CN117641947A - Method for preparing p-i-n type perovskite battery device by electron beam evaporation - Google Patents
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the technical field of photovoltaic devices, and discloses a p-i-n perovskite device structure prepared by electron beams and a preparation method thereof. The electron beam preparation p-i-n perovskite solar cell device comprises a substrate, an anode (ITO) and an electron beam evaporation cavity transport layer (NiO) which are sequentially laminated x ) Perovskite light absorption layer, electron beam evaporation electronTransport layer (Nb) 2 O 5 ) And electron beam evaporation cathodes (Ag and Ti). Each corresponding functional layer is made of a metal oxide semiconductor material capable of functioning as the corresponding function. The p-i-n type perovskite solar cell device prepared by the electron beam and the preparation method thereof have the advantages of higher energy conversion efficiency and higher open-circuit voltage, lower processing cost and capability of realizing large-area processing, thereby having 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 p-i-n type perovskite device prepared by electron beam evaporation and a method thereof.
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 dye-sensitized perovskite solar cells with solar conversion efficiencies of 3-4% in 2009 (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 years.
Such perovskite materials generally have ABX 3 Wherein A is a basic chemical formula + Typically organic cations (most commonly methylamine ions, CH 3 NH 3 + ，MA + )，B 2+ Is an inorganic cation (typically Pb 2+ )，X - As halogen anions (generally I - 、Cl - Or Br (Br) - :MAPb(I，Br，Cl) 3 ). 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. Using formamidine ion (CH (NH) 2 ) 2 + ，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, whenDense TiO 2 The selective electron transport layer is also provided with a layer made of TiO 2 A mesoporous layer composed of nano particles. On one hand, the mesoporous layer is used as a skeleton for depositing the perovskite film, and on the other hand, the distance of electron diffusion can be reduced, so that the electron collection efficiency is improved. 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, on the order of 150-200 nanometers, can be used, while forming a continuous dense perovskite light absorbing layer thereon, resulting in better device performance. 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 planar perovskite solar cell is easier to realize commercialization finally.
The perovskite solar cell device structures commonly found today include mesoporous, planar (n-i-p) and planar inversion (p-i-n). The n-type electron transport materials used in the current planar structures are typically metal oxide semiconductor materials, the p-type hole transport materials are typically organic hole transport materials, and the organic hole transport materials used often need to be doped with other substances due to their low mobility to obtain high energy conversion efficiency, which limits further commercial applications. The n-type electron transport materials used in the planar inversion structure at present are generally fullerenes and derivatives thereof, and the materials have the defects of high production cost, difficult purification and the like which restrict the mass production of the materials. Thus, development of a low-cost large-area stable planar perovskite solar cell device and a structure thereof is urgent.
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 for fabricating a p-i-n type perovskite solar cell device using electron beam evaporation.
Another object of the present invention is to provide a method for preparing a transport layer material for use in a p-i-n type perovskite solar cell device.
The invention aims at realizing the following technical scheme:
a p-i-n type perovskite solar cell device prepared by electron beam evaporation comprises a substrate, an anode, an electron beam evaporation cavity transmission layer, a perovskite light absorption layer, an electron beam evaporation electron transmission layer and an electron beam evaporation cathode which are sequentially stacked, wherein the structure schematic diagrams are shown in fig. 1 and 2.
The substrate is a hard substrate such as glass, quartz, sapphire, etc., and a flexible substrate such as polyimide, polyethylene terephthalate, polyethylene naphthalate or other polyester-based materials, metal, alloy or stainless steel films, etc.
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 a blended or unblended perovskite light absorbing material; 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 p-i-n type perovskite solar cell device by using the electron beam comprises the following steps of:
and taking a substrate material with an anode layer, and sequentially preparing a hole transmission layer, a perovskite light absorption layer, an electron transmission layer and a cathode on the anode layer to obtain the p-i-n type perovskite solar cell device.
The preparation method comprises one or more of electron beam evaporation, thermal evaporation, spin coating, brush coating, spray coating, dip coating, roller coating, printing or ink-jet printing.
The preparation method of the invention and the obtained device have the following advantages and beneficial effects:
(1) The device can be prepared in a large area at a low temperature, which is beneficial to reducing the cost of preparing the device;
(2) The device related by the invention can be prepared in a large area at a lower temperature by utilizing an electron beam evaporation hole transport layer, and a feasible implementation scheme is provided for realizing the large-area preparation of perovskite solar cell devices;
(3) The electron transport layer of the device can be prepared in a large area at a lower temperature, and a feasible implementation scheme is provided for realizing the perovskite solar cell device.
(4) The titanium metal is used for the cathode material of the perovskite battery of the device, and a feasible implementation scheme is provided for obtaining low cost and high stability of the photovoltaic device.
(5) The metal oxide used for the hole transport layer and the electron transport layer of the perovskite battery of the device provides a feasible implementation scheme for obtaining low cost and high stability of the photovoltaic device.
(6) The p-i-n perovskite battery of the device can obtain higher open-circuit voltage, and provides a feasible implementation scheme for obtaining high open-circuit voltage for a photovoltaic device.
Drawings
FIG. 1 is a schematic diagram of a p-i-n perovskite solar cell device of the invention utilizing electron beam evaporation equipment;
FIG. 2 is a schematic diagram showing the layered structure of a p-i-n perovskite solar cell device according to the invention, in turn ITO/NiO x /Active layer/Nb 2 O 5 /Ag and ITO/NiO x /Active layer/Nb 2 O 5 /Ti；
Fig. 3 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 1;
fig. 4 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 2;
fig. 5 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 3;
fig. 6 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 4;
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 90 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 ℃. The dried ITO substrate is treated by ultraviolet ozone cleaning equipment for 15 minutes, so that organic impurities attached to the surface are further removed. 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, the evaporated nickel oxide is annealed in the air at 300 ℃ for one hour, and then the nickel oxide is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, a mixed perovskite photoactive layer with CsMAFAPbIBr as a component is prepared by one-step spin coating, then heated at 110 ℃ for 60 minutes on a heating table, and then the device is loaded into an electron beam evaporation device, 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 ) Due to the use of electron beam evaporation equipmentThe preparation of the hole transport layer and the electron transport layer can realize a large area, so that a large-area battery device can be prepared by using different masks; and using electron beam evaporation of metallic silver as a 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 transport layer is controlled to be 30 nanometers and the thickness of the cathode layer material silver is controlled to be not less than 80 nanometers respectively. The structure of the obtained p-i-n perovskite solar cell device is as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The p-i-n perovskite solar cell device obtained in this example was subjected to 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.
The p-i-n perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 3.
The present example results in a highly efficient perovskite solar cell device. Higher energy conversion efficiency is exhibited in a p-i-n type perovskite device structure using a metal oxide for both the hole transport layer and the electron transport layer.
Example 2
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 90 nm, and the sheet resistance was about 20 ohm/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 ℃. The dried ITO substrate is treated for 15 minutes by ultraviolet ozone cleaning equipmentAnd (3) further removing the organic impurities attached to the surface. 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, the evaporated nickel oxide is annealed in the air at 300 ℃ for one hour, and then the nickel oxide is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, a mixed perovskite photoactive layer with CsMAFAPbIBr as a component is prepared by one-step spin coating, then heated at 110 ℃ for 60 minutes on a heating table, and then the device is loaded into an electron beam evaporation device, 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 electron beam evaporation equipment is used for preparing the hole transmission layer and the electron transmission layer, so that a large area of battery devices can be prepared by using different masks; and using electron beam evaporation of metallic silver as a 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 transport layer is controlled to be 25 nanometers and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers respectively. The structure of the obtained p-i-n perovskite solar cell device is as follows: ITO glass substrate/NiO x (25 nm)/perovskite layer (550 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The p-i-n perovskite solar cell device obtained in this example was subjected to a photoelectric performance test:
the p-i-n perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (25 nm)/perovskite layer (550 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 4.
Example 3
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 90 nm, and the sheet resistance was about 20 ohm/square. Sequentially using micron-sized semiconductor special-purpose detergent to removeThe substrate was ultrasonically cleaned with ionized water, acetone, and isopropyl alcohol for 15 minutes to remove dirt from the substrate surface. And then placing the mixture into an incubator to be dried at 80 ℃. The dried ITO substrate is treated by ultraviolet ozone cleaning equipment for 15 minutes, so that organic impurities attached to the surface are further removed. 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, the evaporated nickel oxide is annealed in the air at 300 ℃ for one hour, and then the nickel oxide is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, preparing a mixed perovskite photoactive layer with CsMAFAPbIBr as a component by one-step spin coating, heating at 110deg.C on a heating table for 60 min, loading the device into electron beam evaporation equipment, and turning on a cooling pump to obtain a product with vacuum degree of less than 5×10 -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 electron beam evaporation equipment is used for preparing the hole transmission layer and the electron transmission layer, so that a large area of battery devices can be prepared by using different masks; and using electron beam evaporation of metallic silver as a 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 transport layer is controlled to be 20 nanometers and the thickness of the cathode layer material silver is controlled to be not less than 80 nanometers respectively. The structure of the obtained p-i-n perovskite solar cell device is as follows: ITO glass substrate/NiO x (20 nm)/perovskite layer (550 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The p-i-n perovskite solar cell device obtained in this example was subjected to a photoelectric performance test:
the p-i-n perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (20 nm)/perovskite layer (550 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 5.
Example 4
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 90 nm, and the sheet resistance was about 20 ohm/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 ℃. The dried ITO substrate is treated by ultraviolet ozone cleaning equipment for 15 minutes, so that organic impurities attached to the surface are further removed. 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, the evaporated nickel oxide is annealed in the air at 300 ℃ for one hour, and then the nickel oxide is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, preparing a mixed perovskite photoactive layer with CsMAFAPbIBr as a component by one-step spin coating, heating at 110deg.C on a heating table for 60 min, loading the device into electron beam evaporation equipment, and turning on a cooling pump to obtain a product with vacuum degree of less than 5×10 -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 electron beam evaporation equipment is used for preparing the hole transmission layer and the electron transmission layer, so that a large area of battery devices can be prepared by using different masks; electron beam evaporation of metallic titanium was used 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 transport layer is controlled to be 25 nanometers and the thickness of the cathode layer material titanium is controlled to be not less than 80 nanometers respectively. The structure of the obtained p-i-n perovskite solar cell device is as follows: ITO glass substrate/NiO x (25 nm)/perovskite layer (550 nm)/Nb 2 O 5 (60 nm)/titanium (100 nm).
The p-i-n perovskite solar cell device obtained in this example was subjected to a photoelectric performance test:
the p-i-n perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (25 nm)/perovskite layer (550 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/titanium (100 nm) is shown in fig. 6.
The high efficiency perovskite solar cell device obtained in this example, particularly the open circuit voltage, exhibits a high value, and the open circuit voltage is generally low in the p-i-n type perovskite solar cell device. Higher energy conversion efficiency is exhibited in the p-i-n type perovskite battery device structure.
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. An electron beam prepared p-i-n type perovskite device structure is characterized in that: the p-i-n type battery device structure prepared by electron beam evaporation 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 electron beam evaporation cathode Ag.
2. An electron beam prepared p-i-n type perovskite device structure is characterized in that: the p-i-n type battery device structure prepared by electron beam evaporation 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 electron beam evaporation cathode Ti.
3. An electron beam prepared p-i-n perovskite device structure and a preparation method thereof as claimed in claim 1 or 2, wherein: the substrate is a glass, quartz, sapphire, polyimide, polyethylene terephthalate, polyethylene naphthalate, 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.
4. An electron beam prepared p-i-n perovskite device structure and a preparation method thereof as claimed in claim 1 or 2, 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.
5. An electron beam prepared p-i-n perovskite device structure and a preparation method thereof as claimed in claim 1 or 2, 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.
6. An electron beam-produced p-i-n perovskite device structure according to claims 1, 2, characterized in that: the perovskite photoactive layer is prepared from a blended or unblended perovskite light absorbing material; the light absorbing layer is a single layer or multiple layers.
7. An electron beam-prepared p-i-n perovskite device structure according to claim 1, 2, wherein said electron transport layer is not limited to a single layer, including the multilayer case of an added hole, exciton blocking layer.
8. An electron beam-produced p-i-n perovskite device structure according to claims 1, 2, characterized in that: 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.
9. An electron beam-prepared p-i-n perovskite device structure and a preparation method thereof as claimed in any one of claims 1 to 8, characterized by comprising the steps of: and taking a substrate material with an anode layer, and then sequentially preparing a hole transport layer, a perovskite photoactive layer, an electron transport layer and a cathode on the anode layer to obtain the p-i-n type perovskite device prepared by the electron beam.
10. An electron beam-produced p-i-n perovskite device structure and a method of producing the same as defined in claim 9 wherein: the preparation method comprises one or more of electron beam evaporation, thermal evaporation, spin coating, brush coating, spray coating, dip coating, roller coating, printing or ink-jet printing.
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