CN115188891A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- CN115188891A CN115188891A CN202210656730.1A CN202210656730A CN115188891A CN 115188891 A CN115188891 A CN 115188891A CN 202210656730 A CN202210656730 A CN 202210656730A CN 115188891 A CN115188891 A CN 115188891A
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
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- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/83—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising arrangements for extracting the current from the cell, e.g. metal finger grid systems to reduce the serial resistance of transparent electrodes
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Abstract
The invention relates to the technical field related to solar cells, in particular to a perovskite solar cell, which is sequentially provided with a transparent conductive substrate layer, a first contact layer, a perovskite light absorption layer, a second contact layer and a conductive electrode layer from bottom to top; the transparent conductive substrate layer comprises a transparent substrate layer and a transparent oxide conductive layer, and a plurality of conductive contact layers are arranged between the first contact layer and the transparent conductive substrate layer; according to the invention, the conductive electrode is deeply inserted into the first contact layer in a manner of preparing the conductive contact layer, and the conductivity of the ITO film is improved, so that the conductive contact layer increases the contact area and the extraction speed of the conductive electrode on a photon-generated carrier, reduces the carrier recombination, and further improves the photoelectric property of perovskite solar energy; the conductive contact layer is simple in preparation process, high in feasibility and repeatability, free of influence on the surface appearance of the perovskite thin film and beneficial to preparation of perovskite solar cells.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite solar cell and a preparation method thereof.
Background
As a new pet in the photovoltaic industry, the perovskite cell has been developed for 13 years, and the photoelectric conversion efficiency of the perovskite cell is rapidly increased from 3.8% to 25.7%. The perovskite material is a remarkable label of perovskite due to low cost, high efficiency and good tolerance to defects, and more researchers think that the perovskite material has the potential exceeding that of a crystalline silicon battery and a CIGS thin-film battery, so that the perovskite material is also evaluated as one of ten scientific breakthroughs in 2013 by 'Science'.
At present, the photoelectric conversion efficiency of perovskite cells in most laboratories is lower than 22%, although the photoelectric conversion efficiency of perovskite devices can be improved to more than 23% by means of interface modification, material system optimization, process optimization and the like, the preparation process is complicated, the requirement on the quality of the film is high, for example, the process for processing the perovskite absorption layer and the contact layer by adopting the interface modification method is unstable and poor in repeatability, and therefore, an efficiency improvement scheme of perovskite cells with low requirement on the quality of perovskite films and high repeatability is absent at present.
In the prior art, the perovskite battery is prepared by adopting a planar structure, so that the problems of poor film quality and excessive recombination centers exist, and meanwhile, the ITO substrate has low conductivity, so that the transmission of current carriers is not facilitated, and the device has low photoelectric conversion efficiency.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide a perovskite solar cell and a preparation method thereof, which adopt a local contact type contact layer preparation mode to improve the problems of low efficiency and poor repeatability of the perovskite solar cell.
In order to achieve the purpose, the invention provides the following technical scheme: a perovskite solar cell is provided with a transparent conductive substrate layer, a first contact layer, a perovskite light absorption layer, a second contact layer and a conductive electrode layer from bottom to top in sequence; the transparent conductive substrate layer comprises a transparent substrate layer and a transparent oxide conductive layer, a plurality of conductive contact layers are arranged between the first contact layer and the transparent conductive substrate layer, and the conductive contact layers are embedded into the first contact layer and the transparent conductive substrate layer.
Compared with the prior art, the invention has the beneficial effects that:
(1) By means of preparing the conductive contact layer, the conductive electrode is deep into the first contact layer, and the conductivity of the ITO film is improved, so that the contact area of the conductive contact layer is increased, the extraction speed of the conductive electrode on a photon-generated carrier is increased, the carrier recombination is reduced, and the photoelectric performance of the perovskite solar energy is improved;
(2) The preparation process of the conductive contact layer is simple and easy to implement, low in cost, high in implementability and repeatability, free of influence on the surface morphology of the perovskite thin film, and beneficial to preparation of the efficient perovskite solar cell.
Further, a plurality of the conductive contact layers are arranged in an array.
Further, the transparent substrate layer is at least one of glass, PET, PEN, PEI and PMMA.
Further, the transparent conductive oxide layer is made of at least one of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide and IGO indium-doped oxide.
Furthermore, the material of the conductive contact layer is at least one of transparent conductive oxides such as FTO, ITO, AZO, ATO, IGO and the like or conductive metals such as Ag, au, fe, al, mg, ni, cu, na and the like.
Further, the material of the conductive contact layer may be the same as or different from the material of the transparent conductive oxide layer.
Further, the conductive contact layer is deposited in at least one of mask PVD deposition, screen printing, chemical bath deposition and sol-gel method.
Further, one of the first contact layer and the second contact layer is made of at least one of N-type semiconductors SnO2, tiO2 and ZnSnO4, and the other is made of at least one of P-type semiconductors Spiro-oMeTad, niO and CuSCN.
Further, the perovskite layer is made of a perovskite material with an ABX3 type crystal structure.
Further, A is at least one of Cs +, CH (NH 2) 2+, CH3NH3+ and C (NH 2) 3+, B is at least one of Pb2+ and Sn2+, and X is at least one of Br-, I-and Cl-.
Further, the conductive electrode layer is made of at least one of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide, IGO indium-doped tin oxide, and Ag, cu, al, and Au.
Drawings
FIG. 1 is a schematic overall sectional structure of an embodiment of the present invention;
FIG. 2 is a schematic view of a manufacturing process according to an embodiment of the present invention;
fig. 3 is a schematic top view of a conductive contact layer according to an embodiment of the invention.
In the figure: 11. a perovskite absorption layer; 12. a second contact layer; 13. a conductive electrode; 14. a glass substrate layer; 15. a transparent oxide conductive layer; 16. a first contact layer; 17. a conductive contact layer.
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 it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example (b):
referring to fig. 1, the present invention provides a large-area perovskite solar cell as shown in fig. 1, the perovskite solar cell sequentially comprises a perovskite cell from bottom to top, the perovskite cell comprises a transparent substrate layer 14, a transparent conductive oxide layer 15, a conductive contact layer 17, a first contact layer 16, a perovskite light absorption layer 11, a second contact layer 12 and a conductive electrode layer 13, the transparent conductive substrate comprises a transparent conductive oxide layer 15 and a transparent substrate layer 14, a thin conductive contact layer 17 is deposited on the upper surface of the transparent conductive oxide layer 15 according to a pattern, the conductive contact layers 17 are arranged on the surface of the transparent conductive oxide layer 15 in an array manner, the first contact layer 16 is deposited on the conductive contact layer 17 at one time, the conductive contact layer 17 is embedded in the transparent oxide layer 15 and the first contact layer 16, so as to ensure current flow, and the perovskite light absorption layer 11, the second contact layer 12 and the conductive electrode layer 13 are sequentially deposited on the upper surface of the first contact layer 16.
When the solar cell module is used and operated, the transparent substrate layer 14 is positioned above and directly contacts with sunlight, the light transmission is required to be ensured, and the transparent substrate layer 1 is at least one of glass, PET, PEN, PEI and PMMA;
the transparent conductive oxide layer 15 is made of at least one of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide and IGO indium-doped tin oxide, and the wavelength of laser etching is at least one of 405nm, 445nm, 460nm, 473nm, 532nm, 589nm, 635nm, 650nm, 808nm, 980nm and 1064 nm; preferably 532nm/1064nm, i.e. to act as an etch trench for depositing the conductive contact layer 17, facilitating the embedding of the conductive contact layer 17.
The conductive contact layer 17 is embedded into the first contact layer 16 and the transparent conductive oxide layer 15, so that conductive work is achieved, the conductive contact layer 17 is formed by a plurality of uniformly distributed devices, as shown in fig. 3, materials can be saved, work efficiency is improved, it is required to ensure that a conductive electrode can better extract photogenerated carriers, the conductive contact layer is made of transparent conductive oxides such as FTO, ITO, AZO, ATO, IGO and the like or at least one of conductive materials such as Ag, au, fe, al, mg, ni, cu, na, graphite and the like, the conductive contact layer 17 can be the same as or different from the transparent conductive oxide layer, the deposition mode of the conductive contact layer 17 is selected from at least one of mask PVD deposition, screen printing, chemical bath deposition and sol-gel methods, preferably mask PVD deposition, and has a better effect.
The materials of the first contact layer 12 and the second contact layer 16 are at least one of N-type semiconductors SnO2, tiO2, znSnO4 or P-type semiconductors Spiro-oMeTad, niO, cuSCN, the N-type semiconductor is used for transmitting electrons, the P-type semiconductor is used for transmitting holes, the materials of the first contact layer 12 and the second contact layer 16 are not the same, but both the N-type semiconductor and the P-type semiconductor can be selected at will, and when one of the contact layer materials is the N-type semiconductor, the other contact layer material needs to be the P-type semiconductor.
The perovskite layer 5 is made of a perovskite material with an ABX3 type crystal structure, A is at least one of Cs +, CH (NH 2) 2+, CH3NH3+ and C (NH 2) 3+, B is at least one of Pb2+ and Sn2+, and X is at least one of Br-, I-and Cl-; the conductive electrode layer 7 is made of at least one of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide, IGO indium-doped gallium and Ag, cu, al and Au;
a method for manufacturing a perovskite solar cell is shown in fig. 2, and comprises the following steps:
the method comprises the following steps: etching of transparent conductive glass 1+2
Adopting FTO glass with the square resistance of 5 omega/9633and the transmittance of 92 percent, using laser with the wavelength of 532nm and the power of 10W, and etching according to the graph shown in figure 3 to obtain the FTO glass with an etching structure, wherein the depth of an etching groove is 1/2 of the thickness of the FTO conducting layer; because the conductivity of the conductive contact layer 3 is higher than that of the transparent conductive oxide, the conductivity of the conductive substrate after compounding is improved by etching the TCO and depositing the conductive contact layer at the etching position, and meanwhile, the contact area is increased due to the existence of the etching groove, which is equivalent to the improvement of the carrier collection capacity.
Step two: cleaning of transparent conductive glass substrate 1+2
Sequentially adopting a detergent, deionized water, acetone and ethanol to respectively carry out ultrasonic cleaning on the etched FTO substrate for 20min, then carrying out purging by high-purity nitrogen and then cleaning by using an oxygen plasma cleaning machine for 10min to obtain a clean transparent conductive substrate 1+2;
step three: preparation of the electrically conductive contact layer 3
Placing the transparent conductive substrate with the cleaned surface on a mask with a specific pattern, and depositing in a thermal evaporation mode; during operation, when the vacuum degree of the chamber is reduced to below 5.0x10 < -4 > Pa, evaporation is started, the current of the heating disc is controlled to be stabilized at 25A, a 150nm gold electrode is deposited on the substrate at the speed of 1A/s, and the obtained conductive contact layer completely covers the etching groove and is 10nm higher than the FTO electrode;
step four: preparation of the first contact layer 4
Mixing SnO2 dispersion liquid and deionized water in a volume ratio of 1:7 to obtain SnO2 precursor liquid, and depositing a 20nm SnO2 electron transport layer on the substrate in a Slot-die coating manner, wherein the first contact layer completely covers the conductive contact layer, and the thickness of the conductive contact layer 3 is 1/2 of the thickness of the first contact layer 4;
step five: preparation of perovskite light absorption layer 5
Mixing the components in a molar ratio of 1:1.01, adding CH3NH3I powder and PbI2 into a mixed solvent system of DMF/DMSO (volume ratio is 3.
Step six: preparation of the second contact layer 6
A slit-die coating method is adopted to prepare a Spiro-oMeTad wet film on a perovskite light absorption layer 5 substrate, and a heating and drying method is adopted for 10min to finally obtain a hole transport layer with the film thickness of 120nm.
Step seven: preparation of the conductive electrode layer 7
Continuing to deposit a gold electrode on the second contact layer; in operation, evaporation was started when the vacuum degree of the chamber was reduced to 5.0X10-4Pa or less, and at the same time, the current of the heating plate was controlled to be stabilized at 25A, and 70nm of gold electrode was deposited on the substrate at a rate of 1A/s.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (21)
1. A perovskite solar cell, characterized in that: the solar cell is sequentially provided with a transparent conductive substrate layer, a first contact layer, a perovskite light absorption layer, a second contact layer and a conductive electrode layer from bottom to top; the transparent conductive substrate layer comprises a transparent substrate layer and a transparent oxide conductive layer, a plurality of conductive contact layers are arranged between the first contact layer and the transparent conductive substrate layer, and the conductive contact layers are embedded into the first contact layer and the transparent conductive substrate layer.
2. The perovskite solar cell of claim 1, wherein: and a plurality of conductive contact layers are arranged in an array.
3. A perovskite solar cell according to claim 1, characterized in that: the transparent substrate layer is at least one of glass, PET, PEN, PEI and PMMA.
4. The perovskite solar cell of claim 2, wherein: the transparent conductive oxide layer is made of at least one of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide and IGO indium-doped oxide.
5. A perovskite solar cell according to claim 1, characterized in that: the conductive contact layer is made of at least one of transparent conductive oxides such as FTO, ITO, AZO, ATO and IGO or conductive metals such as Ag, au, fe, al, mg, ni, cu and Na.
6. The perovskite solar cell according to claim 4, wherein: the material of the conductive contact layer may be the same as or different from the material of the transparent conductive oxide layer.
7. The perovskite solar cell of claim 5, wherein: the conductive contact layer is deposited in at least one of mask PVD deposition, screen printing, chemical bath deposition and sol-gel method.
8. A perovskite solar cell according to claim 1, characterized in that: one of the first contact layer and the second contact layer is made of at least one of N-type semiconductors SnO2, tiO2 and ZnSnO4, and the other one of the first contact layer and the second contact layer is made of at least one of P-type semiconductors Spiro-oMeTad, niO and CuSCN.
9. A perovskite solar cell according to claim 1, characterized in that: the perovskite layer is made of perovskite material with an ABX3 type crystal structure.
10. The perovskite solar cell of claim 8, wherein: the A is at least one of Cs +, CH (NH 2) 2+, CH3NH3+ and C (NH 2) 3+, the B is at least one of Pb2+ and Sn2+, and the X is at least one of Br-, I-and Cl-.
11. A perovskite solar cell according to claim 1, characterized in that: the conductive electrode layer is made of at least one of FTO fluorine-doped tin oxide, ITO indium-doped tin oxide, AZO aluminum-doped zinc oxide, ATO aluminum-doped tin oxide, IGO indium-doped oxidized gallium and Ag, cu, al and Au.
12. A preparation method of a perovskite solar cell comprises the following steps:
(a) Etching the transparent conductive substrate according to a specific pattern by using laser;
(b) Ultrasonically cleaning the transparent conductive substrate for 20min by sequentially adopting a detergent, deionized water, acetone and ethanol, then purging the transparent conductive substrate by using high-purity nitrogen, and cleaning the transparent conductive substrate for 20min by using an oxygen plasma cleaning machine to obtain a clean transparent conductive substrate;
(c) Placing the transparent conductive substrate on a mask plate with a specific pattern, and depositing a conductive contact layer in a thermal evaporation mode;
(d) Depositing a first contact layer on the substrate;
(e) Depositing a perovskite light absorbing layer on the first contact layer;
(f) Depositing a second contact layer on the transparent conductive substrate;
(g) Continuously depositing a conductive electrode layer on the surface of the second contact layer to obtain a perovskite battery piece;
the method of manufacturing a perovskite solar cell as claimed in claim 11, wherein: the depth of the laser etching groove in the step (a) is 10-200nm, and the depth of the laser etching groove is 1/5-1 of the thickness of the transparent conductive oxide layer.
13. The method of manufacturing a perovskite solar cell as claimed in claim 12, wherein: the wavelength of the laser is at least one of 405nm, 445nm, 460nm, 473nm, 532nm, 589nm, 635nm, 650nm, 808nm, 980nm and 1064 nm.
14. The method according to claim 11, wherein the perovskite solar cell is prepared by: in the step (c), the thickness of the conductive contact layer is 10-100nm, the thickness of the conductive contact layer is 1/5-4/5 of the thickness of the first contact layer, and the conductivity of the conductive contact layer and the ITO composite layer is lower than that of the transparent oxide.
15. The method of manufacturing a perovskite solar cell as claimed in claim 14, wherein: the deposition mode is at least one of mask PVD deposition, screen printing, chemical bath deposition and sol-gel method.
16. The method according to claim 11, wherein the perovskite solar cell is prepared by: the thickness of the first contact layer in the step (d) is 20-40nm.
17. The method of manufacturing a perovskite solar cell as claimed in claim 11, wherein: the thickness of the perovskite layer in the step (e) is 350 to 500nm.
18. The method of manufacturing a perovskite solar cell as claimed in claim 11, wherein: the thickness of the second contact layer in the step (f) is 80-120nm.
19. The method of manufacturing a perovskite solar cell as claimed in claim 18, wherein: the deposition method is one of spinning coating, slot-die coating, sector blanking, spray coating and Chemical Vapor Deposition (CVD).
20. The method of manufacturing a perovskite solar cell as claimed in claim 11, wherein: the thickness of the conductive electrode layer in the step (f) is 10-100nm.
21. The method of fabricating a perovskite solar cell as claimed in claim 20, wherein: the deposition mode of the step (f) is at least one of magnetron sputtering, thermal evaporation and screen printing.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116234338A (en) * | 2023-04-27 | 2023-06-06 | 广东爱旭科技有限公司 | Solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116234338A (en) * | 2023-04-27 | 2023-06-06 | 广东爱旭科技有限公司 | Solar cell |
| CN116234338B (en) * | 2023-04-27 | 2023-10-10 | 广东爱旭科技有限公司 | Solar cell |
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