CN117637882A - Method for improving performance of perovskite solar cell - Google Patents
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Abstract
The invention belongs to the technical field of photovoltaic devices, and discloses a method for improving the performance of a perovskite device. The perovskite solar cell device and the preparation method thereof comprise a substrate, an anode (ITO) and an electron beam evaporation cavity transport layer (NiO) which are sequentially laminated x ) Perovskite light absorbing layer (CsPbI) 2 Br), electron beam evaporation electron transport layer (Nb) 2 O 5 ) And an electron beam evaporation cathode (Ag); and annealing the prepared device to further improve the performance of the device. Each corresponding functional layer is made of a material capable of functioning as a respective function. The method for improving the performance of the perovskite device obtains higher energy conversion efficiency, and the perovskite battery device has lower processing cost and can realize large-area processing, so that the method has good application prospect in the field of solar cells.
Description
Technical Field
The invention belongs to the technical field of photovoltaic devices, and particularly relates to a perovskite solar cell with a hole transport layer and an electron transport layer both of which are metal oxides, and a method for improving performance of the perovskite solar cell.
Background
The Miyasaka professor task group, university of Japanese tung shadow shore, early 2006 tried to use perovskite materials as light absorbing materials in dye-sensitized solar cells, they reported for the first time in 2009 dye-sensitized perovskite solar cells with a solar conversion efficiency of 3.8% (J.Am. Chem. Soc.,2009,131,6050). Next, the Nam-Gyu Park professor group of university of Korea improved energy conversion efficiency by nearly doubling (nanoscales, 2011,3,4088) by optimizing precursor solution concentration and annealing temperature, and perovskite solar cells really paid attention to their use of perovskite materials in all solid state structures like organic thin film solar cells, and improved energy conversion efficiency and stability (Sci.Rep., 2012,2,591). Because perovskite solar cells have significant advantages such as low raw material and manufacturing costs, and with the great investment in research efforts in related fields, the energy conversion efficiency of perovskite solar cells has been rapidly improved in recent decades.
Such perovskite materials generally have ABX 3 Wherein A is a basic chemical formula + Typically monovalent cations (typically methylamine ions (MA + ) Formamidine (FA) + ) Cesium ions (Cs) + ))，B 2+ Is an inorganic cation (typically Pb 2+ )，X - As halogen anions (generally I - 、Cl - And Br (Br) - ). The band gap of the perovskite material can be continuously regulated within 1.6 to 3.2 electron volts according to the types of halogen elements used. Formamidine ion (FA + ) Replacement MA + Or using Sn 2+ To replace Pb 2+ Or the band gap of the perovskite material can be further regulated by adopting methods such as mixed ions and the like, so that the sunlight absorption in a wider range is realized. Mesoporous structures are common because perovskite solar cells were originally evolved from dye sensitized solar cells. In this structure, in dense TiO 2 The selective electron transport layer is also provided with a layer made of TiO 2 A mesoporous layer composed of nano particles. The mesoporous layer is used as a framework for depositing the perovskite film, and can reduce the distance of electron diffusion so as to improve the electron collection efficiency. The mesoporous thickness used in the initial studies was about 500-600 nm, and the perovskite light absorbing material was completely infiltrated into the mesoporous framework. However, as research proceeds, it has been found that thinner mesoporous layers can be used at about 150-200 nm, whileA continuous dense perovskite light absorbing layer is formed thereon to provide a high performance device. Because the diffusion length of electrons and holes in the perovskite material is long, the perovskite solar cell with higher efficiency can be obtained by using a planar structure after the mesoporous layer is completely removed, and compared with the mesoporous perovskite solar cell, the planar perovskite solar cell with simpler structure has obvious advantages in preparation structure, so that the perovskite solar cell with the planar structure is easier to realize commercialization.
The organic groups currently used in organic-inorganic hybrid perovskite solar cells make the final device less thermally stable, while the use of inorganic cations instead of organic cationic methylamines (MA + ) And Formamidine (FA) + ) Is one of the main ways to achieve high efficiency by improving heat stability, and uses cesium (Cs) + ) The organic cation is replaced to obtain the full inorganic perovskite device, and the full inorganic component CsPbI 2 Br has proper energy band (1.8-1.9 electron volts), is favorable for being integrated with the existing silicon-based solar cell to prepare a series cell, and can further obtain a high-efficiency cell device. The organic hole transport materials currently used in high performance perovskite solar cells often require dopant doping due to their low mobility, however, the dopant tends to diffuse into the perovskite layer causing decomposition, which limits their further commercial application. Perovskite materials are polycrystalline structure films in photovoltaic devices, perovskite crystal structures prepared by a solution method at present can cause a perovskite film body or grain boundary or more defect states between interfaces contacted with a transmission layer due to defects of an internal structure or components and the like, the defects can reduce the performance and stability of the devices, and the method for treating the prepared complete perovskite photovoltaic devices by a proper method to reduce the defect states is an effective measure for improving the performance and stability of the complete perovskite photovoltaic devices.
Disclosure of Invention
In order to solve the above drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide a method of improving the performance of a perovskite battery device.
Another object of the present invention is to provide a photoactive layer for a perovskite solar cell device using an inorganic perovskite component.
Another object of the present invention is to provide a hole transport layer using nickel oxide as a perovskite solar cell device.
Another object of the present invention is to provide an electron transport layer using niobium oxide as a perovskite solar cell device.
The invention aims at realizing the following technical scheme:
a hole transport layer using nickel oxide as a perovskite solar cell device comprises a substrate, an anode, an electron beam evaporation hole transport layer, a perovskite light absorption layer, an electron beam evaporation electron transport layer and an electron beam evaporation cathode which are sequentially stacked, wherein the prepared perovskite solar cell device is placed on a heating table for annealing treatment, the annealing temperature is adjusted from 60 ℃ to 100 ℃ at intervals of 10 ℃, and the thermal annealing treatment is carried out for 30 minutes at each temperature, and the structural schematic diagram is shown in figure 1.
The substrate is a hard substrate such as glass, quartz, sapphire and the like, and a metal, alloy or stainless steel film and the like.
The anode and the cathode are metal or metal oxide or poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) and modified products thereof; the metal is preferably aluminum, silver-magnesium alloy, silver, gold, titanium and copper; the metal oxide is preferably one or a combination of more than two of Indium Tin Oxide (ITO), fluorine-doped tin dioxide (FTO), zinc oxide (ZnO) and Indium Gallium Zinc Oxide (IGZO).
The hole transport layer may be a single transport layer or a multilayer comprising electron and exciton blocking layers.
The perovskite light absorbing material is prepared from perovskite light absorbing materials of blended or non-blended halogen; the perovskite material light absorption layer can be a single-layer or a multi-layer modification layer.
The electron transport layer may be a single transport layer or a multilayer comprising hole and exciton blocking layers.
An anode buffer layer (also called anode interface layer) can be added between the anode and the hole transport layer; a cathode buffer layer (also called a cathode interface layer) can be added between the cathode and the electron transport layer.
The method for preparing the annealed perovskite solar cell device comprises the following steps of:
and taking a substrate material with an anode layer, and sequentially preparing a hole transport layer, a perovskite light absorption layer, an electron transport layer and a cathode on the anode layer to obtain the perovskite solar cell device.
The prepared perovskite battery device is subjected to thermal annealing treatment, and the heating method comprises contact type heating, such as direct heating of a heating table, or non-contact type heating, such as radiation heating, or the like, or a combination of the heating methods.
The method for preparing the device comprises one or more of electron beam evaporation, thermal evaporation, knife coating, spin coating, brush coating, spray coating, dip coating, roller coating, printing, slit coating or ink jet printing.
The preparation method of the invention and the obtained device have the following advantages and beneficial effects:
(1) The method disclosed by the invention is used for processing the device after the device is prepared and molded so as to further improve the performance of the device;
(2) The device provided by the invention uses electron beam vapor plating nickel oxide as a hole transport layer, and provides a feasible implementation scheme for realizing large-area low-cost preparation of perovskite solar cell devices;
(3) The electron transport layer of the device can realize a large-area uniform film by utilizing electron beam evaporation of niobium oxide, and provides a feasible implementation scheme for realizing large-area low-cost preparation of perovskite solar cell devices.
Drawings
FIG. 1 is a schematic diagram of a layered structure of a perovskite solar cell device of the invention, in turn ITO/NiO x /CsPbI 2 Br/Nb 2 O 5 Schematic of annealing the device;
FIG. 2 is a graph showing the current density vs. voltage characteristics of the perovskite solar cell device obtained in example 2 before and after annealing;
FIG. 3 is a graph showing the current density vs. voltage characteristics of the perovskite solar cell device obtained in example 3 before and after annealing;
FIG. 4 is a graph showing the current density vs. voltage characteristics of the perovskite solar cell device obtained in example 4 before and after annealing;
FIG. 5 is a graph showing the current density vs. voltage characteristics of the perovskite solar cell device obtained in example 5 before and after annealing;
FIG. 6 is a graph showing the current density vs. voltage characteristics of the perovskite solar cell device obtained in example 6 before and after annealing;
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
Several ITO conductive glass substrates of the same batch number are taken, the thickness of the ITO is about 200 nanometers, and the square resistance is about 20 ohms/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, the energy conversion efficiency of the perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and the evaporated nickel oxide substrate is annealed at 300 ℃ in air for 1 hour and then transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 42 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and a large-area uniform film can be obtained by using electron beam evaporation equipment to prepare the hole transport layer and the electron transport layer, so that battery devices with large areas and different shapes can be prepared by using different masks; evaporating metallic silver as the cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer metal silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
and after the device is prepared, the device is taken out of the evaporation cavity. Testing was then performed in air with a SAN-ELECTRIC (XES-40S 2-CE) solar simulator lamp, and device current voltage information was determined by 2400 power meter manufactured by Ginkilli corporation (Keithley). The current density, the filling factor and the power conversion efficiency of the device can be respectively calculated through the information such as current, voltage, light intensity and the like.
Example 2
Performing performance test on a certain device prepared in the embodiment 1 to obtain the performance of the device before annealing; then placing the device on a heating table for thermal annealing treatment, setting the temperature of the heating table to 60 ℃, and testing after annealing the device for 30 minutes to obtain the performance of the annealed device; and comparing the current density-voltage characteristic curves of the devices obtained by testing before and after annealing.
Perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristics of (60 nm)/silver (100 nm) before and after annealing are shown in fig. 2.
Example 3
Performing performance test on a certain device prepared in the embodiment 1 to obtain the performance of the device before annealing; then placing the device on a heating table for thermal annealing treatment, setting the temperature of the heating table to 70 ℃, and testing after annealing the device for 30 minutes to obtain the performance of the annealed device; and comparing the current density-voltage characteristic curves of the devices obtained by testing before and after annealing.
Perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristics of (60 nm)/silver (100 nm) before and after annealing are shown in fig. 3.
Example 4
Performing performance test on a certain device prepared in the embodiment 1 to obtain the performance of the device before annealing; then placing the device on a heating table for thermal annealing treatment, setting the temperature of the heating table to 80 ℃, and testing after annealing the device for 30 minutes to obtain the performance of the annealed device; and comparing the current density-voltage characteristic curves of the devices obtained by testing before and after annealing.
Perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristics of (60 nm)/silver (100 nm) before and after annealing are shown in fig. 4.
Example 5
Performing performance test on a certain device prepared in the embodiment 1 to obtain the performance of the device before annealing; then placing the device on a heating table for thermal annealing treatment, setting the temperature of the heating table to 90 ℃, and testing after annealing the device for 30 minutes to obtain the performance of the annealed device; and comparing the current density-voltage characteristic curves of the devices obtained by testing before and after annealing.
Perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (300-400 nm)/Nb 2 O 5 Current density before and after (60 nm)/silver (100 nm) annealingThe voltage characteristic is shown in fig. 5.
Example 6
Performing performance test on a certain device prepared in the embodiment 1 to obtain the performance of the device before annealing; then placing the device on a heating table for thermal annealing treatment, setting the temperature of the heating table to be 100 ℃, and testing after annealing the device for 30 minutes to obtain the performance of the annealed device; and comparing the current density-voltage characteristic curves of the devices obtained by testing before and after annealing.
Perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 6.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A method of improving the performance of a perovskite device, comprising: the perovskite battery device structurally comprises a substrate, an anode ITO and an electron beam evaporation cavity transport layer NiO which are sequentially laminated x Perovskite photoactive layer, electron beam evaporation electron transport layer Nb 2 O 5 And evaporating cathode Ag, and annealing the prepared device to obtain a device with higher performance.
2. A method of improving the performance of a perovskite device as claimed in claim 1, wherein: the substrate is a glass, quartz, sapphire, metal, alloy or stainless steel film; the anode and the cathode are metal, metal oxide, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) or modified products thereof.
3. A method of improving the performance of a perovskite device as claimed in claim 1, wherein: the metal refers to aluminum, silver, gold or silver magnesium alloy, titanium, copper and the like which can be used as electrodes; the metal oxide refers to one or a combination of more than two of indium tin oxide, fluorine-doped tin dioxide, zinc oxide, indium gallium zinc oxide and the like which can serve as electrodes.
4. A method of improving the performance of a perovskite device as claimed in claim 1, wherein: the hole transport layer is not limited to a single layer, but includes a multilayer case where electron and exciton blocking layers are added.
5. A method of improving the performance of a perovskite device as claimed in claim 1, wherein: the perovskite photoactive layer is prepared from perovskite light absorbing materials with different components, which are blended or unblended; the light absorbing layer is a single layer or multiple layers.
6. A method of enhancing the performance of a perovskite device according to claim 1, wherein said electron transport layer is not limited to a single layer, including the multilayer case of an added hole, exciton blocking layer.
7. A method of improving the performance of a perovskite device as claimed in claim 1, wherein: an anode buffer layer can be added between the anode and the hole transport layer; a cathode buffer layer can be added between the cathode and the electron transport layer.
8. A method of improving the performance of a perovskite device as claimed in claim 1, wherein: the thermal annealing method comprises a contact type heating mode such as direct heating of a heating table or non-contact type heating such as thermal annealing treatment of a device by using heat radiation.
9. A method of enhancing the performance of a perovskite device as claimed in any one of claims 1 to 8, comprising the steps of: and taking a substrate material with an anode layer, sequentially preparing a hole transport layer nickel oxide, a perovskite photoactive layer, an electron transport layer niobium oxide and a cathode on the anode layer to obtain the perovskite battery device, and then carrying out annealing treatment on the device.
10. A method of improving the performance of a perovskite device as claimed in claim 9, wherein: the preparation method comprises one or more of electron beam evaporation, thermal evaporation, spin coating, knife coating, brush coating, spray coating, dip coating, roller coating, printing, slit coating or ink jet printing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311647043.4A CN117637882A (en) | 2023-12-04 | 2023-12-04 | Method for improving performance of perovskite solar cell |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311647043.4A CN117637882A (en) | 2023-12-04 | 2023-12-04 | Method for improving performance of perovskite solar cell |
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