG. 9, a second TiO is deposited on the n-AlGaInP layer 2 Layer 801, spin-coating polystyrene nanoparticles as a mask on the surface, and vapor-depositing a third TiO 2 Layer 802, in the third TiO 2 The surface of layer 802 forms tapered protrusions 803.
Then, as shown in FIG. 1In the third TiO 2 Layer 802 surface vapor deposition of HfO in sequence 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Layer 806 is used as an anti-reflective composite film, the anti-reflective film except for the positive and negative electrode regions is protected by photolithography, and the HfO in the region where the p-electrode layer 30 is located is dry etched away by dry etching 2 Layer 804, al 2 O 3 Layer 805 and a second MgF 2 Layer 806 to complete the preparation of the anti-reflective layer 80.
Finally, the Cu substrate 10 is thinned to 50 μm to 200 μm using a chemical mechanical polishing technique, and the unit cells are cut by laser, thus completing the fabrication of the battery device.
The foregoing disclosure is not intended to be limited to any form of embodiment, but is not intended to limit the disclosure, and any simple modification, equivalent changes and adaptations of the embodiments according to the technical principles of the disclosure are intended to be within the scope of the disclosure, as long as the modifications or equivalent embodiments are possible using the technical principles of the disclosure without departing from the scope of the disclosure.
Claims (6)
1. A solar cell, the solar cell comprising: a substrate (10) and a mirror layer (20), a p-electrode layer (30), a p-type ohmic contact layer (40), a battery layer (50), an n-type AlGaInP layer (60), an n-electrode layer (70) and an antireflection layer (80) which are sequentially laminated on the substrate (10);
the cell layer (50) comprises a GaInAs cell layer (501), a first tunneling junction (502), a GaInAsP cell layer (503), a second tunneling junction (504), a GaAs cell layer (505), a third tunneling junction (506), an AlGaAs cell layer (507), a fourth tunneling junction (508) and an AlGaInP cell layer (509) which are sequentially stacked on the p-type ohmic contact layer (40);
the anti-reflection layer (80) comprises a second TiO layer sequentially laminated on the n-type AlGaInP layer (60) 2 Layer (801) and third TiO 2 A layer (802), the third TiO 2 The surface of the layer (802) remote from the substrate (10) has a plurality of conical projections (803); the anti-reflection layer (80) further comprises a third TiO layer laminated in order on the third TiO layer 2 HfO on layer (802) 2 Layer (804), al 2 O 3 Layer (805) and second MgF 2 Layer (806), the HfO 2 Refractive index of layer (804), the Al 2 O 3 Refractive index of layer (805) and the second MgF 2 The refractive index of the layer (806) becomes sequentially larger or smaller;
the n-electrode layer (70) comprises an n-type ohmic contact layer (701) and a first metal protrusion (702), the n-type ohmic contact layer (701) is positioned on the surface of the n-type AlGaInP layer (60) far away from the substrate (10), a first via hole (807) penetrating through the n-type ohmic contact layer (701) is arranged on the anti-reflection layer (80), and the first metal protrusion (702) is positioned in the first via hole (807) and extends to the outside of the anti-reflection layer (80) through the first via hole (807);
the second TiO 2 The layer (801) has a recess (A) exposing the p-type ohmic contact layer (40), the HfO 2 A layer (804), the Al 2 O 3 Layer (805) and the second MgF 2 A layer (806) covering the second TiO 2 A layer (801) and a surface of the recess (a); the p-electrode layer (30) comprises a metal electrode layer (301) and a second metal bump (302), the metal electrode layer (301) is positioned between the reflector layer (20) and the p-type ohmic contact layer (40), and the p-type ohmic contact layer (40) and the HfO are arranged on the substrate 2 A layer (804), the Al 2 O 3 Layer (805) and the second MgF 2 And second through holes (401) penetrating through the metal electrode layer (301) are formed in the layers (806), and the second metal protrusions (302) are located in the second through holes (401) and extend into the grooves (A) through the second through holes (401).
2. The solar cell according to claim 1, wherein the GaInAs cell layer (501), the GaInAsP cell layer (503), the GaAs cell layer (505), the AlGaAs cell layer (507) and the AlGaInP cell layer (509) each comprise a back reflection layer (511), a base layer (512), an emitter layer (513) and a window layer (514) laminated in this order.
3. The solar cell according to claim 1, characterized in that the mirror layer (20) comprises a first TiO laminated in sequence on the substrate (10) 2 Layer (202) and first MgF 2 A layer (201), the first MgF 2 The refractive index of the layer (201) is 1.28-1.30, and the first TiO 2 The refractive index of the layer (202) is 2.5-2.6.
4. A solar cell according to claim 3, characterized in that the mirror layer (20) further comprises an Au layer (203), the Au layer (203) being located at the substrate (10) and the first MgF 2 Between the layers (201).
5. The solar cell according to claim 1, wherein the first metal protrusions (702) are stripe-shaped, the second metal protrusions (302) are each frame-shaped, and the second metal protrusions (302) surround the cell layer.
6. A method of manufacturing a solar cell, the method comprising:
providing a substrate;
sequentially growing an n-type AlGaInP layer, a battery layer and a p-type ohmic contact layer on the substrate, wherein the battery layer comprises an AlGaInP battery layer, a fourth tunneling junction, an AlGaAs battery layer, a third tunneling junction, a GaAs battery layer, a second tunneling junction, a GaInAsP battery layer, a first tunneling junction and a GaInAs battery layer which are sequentially laminated on the n-type AlGaInP layer;
sequentially forming a p electrode layer and a reflecting mirror layer on the surface of the p-type ohmic contact layer;
arranging a substrate on the surface of the reflector layer, and removing the substrate;
forming an anti-reflection layer on the surface of the n-type AlGaInP layer, wherein the anti-reflection layer comprises a second TiO sequentially laminated on the n-type AlGaInP layer 2 Layer and third TiO 2 A layer of the third TiO 2 The surface of the layer away from the substrate is provided withA plurality of tapered protrusions; the anti-reflection layer further comprises a third TiO layer laminated in sequence on the third TiO layer 2 HfO on layer 2 Layer, al 2 O 3 Layer and second MgF 2 A layer of HfO 2 Refractive index of layer, the Al 2 O 3 Refractive index of layer and the second MgF 2 The refractive index of the layers becomes sequentially larger or smaller; the n electrode layer comprises an n type ohmic contact layer and a first metal protrusion, the n type ohmic contact layer is positioned on the surface of the n type AlGaInP layer, which is far away from the substrate, a first via hole penetrating through the n type ohmic contact layer is arranged on the anti-reflection layer, and the first metal protrusion is positioned in the first via hole and extends out of the anti-reflection layer through the first via hole; the second TiO 2 The layer is provided with a groove exposing the p-type ohmic contact layer, the HfO 2 Layer of the Al 2 O 3 Layer and the second MgF 2 Layer is covered on the second TiO 2 The surfaces of the layer and the grooves; the p-electrode layer comprises a metal electrode layer and a second metal protrusion, the metal electrode layer is positioned between the reflecting mirror layer and the p-type ohmic contact layer, and the p-type ohmic contact layer and the HfO are arranged on the reflecting mirror layer 2 Layer of the Al 2 O 3 Layer and the second MgF 2 And the layers are respectively provided with a second via hole penetrating through the metal electrode layer, and the second metal bulge is positioned in the second via hole and extends into the groove through the second via hole.
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