CN110600614B - Tunneling junction structure of perovskite/perovskite two-end laminated solar cell - Google Patents
Tunneling junction structure of perovskite/perovskite two-end laminated solar cell Download PDFInfo
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Abstract
The invention discloses a tunneling junction structure of a perovskite/perovskite two-end laminated solar cell and application thereof. The tunneling junction structure comprises a tunneling composite layer, wherein a compact layer is arranged on one side of the tunneling composite layer, a transmission layer is arranged on the other side of the tunneling composite layer, and the tunneling composite layer is made of a metal material. 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 double-end laminated solar cell, has simple preparation process and lower cost, and is suitable for large-area industrial mass production.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a tunneling junction structure of a perovskite/perovskite two-end laminated solar cell and application thereof.
Background
Tandem solar cells are an efficient, most feasible way to achieve higher photoelectric conversion efficiency compared to single junction solar cells. From the highest photoelectric conversion efficiency of solar cells of various materials and structures provided by the us renewable energy laboratory (NREL), the highest multi-junction cell efficiency currently exceeds 38%, while the best single-junction device is about 29%. However, the materials for realizing such high efficiency cells are group III-V semiconductors, and high temperature and low growth rate are generally required to obtain high quality III-V semiconductor materials, so that the III-V stacked cell is very expensive and cannot realize large-scale ground power generation applications.
The organic-inorganic hybrid perovskite solar cell is widely concerned in the photovoltaic field all over the world due to the advantages of low cost and high efficiency, and the certification efficiency of a unijunction cell reaches over 25 percent from 2009 report to the present day. However, perovskite materials for realizing high-efficiency single-junction perovskite solar cells have band gaps of about 1.5 eV and have limited absorption of solar spectra.
In order to obtain higher photoelectric conversion efficiency of the perovskite cell, a perovskite-based two-end laminated cell is the most effective way to break through the limit of single junction efficiency. In the perovskite/perovskite both-end laminated solar cell, the perovskite with a wide band gap is used as a top cell to absorb sunlight with a short wavelength part, the perovskite with a narrow band gap is used as a bottom cell to absorb sunlight with a long wavelength part, the utilization rate of a solar spectrum can be improved, the thermal relaxation loss of a current carrier in a single junction cell is reduced, and the photoelectric conversion efficiency is improved. The perovskite/perovskite two-end laminated solar cell has low energy consumption in preparation, and the preparation method is simple by adopting a solution method. However, in the existing perovskite/perovskite two-end laminated solar cell, when the second layer of perovskite is prepared by a solution method, the prepared perovskite of the first layer is easy to damage, so a compact solvent barrier layer is needed in the middle, and the effect of laminating, series connection and interconnection needs to be achieved. In the tunneling junction structure adopted by most of the reported perovskite/perovskite two-end laminated cells, the dense layer and the tunneling composite layer are indium-doped tin oxide (ITO) prepared by sputtering, and the thickness of the indium-doped tin oxide (ITO) generally needs about 100 nm to play a role of solvent barrier. However, as the thickness of the ITO increases, the manufacturing cost increases in addition to increasing the parasitic absorption of the ITO itself. And the ITO has good conductivity, so that short circuit of adjacent batteries is easily caused in the preparation of battery components.
Disclosure of Invention
The invention aims to solve the problem of solvent orthogonality in the perovskite/perovskite double-end laminated solar cell prepared by the existing solution method, reduce the loss of open-circuit voltage and short-circuit current of the laminated cell in a tunneling junction, provide a tunneling junction structure with a compact layer and a metal layer, have the function of carrier tunneling recombination, simplify the preparation process of the perovskite/perovskite double-end laminated solar cell, and can be applied to the preparation of a large-area and high-efficiency perovskite/perovskite double-end laminated solar cell.
In order to achieve the above object, the present invention adopts the following technical means:
a tunneling junction structure of a perovskite/perovskite two-end laminated solar cell comprises a tunneling composite layer, wherein a compact layer is arranged on one side of the tunneling composite layer, and a transmission layer is arranged on the other side of the tunneling composite layer.
Further, the tunneling composite layer is made of a metal material, which includes, but is not limited to, gold, palladium, silver, titanium, chromium, nickel, aluminum, or copper.
Furthermore, the tunneling composite layer is a continuous metal film, a metal nanoparticle film or an uncompacted metal island-shaped structure layer.
Further, the compact layer and the transmission layer are both made of n-type or p-type semiconductor materials.
Further, the compact layer is made of an n-type semiconductor material, and the transmission layer is made of a p-type semiconductor material.
Further, the compact layer is made of a p-type semiconductor material, and the transmission layer is made of an n-type semiconductor material.
A perovskite/perovskite two-end laminated solar cell comprises the tunneling junction structure.
Furthermore, the laminated solar cell is of a p-i-n structure and sequentially comprises a transparent conductive substrate, a p-type hole transport layer, a wide-band gap perovskite, an n-type electron transport layer, an n-type compact layer, a tunneling composite layer, a p-type hole transport layer, a narrow-band gap perovskite, an n-type electron transport layer and a back electrode from bottom to top.
Furthermore, the laminated solar cell is of an n-i-p structure and sequentially comprises a transparent conductive substrate, an n-type electron transmission layer, a wide-band gap perovskite, a p-type hole transmission layer, a p-type compact layer, a tunneling composite layer, an n-type electron transmission layer, a narrow-band gap perovskite, a p-type hole transmission layer and a back electrode from bottom to top.
The invention adopts a compact n-type or p-type semiconductor material as a compact barrier layer of a solvent, a thin metal layer as a tunneling composite layer of a laminated cell at two ends, and a p-type or n-type transmission layer corresponding to the compact barrier layer to form a simple tunneling junction structure. On one hand, the addition of the compact barrier layer can solve the problem of solvent orthogonality in the preparation of the second layer of perovskite; on the other hand, the metal layer has very good conductivity, so that the tunneling recombination effect of electron holes can be achieved, the open-circuit voltage loss at the tunneling junction is reduced, the filling factor of the cell is improved, and the conversion efficiency of the laminated solar cell is improved.
The invention can solve the problems of self parasitic absorption and related device design of the traditional thicker ITO, effectively reduce the open circuit voltage loss of the laminated cell, promote the filling factor of the perovskite/perovskite double-end laminated solar cell, improve the photoelectric conversion efficiency of the perovskite/perovskite double-end laminated solar cell, simplify the preparation process of the perovskite/perovskite laminated solar cell, lower the cost and be suitable for large-area industrial mass production.
Drawings
FIG. 1 is a schematic device structure diagram of a perovskite/perovskite tandem solar cell in the invention, wherein a is a p-i-n structure tandem solar cell, and b is an n-i-p structure tandem solar cell.
FIG. 2 is a scanning electron micrograph of a tandem solar cell of p-i-n structure according to example 1.
Fig. 3 is a current density-voltage curve of the tandem solar cell of p-i-n structure of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments.
As shown in fig. 1, the invention designs a tunneling junction structure of a perovskite/perovskite two-end tandem solar cell, which is composed of a dense layer, a metal layer and a transmission layer, wherein the dense layer is made of an n-type or p-type semiconductor material, the transmission layer is made of a corresponding p-type or n-type semiconductor material, and the n-type and p-type semiconductor materials respectively have electron and hole transmission capabilities.
In the tunneling junction structure, the compact layer protects the top battery from being damaged by the subsequent bottom battery preparation process and has electron (hole) transmission capability; the metal material layer is a tunneling composite layer of the laminated battery and plays a role in carrier tunneling recombination. Through the addition of the compact layer, the problem of solvent orthogonality in the preparation of the second layer of perovskite can be effectively solved, and meanwhile, the metal layer is made of a metal material with good conductivity, so that the tunneling recombination effect of electron holes can be achieved, the open-circuit voltage loss at a tunneling junction is reduced, and the conversion efficiency of the laminated solar cell is improved.
In the present invention, the metal layer may be made of metal materials such as gold, palladium, silver, titanium, chromium, nickel, aluminum, copper, etc., but is not limited to the above-listed metal materials. The metal layer can be a continuous metal film, or a metal nanoparticle film or a non-compact metal island-shaped structure layer. The metal layer can be prepared by deposition methods such as electron beam evaporation, thermal evaporation, magnetron sputtering, atomic layer deposition, spin coating, blade coating and the like.
The dense layer may be prepared by a physical deposition method or a chemical deposition method. Physical deposition methods include, but are not limited to, vacuum evaporation, sputtering, ion beam deposition, pulsed laser deposition, and the like; chemical deposition methods include, but are not limited to, chemical vapor deposition, atomic layer deposition, sol-gel spin coating, and the like.
The tunneling junction structure is applied to a perovskite/perovskite two-end laminated solar cell, and the laminated cell with two structures can be designed. As shown in fig. 1 a, the structure is a p-i-n structure, and sequentially comprises a transparent conductive substrate, a p-type hole transport layer, a wide band gap perovskite, an n-type electron transport layer, an n-type dense layer, a tunneling composite layer, a p-type hole transport layer, a narrow band gap perovskite, an n-type electron transport layer and a back electrode from bottom to top; as shown in fig. 1 b, the n-i-p structure sequentially includes, from bottom to top, a transparent conductive substrate, an n-type electron transport layer, a wide band gap perovskite, a p-type hole transport layer, a p-type dense layer, a tunneling composite layer, an n-type electron transport layer, a narrow band gap perovskite, a p-type hole transport layer, and a back electrode.
Specifically, in the p-i-n structure:
the n-type compact layer can be titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO), vanadium oxide (V)2O5) Zinc tin oxide (Zn)2SnO4) One or more n-type semiconductor materials, but not limited to the n-type semiconductor materials listed above;
the p-type hole transport layer can be nickel oxide (NiO) or 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]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 other p-type semiconductor materials, but are not limited to the p-type semiconductor materials listed above.
Specifically, in the n-i-p structure:
the p-type dense layer can be nickel oxide (NiO) or molybdenum oxide (MoO)3) Cuprous oxide (Cu)2O), copper iodide (CuI), copper phthalocyanine (CuPc), cuprous thiocyanate (CuSCN), but not limited to the above listed p-type semiconductor materials;
the n-type hole transport layer can be titanium oxide (TiO)2) Tin oxide (SnO)2) Zinc oxide (ZnO), fullerene (C)60) Graphene, fullerene derivatives [6,6]phenyl-C61-methyl butyrate (PCBM) and the like, but is not limited to the n-type semiconductor materials listed above.
The above-described scheme is further illustrated below with reference to specific examples.
Example 1
In this example 1, a perovskite/perovskite two-end stacked solar cell is prepared by using the structure shown in fig. 1 a, and the specific preparation process is as follows:
1. a layer of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) with the thickness of about 20 nm is prepared on a cleaned ITO substrate to be used as a hole transport layer.
2. Depositing a layer of wide band gap perovskite on the prepared hole transport layer, wherein the thickness of the wide band gap perovskite is about 300 nm.
3. Preparation of a layer of fullerene (C) by thermal evaporation60) As an electron transport layer, the thickness was about 20 nm.
4. Using atomic layer deposition on C60A layer of SnO is grown on the surface2As a dense layerAnd the thickness is 20 nm.
5. The tunneling composite layer adopts Au evaporated by thermal evaporation, and the thickness is 2 nm.
6. The p-type hole transport layer was prepared using poly-3, 4-ethylenedioxythiophene polystyrene sulfonate (PEDOT: PSS).
7. In the preparation of the prepared PEDOT: and preparing a second layer of narrow-band-gap perovskite on the PSS layer, wherein the thickness is about 700 nm.
8. Preparation of a layer C by thermal evaporation60And 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) as electron transport layers, with thicknesses of 30 and 7 nm, respectively.
9. Finally, a layer of Cu with the thickness of 150 nm is evaporated by thermal evaporation to be used as a back electrode.
Fig. 2 is a scanning electron micrograph (cross-sectional view) of the resulting tandem solar cell.
SnO prepared by Atomic Layer Deposition (ALD)2The compactness is very good, plays a role in blocking a solvent, and the good conductivity of Au provides good tunneling recombination. As shown in fig. 3, without the Au tunneling composite layer, the photoelectric conversion efficiency of the device is 14.5%; and after Au is used as a tunneling composite layer, the photoelectric conversion efficiency can be improved to 20.9%.
Claims (7)
1. A tunneling junction structure of a perovskite/perovskite two-end laminated solar cell is characterized in that: the tunneling composite layer is arranged on one side of the tunneling composite layer, and a compact layer and a transmission layer are arranged on the other side of the tunneling composite layer;
the tunneling composite layer is made of a metal material, and the metal material is selected from gold, palladium, silver, titanium, chromium, nickel, aluminum or copper;
the tunneling composite layer is a continuous metal film, a metal nanoparticle film or a non-compact metal island-shaped structure layer.
2. The tunneling junction structure of claim 1, wherein: the compact layer and the transmission layer are both made of n-type or p-type semiconductor materials.
3. The tunneling junction structure of claim 2, wherein: the compact layer is made of an n-type semiconductor material, and the transmission layer is made of a p-type semiconductor material.
4. The tunneling junction structure of claim 2, wherein: the compact layer is made of a p-type semiconductor material, and the transmission layer is made of an n-type semiconductor material.
5. A perovskite/perovskite two-end tandem solar cell, characterized by: comprising the tunnel junction structure of claim 1.
6. The perovskite/perovskite two-end-stacked solar cell according to claim 5, wherein: the laminated solar cell is of a p-i-n structure and sequentially comprises a transparent conductive substrate, a p-type hole transmission layer, a wide-band gap perovskite, an n-type electron transmission layer, an n-type compact layer, a tunneling composite layer, a p-type hole transmission layer, a narrow-band gap perovskite, an n-type electron transmission layer and a back electrode from bottom to top.
7. The perovskite/perovskite two-end-stacked solar cell according to claim 5, wherein: the laminated solar cell is of an n-i-p structure and sequentially comprises a transparent conductive substrate, an n-type electron transmission layer, a wide-band gap perovskite, a p-type hole transmission layer, a p-type compact layer, a tunneling composite layer, an n-type electron transmission layer, a narrow-band gap perovskite, a p-type hole transmission layer and a back electrode from bottom to top.
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| CN112909181A (en) * | 2021-02-08 | 2021-06-04 | 南京大学 | Tunneling junction of perovskite/perovskite two-end laminated solar cell |
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