CN112909181A - Tunneling junction of perovskite/perovskite two-end laminated solar cell - Google Patents
Tunneling junction of perovskite/perovskite two-end laminated solar cell Download PDFInfo
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
- H10K30/57—Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K30/80—Constructional details
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- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the technical field of solar cells, in particular to a tunneling junction of a perovskite/perovskite double-end laminated solar cell; the tunneling junction comprises a compact n-type or p-type semiconductor material, a tunneling composite layer and a p-type or n-type semiconductor material, and the n-type and p-type semiconductor materials respectively have electron and hole transmission capacities; the tunneling composite layer is a perovskite/perovskite two-end laminated solar cell tunneling composite layer based on transparent conductive metal oxide nanocrystals; according to the tunneling junction of the perovskite/perovskite two-end laminated solar cell, the metal oxide nanocrystalline with good conductivity is used as a tunneling composite layer in the perovskite/perovskite laminated solar cell, so that the short-circuit current density of the perovskite/perovskite laminated solar cell is improved, and the problem of instability of the cell caused by diffusion of metal materials is solved.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a tunneling junction of a perovskite/perovskite double-end laminated solar cell.
Background
The organic-inorganic hybrid perovskite solar cell has the advantages of low cost and high efficiency, receives wide attention in the photovoltaic field all over the world, the highest efficiency reported at present reaches 25.5 percent and is close to the highest efficiency of a crystalline silicon solar cell, and the perovskite has the advantage of adjustable band gap (the band gap can be adjusted to be in a range of 1.2eV-3.5eV), so that the perovskite is an ideal material for preparing a laminated cell.
In order to obtain higher photoelectric conversion efficiency, a perovskite with a wide band gap of 1.77eV is used as a top cell for absorbing ultraviolet light and visible light, a perovskite with a narrow band gap of 1.22eV is used as a bottom cell for absorbing near infrared light, tin oxide is deposited by combining a compact atomic layer, noble metal gold and organic hole transport layer poly (3, 4-ethylenedioxythiophene) (PEDOT: PSS) are thermally evaporated to be used as a tunneling junction, and a high-efficiency perovskite/perovskite laminated solar cell is obtained.
According to the CN201910885774.X tunneling junction structure of a perovskite/perovskite two-end laminated solar cell, the tunneling junction structure can effectively reduce the open-circuit voltage loss of the laminated cell, improve the filling factor of the perovskite/perovskite laminated solar cell, improve the photoelectric conversion efficiency of the perovskite/perovskite two-end laminated solar cell, and is simple in preparation process, lower in cost and suitable for large-area industrial mass production.
However, in the prior art, the metal material serving as the tunneling composite layer is prone to cause instability of the laminated battery, the metal material is expensive in cost and complex in purification and preparation, and in addition, the absorption of the metal itself is generally high, so that the light absorption of the bottom battery is prone to be influenced when the metal material serves as the tunneling composite layer, and finally the problem that the overall short-circuit current density of the laminated battery is limited is caused.
Therefore, the invention provides a novel stable tunneling junction constructed by adopting the metal oxide nanocrystalline with good conductivity and stable chemical property as a tunneling composite layer in the perovskite/perovskite tandem solar cell, improves the efficiency and stability of the perovskite/perovskite tandem solar cell, and solves the technical problems.
Disclosure of Invention
In order to solve the problems that in the prior art, a metal material is used as a tunneling composite layer to easily cause instability of a laminated cell, the metal material is high in cost, complex in purification and preparation, and generally high in absorption of metal, light absorption of a bottom cell is easily influenced when the metal material is used as the tunneling composite layer, and finally the whole short-circuit current density of the laminated cell is limited, the invention provides a tunneling junction of a perovskite/perovskite two-end laminated solar cell.
The technical scheme adopted by the invention for solving the technical problems is as follows: the tunneling junction of the perovskite/perovskite two-end laminated solar cell comprises a compact n-type or p-type semiconductor material, a tunneling composite layer and a p-type or n-type semiconductor material, wherein the n-type and p-type semiconductor materials respectively have electron and hole transmission capacities; the tunneling composite layer is a perovskite/perovskite two-end laminated solar cell tunneling composite layer based on transparent conductive metal oxide nanocrystals.
Preferably, the tunneling composite layer is made of a metal oxide nanocrystalline material.
Preferably, the metal oxide nanocrystalline material includes Indium Zinc Oxide (IZO), Indium Tin Oxide (ITO), and indium hydroxide hydride (In)2O3H), aluminum-doped zinc oxide (AZO) and zinc-doped tin oxide (ZTO).
Preferably, the metal oxide nanocrystal is prepared by an evaporation condensation method, a chemical vapor reaction method, a precipitation method, a spraying method, a sol-gel method, a mechanical crushing method, a solid state reaction method and an amorphous crystallization method, and can be stably dispersed in a processing solvent.
Preferably, the dispersion solvent of the metal oxide nanocrystal includes water, methanol, ethanol, isopropanol, toluene, chlorobenzene, o-dichlorobenzene, chloroform, methyl formate, ethyl formate, and ethyl acetate.
Preferably, the preparation method of the tunneling composite layer comprises spin coating, electrochemical deposition, soaking, blade coating, slit coating and ink-jet printing.
Preferably, the n-type is denseThe layer comprising titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO) and zinc tin oxide (Zn)2SnO4) The one or more n-type semiconductor materials, but not limited to the n-type semiconductor materials, and the corresponding p-type hole transport layer materials thereof described above, include nickel oxide (NiO), molybdenum oxide (MoO)3) Cuprous oxide (Cu)2O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), redox graphene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), 2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]And (3) a combination of one or more materials such as (9, 9' -spirobifluorene (Spiro-OMeTAD), poly (3, 4-ethylenedioxythiophene), polystyrene sulfonate (PEDOT: PSS), 4-butyl-N, N-diphenylaniline homopolymer (Ploy-TPD), polyvinyl carbazole (PVK) and the like, but is not limited to the p-type hole transport layer material.
Preferably, the p-type dense layer material comprises nickel oxide (NiO) and molybdenum oxide (MoO)3) Cuprous oxide (Cu)2One or more p-type semiconductor materials such as O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), but not limited to the above p-type semiconductor materials, and the corresponding n-type hole transport layer material includes titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO), fullerene (C)60) Graphene, fullerene derivatives [6,6]-phenyl-C61-methyl butyrate (PCBM), but is not limited to n-type hole transport layer materials.
The invention has the following beneficial effects:
1. according to the tunneling junction of the perovskite/perovskite two-end laminated solar cell, the metal oxide nanocrystalline with good conductivity is used as a tunneling composite layer in the perovskite/perovskite laminated solar cell, so that the short-circuit current density of the perovskite/perovskite laminated solar cell is improved, and the problem of instability of the cell caused by diffusion of metal materials is solved.
2. According to the tunneling junction of the perovskite/perovskite double-end laminated solar cell, the transparent conductive metal oxide nanocrystalline is adopted to replace a precious metal composite layer, so that the material cost is greatly reduced, the parasitic absorption problem of precious metal is solved, the light transmittance is improved, the short-circuit current density of the cell is improved, the problem that the cell is unstable due to the diffusion of metal serving as the composite layer is solved, the great gain on the short-circuit current density is realized, and the stability of the cell is greatly improved.
Drawings
The invention will be further explained with reference to the drawings.
Fig. 1 is a schematic diagram of device structures of two tandem solar cells and a schematic diagram of structural design of a corresponding tunneling junction according to the present invention.
Fig. 2 is a scanning electron micrograph of a perovskite tandem solar cell of the present invention.
Fig. 3 is a current density-voltage curve obtained by comparing the transparent conductive oxide nanocrystals of the present invention with gold as the tunneling composite layer.
Figure 4 is a 85 ℃ thermal stability aging test comparing the transparent conductive oxide nanocrystals of the present invention with gold as the tunneling composite layer.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
As shown in fig. 1 to 4, the tunnel junction of the perovskite/perovskite double-end stacked solar cell according to the present invention includes a dense n-type or p-type semiconductor material, a tunnel composite layer, and a p-type or n-type semiconductor material, and the n-type and p-type semiconductor materials have electron and hole transport capabilities, respectively; the tunneling composite layer is a perovskite/perovskite two-end laminated solar cell tunneling composite layer based on transparent conductive metal oxide nanocrystals; when in work, the metal in the prior art as a tunneling composite layer is easy to cause the metal to diffuse to the perovskite light absorption layer, which causes the performance attenuation and instability of the laminated cell, meanwhile, metal has higher parasitic absorption as a tunneling composite layer in the perovskite/perovskite laminated battery, so that the light absorption of the battery in the laminated battery is reduced, the short-circuit current density of the laminated battery is finally reduced, and the noble metal tunneling layer has higher cost, the preparation method is complex and the like, through the tunneling junction of the perovskite/perovskite double-end laminated solar cell, by adopting the metal oxide nanocrystalline with better conductivity as a tunneling composite layer in the perovskite/perovskite laminated solar cell, the short-circuit current density of the perovskite/perovskite laminated solar cell is improved, and the problem of unstable cell caused by diffusion of metal materials is solved.
As an embodiment of the present invention, the tunneling composite layer is made of a metal oxide nanocrystal material; during operation, because the metal takes place slow interdiffusion easily in perovskite cell and leads to device stability to descend, metal self absorbs the effective absorption that influences end battery more easily moreover, and the diffusion problem of metal has just in time been solved to the metal oxide nanocrystalline, and metal oxide's light transmissivity is generally better moreover, has reduced the parasitic absorption of tunneling composite bed to promote the conversion efficiency of tandem solar cell, and electric conductivity is better.
In one embodiment of the present invention, the metal oxide nanocrystal material includes Indium Zinc Oxide (IZO), Indium Tin Oxide (ITO), and indium hydroxide hydride (In)2O3H), aluminum-doped zinc oxide (AZO) and zinc-doped tin oxide (ZTO); when in work, the transparent conductive indium-doped tin oxide nanocrystalline is adopted as the tunneling composite layer of the perovskite/perovskite laminated solar cell, which not only has good tunneling composite effect, the parasitic absorption of the indium-doped tin oxide nanocrystal is smaller than that of metal, so that larger short-circuit current density can be obtained, the photoelectric conversion efficiency of the perovskite/perovskite laminated solar cell adopting noble metal as a tunneling composite layer is 23.8 percent, the photoelectric conversion efficiency of the perovskite/perovskite laminated solar cell adopting the transparent conductive indium-doped tin oxide nanocrystal as the tunneling composite layer is improved to 25.1 percent, and in a thermal stability test at 85 ℃, the perovskite/perovskite laminated solar cell adopting the transparent conductive indium-doped tin oxide nanocrystal as a tunneling composite layer can still maintain the initial efficiency of more than 90 percent after an aging test for about 500 hours.
As an embodiment of the present invention, the metal oxide nanocrystal is prepared by an evaporation condensation method, a chemical vapor reaction method, a precipitation method, a spray method, a sol-gel method, a mechanical pulverization method, a solid state reaction method, and an amorphous crystallization method, and can be stably dispersed in a processing solvent.
As an embodiment of the present invention, the dispersion solvent of the metal oxide nanocrystal includes water, methanol, ethanol, isopropanol, toluene, chlorobenzene, o-dichlorobenzene, chloroform, methyl formate, ethyl formate, and ethyl acetate.
The preparation method of the tunneling composite layer as one embodiment of the present invention includes spin coating, electrochemical deposition, soaking, blade coating, slit coating, and inkjet printing.
In one embodiment of the present invention, the n-type dense layer includes titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO) and zinc tin oxide (Zn)2SnO4) The one or more n-type semiconductor materials, but not limited to the n-type semiconductor materials, and the corresponding p-type hole transport layer materials thereof described above, include nickel oxide (NiO), molybdenum oxide (MoO)3) Cuprous oxide (Cu)2O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), redox graphene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), 2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]And (3) a combination of one or more materials such as (9, 9' -spirobifluorene (Spiro-OMeTAD), poly (3, 4-ethylenedioxythiophene), polystyrene sulfonate (PEDOT: PSS), 4-butyl-N, N-diphenylaniline homopolymer (Ploy-TPD), polyvinyl carbazole (PVK) and the like, but is not limited to the p-type hole transport layer material.
As an embodiment of the invention, the p-type dense layer material comprises nickel oxide (NiO) and molybdenum oxide (MoO)3) Cuprous oxide (Cu)2One or more p-type semiconductor materials such as O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), but not limited to the above p-type semiconductor materials, and the corresponding n-type hole transport layer material includes titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO), fullerene (C)60) Graphite, graphiteAlkene, fullerene derivatives [6,6 ]]-phenyl-C61-methyl butyrate (PCBM), but is not limited to n-type hole transport layer materials.
The specific working process is as follows:
when the perovskite/perovskite tandem solar cell is in work, the metal oxide nanocrystalline with good conductivity is used as a tunneling composite layer in the perovskite/perovskite tandem solar cell, so that the short-circuit current density of the perovskite/perovskite tandem solar cell is improved, and the problem of instability of the cell caused by diffusion of metal materials is solved; because the metal is easy to generate slow mutual diffusion in the perovskite cell to cause the reduction of the stability of the device, the metal has strong self absorption and is easy to influence the effective absorption of the bottom cell, the metal oxide nanocrystal just solves the problem of metal diffusion, the metal oxide has generally good light transmission, and the parasitic absorption of a tunneling composite layer is reduced, thereby improving the conversion efficiency of the laminated solar cell and having good conductivity; the transparent conductive indium-doped tin oxide nanocrystal is used as a tunneling composite layer of the perovskite/perovskite laminated solar cell, so that a good tunneling composite effect is achieved, the parasitic absorption of the indium-doped tin oxide nanocrystal is smaller than that of metal, a large short-circuit current density can be obtained, the photoelectric conversion efficiency of the perovskite/perovskite laminated solar cell using noble metal as the tunneling composite layer is 23.8%, the photoelectric conversion efficiency of the perovskite/perovskite laminated solar cell using the transparent conductive indium-doped tin oxide nanocrystal as the tunneling composite layer is increased to 25.1%, and in an 85-DEG C thermal stability test, the initial efficiency of the perovskite/perovskite laminated solar cell using the transparent conductive indium-doped tin oxide nanocrystal as the tunneling composite layer can still be maintained by more than 90% after about 500-hour aging test.
In order to verify that the metal oxide nanocrystal with better conductivity is used as a tunneling composite layer in the perovskite/perovskite tandem solar cell and construct a novel and stable tunneling junction effect, the following experiment is made:
example 1
In this example 1, a perovskite/perovskite tandem solar cell is prepared by using the structure shown in fig. 1a, and the specific preparation process is as follows:
a photograph of a cross-section of the cell under a scanning electron microscope using the structure of figure 1a is shown in figure 2.
A layer of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) with the thickness of about 20nm is prepared on a cleaned ITO substrate to be used as a hole transport layer.
Depositing a layer of perovskite on the prepared hole transport layer, wherein the thickness of the perovskite is about 300 nm.
Preparation of a layer C by thermal evaporation60As an electron transport layer, the thickness was about 20 nm.
Using atomic layer deposition on C60A layer of SnO is grown on the surface2And the thickness is 20 nm.
The tunneling composite layer adopts transparent conductive indium-doped tin oxide nanocrystalline with the thickness of about 20 nm.
The p-type hole transport layer was prepared using poly-3, 4-ethylenedioxythiophene polystyrene sulfonate (PEDOT: PSS).
In the preparation of the prepared PEDOT: and preparing a second layer of perovskite on the PSS layer, wherein the thickness is about 900 nm.
A layer of fullerene (C60) and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) double-layer structure is prepared by thermal evaporation as an electron transport layer, and the thickness is respectively 30 nm and 7 nm.
Finally, a layer of Cu with the thickness of 150nm is evaporated and plated by thermal evaporation to be used as an electrode.
The transparent conductive indium-doped tin oxide nanocrystal is used as a tunneling composite layer of the perovskite/perovskite laminated solar cell, so that a good tunneling composite effect is achieved, the parasitic absorption of the indium-doped tin oxide nanocrystal is smaller than that of metal, and a larger short-circuit current density can be obtained, the device result is shown in fig. 3, the photoelectric conversion efficiency of the perovskite/perovskite laminated solar cell adopting the noble metal as the tunneling composite layer is 23.8%, and the photoelectric conversion efficiency of the perovskite/perovskite laminated solar cell adopting the transparent conductive indium-doped tin oxide nanocrystal as the tunneling composite layer is improved to 25.1%; as shown in fig. 4, in a thermal stability test at 85 ℃, the perovskite/perovskite tandem solar cell using the transparent conductive indium-doped tin oxide nanocrystal as the tunneling composite layer can still maintain over 90% of initial efficiency after about 500 hours of aging test, and the stability is obviously superior to that of the tandem cell using gold as the tunneling composite layer.
While there have been shown and described what are at present considered the fundamental principles of the invention, its essential features and advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (8)
1. A tunneling junction for a perovskite/perovskite two-terminal tandem solar cell, characterized by: the tunneling junction comprises a compact n-type or p-type semiconductor material, a tunneling composite layer and a p-type or n-type semiconductor material, and the n-type and p-type semiconductor materials respectively have electron and hole transmission capacities; the tunneling composite layer is a perovskite/perovskite two-end laminated solar cell tunneling composite layer based on transparent conductive metal oxide nanocrystals.
2. The tunneling junction of a perovskite/perovskite double-end-stacked solar cell according to claim 1, wherein: the tunneling composite layer is made of a metal oxide nanocrystalline material.
3. The tunneling junction of a perovskite/perovskite double-end-stacked solar cell according to claim 2, wherein: the metal oxide nanocrystalline material comprises Indium Zinc Oxide (IZO), Indium Tin Oxide (ITO) and indium hydroxide (In)2O3H), aluminum-doped zinc oxide (AZO) and zinc-doped tin oxide (ZTO).
4. The tunneling junction of a perovskite/perovskite double-ended tandem solar cell according to claim 3, wherein: the metal oxide nanocrystal is prepared by an evaporation condensation method, a chemical vapor reaction method, a precipitation method, a spraying method, a sol-gel method, a mechanical crushing method, a solid state reaction method and an amorphous crystallization method, and can be stably dispersed in a processing solvent.
5. The tunneling junction of a perovskite/perovskite double-ended tandem solar cell according to claim 4, wherein: the dispersion solvent of the metal oxide nanocrystal comprises water, methanol, ethanol, isopropanol, toluene, chlorobenzene, o-dichlorobenzene, chloroform, methyl formate, ethyl formate and ethyl acetate.
6. The tunneling junction of a perovskite/perovskite double-ended tandem solar cell according to claim 5, wherein: the preparation method of the tunneling composite layer comprises spin coating, electrochemical deposition, soaking, blade coating, slit coating and ink-jet printing.
7. The tunneling junction of a perovskite/perovskite double-ended tandem solar cell according to claim 6, wherein: the n-type compact layer comprises titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO) and zinc tin oxide (Zn)2SnO4) The one or more n-type semiconductor materials, but not limited to the n-type semiconductor materials, and the corresponding p-type hole transport layer materials thereof described above, include nickel oxide (NiO), molybdenum oxide (MoO)3) Cuprous oxide (Cu)2O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), redox graphene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), 2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]And (3) a combination of one or more materials such as (9, 9' -spirobifluorene (Spiro-OMeTAD), poly (3, 4-ethylenedioxythiophene), polystyrene sulfonate (PEDOT: PSS), 4-butyl-N, N-diphenylaniline homopolymer (Ploy-TPD), polyvinyl carbazole (PVK) and the like, but is not limited to the p-type hole transport layer material.
8. The tunneling junction of a perovskite/perovskite double-ended tandem solar cell according to claim 7, wherein:the p-type compact layer material comprises nickel oxide (NiO) and molybdenum oxide (MoO)3) Cuprous oxide (Cu)2One or more p-type semiconductor materials such as O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), but not limited to the above p-type semiconductor materials, and the corresponding n-type hole transport layer material includes titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO), fullerene (C)60) Graphene, fullerene derivatives [6,6]-phenyl-C61-methyl butyrate (PCBM), but is not limited to n-type hole transport layer materials.
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