CN111446369B - Perovskite photovoltaic cell device and manufacturing method thereof - Google Patents

Perovskite photovoltaic cell device and manufacturing method thereof Download PDF

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CN111446369B
CN111446369B CN202010177594.9A CN202010177594A CN111446369B CN 111446369 B CN111446369 B CN 111446369B CN 202010177594 A CN202010177594 A CN 202010177594A CN 111446369 B CN111446369 B CN 111446369B
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transport layer
perovskite
photovoltaic cell
cell device
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CN111446369A (en
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刘欣
王阳培华
杨定宇
张翠娴
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Chengdu University of Information Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention disclosesA perovskite photovoltaic cell device and a method for manufacturing the same are provided, the perovskite photovoltaic cell device comprising a substrate, an anode, a first hole transport layer (PEDOT: PSS or nickel oxide), a second hole transport layer (conductive organic compound), a perovskite light absorption layer, a first electron transport layer (conductive organic compound (electron transport layer 1)), a second electron transport layer (electron transport layer 2 (Nb)2O5) And a cathode. The perovskite photovoltaic cell device and the preparation method thereof have the advantages of higher performance, lower processing cost and capability of realizing large-area processing, thereby having good application prospect in the field of perovskite photovoltaic cell devices.

Description

Perovskite photovoltaic cell device and manufacturing method thereof
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a perovskite photovoltaic cell device and a manufacturing method thereof.
Background
As early as 2006, the group of subjects taught by Miyasaka at the university of tung sholbine of japan tried perovskite materials as light-absorbing materials for use in dye-sensitized solar cells, and they first reported dye-sensitized perovskite solar cells having a solar conversion efficiency of 3.8% in 2009 (j. Am. chem. soc., 2009, 131, 6050). Next, the problem group of Nam-Gyu Park university at korea university, by optimizing the concentration of the precursor solution and the annealing temperature, the energy conversion efficiency is improved by nearly one time (Nanoscale, 2011, 3, 4088), while the perovskite solar cells really get attention that they use perovskite materials in all-solid-state structures similar to organic thin-film solar cells and greatly improve the energy conversion efficiency and stability (sci. rep. (2012), 2, 591). Since the perovskite solar cell has significant advantages of low raw material and manufacturing costs, and the performance of the perovskite solar cell is rapidly improved in recent years with the great input of research efforts in the related fields.
Such perovskite materials typically have ABX3Of the formula (II) wherein A+Typically a monovalent cation (usually methylamine ion (CH)3NH3 +，MA+) Cesium ionSon (Cs), formamidine ion (FA)+）），B2+Is an inorganic cation (typically Pb)2+），X-Is a halogen anion (generally I)-、Cl-Or Br-). The band gap of the perovskite material can be continuously regulated within 1.6 to 3.2 electron volts according to the type of the halogen element used. Using formamidine ion (CH (NH)2)2 +，FA+) Replacement MA+Or use Sn2+To replace Pb2+Or the band gap of the perovskite material can be further regulated and controlled by adopting a mixed ion method and the like, so that the sunlight absorption in a wider range is realized. Since the perovskite solar cell was originally developed from the dye-sensitized solar cell, the mesoporous structure is common. In this structure, in dense TiO2A layer of TiO is also arranged on the selective electron transport layer2Mesoporous layer composed of nanoparticles. The mesoporous layer is used as a framework for depositing the perovskite film on one hand, and the other hand can reduce the distance of electron diffusion, thereby improving the electron collection efficiency. The thickness of the mesopores used in the initial study was about 500-600 nm, and the perovskite light absorbing material was completely penetrated into the mesoporous framework. However, as the research goes into, it is found that a thinner mesoporous layer of about 150-200 nm can be used, and a continuous and dense perovskite light absorption layer can be formed thereon to obtain better device performance. Because the diffusion length of electrons and holes in the perovskite material is very long, the perovskite solar cell with higher efficiency can be obtained by using a planar structure after the mesoporous layer is completely removed, and the planar perovskite solar cell with a simpler structure has obvious advantages in preparation structure compared with a mesoporous perovskite solar cell, so that the planar perovskite solar cell has higher commercial potential.
The common perovskite solar cell device structure at present comprises a mesoporous type, a planar type (n-i-p) and a planar inverted type (p-i-n). The current n-type electron transport material used in the planar structure is generally a metal oxide semiconductor material, the p-type hole transport material is generally an organic hole transport material, and the organic hole transport material used has low mobility, so that a device is often doped with a dopant to obtain high performance, which limits further commercial application. The n-type electron transport materials used in the planar inversion structure at present are generally fullerene and derivatives thereof, and the materials have the defects of high production cost, difficult purification and the like which restrict the large-scale production of the materials. Therefore, the development of a planar perovskite photovoltaic cell device with low cost, large area and stability and a structure thereof are imminent.
Disclosure of Invention
The invention aims to provide a perovskite photovoltaic cell device and a manufacturing method thereof, wherein the perovskite photovoltaic cell device can obtain higher performance and excellent stability, and a feasible implementation scheme is provided for obtaining high performance of the photovoltaic device; the preparation method can be used for large-area preparation of the perovskite photovoltaic cell device, and is beneficial to reduction of preparation cost.
The invention is realized by the following technical scheme: a perovskite photovoltaic cell device comprises a substrate, an anode layer formed on the substrate, a first hole transport layer (hole transport layer 1) formed on the anode layer using PEDOT: PSS or nickel oxide, a second hole transport layer (hole transport layer 2) formed on the hole transport layer using a conductive organic compound, a perovskite light absorption layer formed on the second hole transport layer and composed of CsPbIBr, a first electron transport layer (electron transport layer 1) formed on the perovskite light absorption layer using a conductive organic compound, a second electron transport layer (electron transport layer 2) formed on the first electron transport layer using niobium pentoxide, and a cathode layer formed on the second electron transport layer.
To further better realize the perovskite photovoltaic cell device of the present invention,
the first hole transport layer further comprises an electron blocking layer and/or an exciton blocking layer;
and/or
The second hole transport layer further comprises an electron blocking layer and/or an exciton blocking layer;
and/or
The first electron transport layer further comprises a hole blocking layer and/or an exciton blocking layer;
and/or
The second electron transport layer further comprises a hole blocking layer and/or an exciton blocking layer;
and/or
An anode buffer layer is also arranged between the anode layer and the first hole transport layer;
and/or
And a cathode buffer layer is arranged between the cathode layer and the second electron transport layer.
A method of manufacturing a perovskite photovoltaic cell device, comprising:
(1) obtaining a substrate;
(2) ultrasonically cleaning the substrate by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence and drying;
(3) forming an anode layer on the substrate;
(4) forming PEDOT on the anode layer, wherein a PSS layer or a nickel oxide layer is used as a first hole transport layer;
(5) forming a conductive organic compound as a second hole transport layer on the first hole transport layer;
(6) spin coating a perovskite light absorption layer having a composition comprising CsPbIBr on the second hole transport layer;
(7) performing heat treatment at 40-100 ℃ obtained in the step (6), namely performing heat treatment on the substrate with the perovskite light absorption layer at 40-100 ℃;
(8) spin-coating a conductive organic compound as a first electron transport layer on the perovskite light absorption layer through step (7);
(9) evaporating a niobium pentoxide layer on the first electron transport layer to form a second electron transport layer;
(10) and forming a cathode layer on the second electron transport layer.
In order to further realize the manufacturing method of the perovskite photovoltaic cell device, the substrate is glass, quartz, sapphire, polyimide, polyethylene terephthalate, polyethylene naphthalate, metal or alloy film, and the like.
In order to better realize the manufacturing method of the perovskite photovoltaic cell device, the anode layer and the cathode layer are made of metal, metal oxide or poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonic acid) and modified products thereof.
In order to better realize the manufacturing method of the perovskite photovoltaic cell device, the metal is aluminum, silver-magnesium alloy, silver or gold and the like; the metal oxide is one or the combination of more than two of indium tin oxide, fluorine-doped tin dioxide, zinc oxide and indium gallium zinc oxide.
To further better realize the manufacturing method of the perovskite photovoltaic cell device, the method further comprises the step of forming an electron blocking layer and/or an exciton blocking layer on the first hole transport layer, namely the electron blocking layer and/or the exciton blocking layer can also be formed on the layer adopting PEDOT, PSS or nickel oxide as the whole first hole transport layer.
Further, to better realize the manufacturing method of the perovskite photovoltaic cell device of the present invention, the method further comprises forming an electron blocking layer and/or an exciton blocking layer on the second hole transport layer, that is, the electron blocking layer and/or the exciton blocking layer may also be formed on the layer using the conductive organic compound as the entire second hole transport layer.
Further, in order to better realize the method for manufacturing a perovskite photovoltaic cell device according to the present invention, the method further comprises forming a hole blocking layer and/or an exciton blocking layer on the perovskite light absorption layer, that is, the hole blocking layer and/or the exciton blocking layer and the conductive organic compound as an integral first electron transport layer may be further formed on the perovskite light absorption layer.
Further, to better realize the manufacturing method of the perovskite photovoltaic cell device, the method further comprises the step of forming a hole blocking layer and/or an exciton blocking layer on the first electron transport layer, namely forming the hole blocking layer and/or the exciton blocking layer and the niobium pentoxide layer on the first electron transport layer to be used as an integral second electron transport layer.
To better realize the manufacturing method of the perovskite photovoltaic cell device, an anode buffer layer is formed between the anode layer and the first hole transport layer.
To better realize the manufacturing method of the perovskite photovoltaic cell device, a cathode buffer layer is formed between the cathode layer and the second electron transport layer.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the perovskite photovoltaic cell device can obtain higher performance and excellent stability, and a feasible implementation scheme is provided for obtaining high performance of the photovoltaic device; the preparation method can be used for large-area preparation of the perovskite photovoltaic cell device, and is beneficial to reduction of preparation cost.
The hole transport layer of the device can be prepared at a lower temperature, and a feasible implementation scheme is provided for realizing the flexible perovskite photovoltaic cell device.
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 preparing a large-area perovskite solar cell device at a low temperature.
Drawings
FIG. 1 is a schematic view of a layered structure of a perovskite photovoltaic cell device according to one embodiment of the present invention, in the order substrate/anode/first hole transport layer (hole transport layer 1 (PEDOT: PSS or NiO)x) Second hole transport layer (hole transport layer 2 (conductive organic compound))/perovskite light absorption layer/first electron transport layer (electron transport layer 1 (conductive organic compound))/second electron transport layer (electron transport layer 2 (Nb))2O5) )/cathode.
Fig. 2 is a chemical structural formula of a conductive organic compound hole transport material used in a perovskite photovoltaic cell device according to one embodiment of the present invention.
Fig. 3 is a chemical structural formula of a conductive organic compound electron transport material used in a perovskite photovoltaic cell device according to one embodiment of the present invention.
Fig. 4 is a graph of current density-voltage characteristics of the resulting perovskite photovoltaic cell device of example 10;
FIG. 5 is a graph of the current density-voltage characteristics of the resulting perovskite photovoltaic cell device of example 11;
fig. 6 is a graph of current density-voltage characteristics of the resulting perovskite photovoltaic cell device of example 12.
Detailed Description
The following examples are given to illustrate the present invention and it is necessary to point out here that the following examples are given only for the purpose of further illustration and are not to be construed as limiting the scope of the invention, which is susceptible to numerous insubstantial modifications and adaptations by those skilled in the art in light of the present disclosure.
Example 1:
a perovskite photovoltaic cell device, as shown in FIG. 1, comprises a substrate, an anode layer formed on the substrate, a first hole transport layer (hole transport layer 1) formed on the anode layer using PEDOT: PSS or nickel oxide, a second hole transport layer (hole transport layer 2) formed on the hole transport layer using a conductive organic compound (as shown in FIG. 2), a perovskite light absorption layer formed on the second hole transport layer and composed of CsPbIBr, a first electron transport layer (electron transport layer 1) formed on the perovskite light absorption layer using a conductive organic compound (as shown in FIG. 3), a second electron transport layer (electron transport layer 2) formed on the first electron transport layer using niobium pentoxide, and a cathode layer formed on the second electron transport layer.
Example 2:
the present embodiment is further optimized based on the above embodiment, and the same parts as the foregoing technical solutions will not be described herein again, as shown in fig. 1, further to better implement the perovskite photovoltaic cell device according to the present invention,
the first hole transport layer further comprises an electron blocking layer and/or an exciton blocking layer;
and/or
The second hole transport layer further comprises an electron blocking layer and/or an exciton blocking layer;
and/or
The first electron transport layer further comprises a hole blocking layer and/or an exciton blocking layer;
and/or
The second electron transport layer further comprises a hole blocking layer and/or an exciton blocking layer;
and/or
An anode buffer layer is also arranged between the anode layer and the first hole transport layer;
and/or
And a cathode buffer layer is arranged between the cathode layer and the second electron transport layer.
Example 3:
this embodiment is further optimized on the basis of any one of the above embodiments, and as shown in fig. 1, the manufacturing method of the perovskite photovoltaic cell device includes:
(1) obtaining a substrate; the substrate may be a rigid substrate such as glass, quartz, sapphire, etc.; or a flexible substrate such as polyimide, polyethylene terephthalate, polyethylene naphthalate, or other polyester-based materials; or metal, alloy or stainless steel film;
(2) ultrasonically cleaning the substrate by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence and drying;
(3) forming an anode layer on the substrate, wherein the anode layer is made of metal, metal oxide or poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) and modified products thereof; the metal can be aluminum, silver-magnesium alloy, silver or gold, etc.; the metal oxide is one or the combination of more than two of indium tin oxide, fluorine-doped tin dioxide, zinc oxide and indium gallium zinc oxide;
(4) forming PEDOT on the anode layer, wherein a PSS layer or a nickel oxide layer is used as a first hole transport layer;
(5) forming a conductive organic compound as a second hole transport layer on the first hole transport layer;
(6) spin coating a perovskite light absorption layer having a composition comprising CsPbIBr on the second hole transport layer;
(7) performing heat treatment at 40-100 ℃ obtained in the step (6), namely performing heat treatment on the substrate with the perovskite light absorption layer at 40-100 ℃;
(8) spin-coating a conductive organic compound as a first electron transport layer on the perovskite light absorption layer through step (7);
(9) evaporating a niobium pentoxide layer on the first electron transport layer to form a second electron transport layer;
(10) in the second electron transport layer (electron transport layer 2 (Nb))2O5) Forming a cathode layer thereon; the cathode layer is metal, metal oxide or poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) and modified products thereof; the metal can be aluminum, silver-magnesium alloy, silver or gold, etc.; the metal oxide is one or the combination of more than two of indium tin oxide, fluorine-doped tin dioxide, zinc oxide and indium gallium zinc oxide.
Example 4:
this embodiment is further optimized based on embodiment 3, and the same portions as those in the foregoing technical solutions will not be repeated herein, and further to better implement the method for manufacturing a perovskite photovoltaic cell device according to the present invention, the method further includes forming an electron blocking layer and/or an exciton blocking layer on the first hole transport layer, that is, the electron blocking layer and/or the exciton blocking layer may also be formed on a layer using PEDOT: PSS or nickel oxide as the entire first hole transport layer.
Example 5:
this embodiment is further optimized based on embodiment 3 or 4, and the same portions as those in the foregoing technical solutions will not be described herein again, and further to better implement the method for manufacturing a perovskite photovoltaic cell device according to the present invention, the method further includes forming an electron blocking layer and/or an exciton blocking layer on the second hole transport layer, that is, an electron blocking layer and/or an exciton blocking layer may also be formed on the layer using a conductive organic compound as the entire second hole transport layer.
Example 6:
this embodiment is further optimized based on embodiment 3 or 4 or 5, and the same portions as those in the foregoing technical solutions will not be described herein again, and further to better implement the manufacturing method of the perovskite photovoltaic cell device according to the present invention, the method further includes forming a hole blocking layer and/or an exciton blocking layer on the perovskite light absorption layer, that is, the hole blocking layer and/or the exciton blocking layer and the conductive organic compound may also be formed on the perovskite light absorption layer to serve as the overall first electron transport layer.
Example 7:
this embodiment is further optimized based on embodiment 3 or 4 or 5 or 6, and the same portions as those in the foregoing technical solutions will not be described herein again, and further to better implement the manufacturing method of the perovskite photovoltaic cell device according to the present invention, the method further includes forming a hole blocking layer and/or an exciton blocking layer on the first electron transport layer, that is, forming a hole blocking layer and/or an exciton blocking layer and a niobium pentoxide layer on the first electron transport layer for use as an integral second electron transport layer.
Example 8:
this embodiment is further optimized based on embodiment 3 or 4 or 5 or 6 or 7, and the same portions as those in the foregoing technical solutions will not be described herein again, and further to better implement the manufacturing method of the perovskite photovoltaic cell device according to the present invention, the method further includes forming an anode buffer layer between the anode layer and the first hole transport layer.
Example 9:
the present embodiment is further optimized based on embodiment 3 or 4 or 5 or 6 or 7 or 8, and the same portions as those in the foregoing technical solutions will not be described herein again, and further to better implement the manufacturing method of the perovskite photovoltaic cell device according to the present invention, the method further includes forming a cathode buffer layer between the cathode layer and the second electron transport layer.
Example 10:
ITO conductive glass with same batch numberThe substrate is several, the specification is 25 mm × 25 mm, the ITO thickness is about 90 nm, and the square resistance is about 20 ohm/square. And ultrasonically cleaning the substrate for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into an oven to be dried at 80 ℃. And then preparing PEDOT: PSS as a hole transport layer 1 on the ITO substrate by a spin coating method, heating the ITO substrate on a heating table for 15 minutes at 125 ℃, then spin coating a conductive organic compound PffBT4T-2DT on the PEDOT: PSS as a hole transport layer 2 by the spin coating method, and then transferring the hole transport layer into a glove box filled with low-water oxygen and high-purity nitrogen. In the glove box, a perovskite light absorption layer with the components of CsPbIBr is prepared by one-step spin coating, then the perovskite light absorption layer is heated on a heating table for 2 minutes at 40 ℃ and 30 minutes at 100 ℃, then a conductive organic compound IEIC is prepared by spin coating on the perovskite light absorption layer, then the device is arranged in an electron beam evaporation equipment, a cooling pump is started, 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. Using a specific mask plate to sequentially evaporate an electron transport layer niobium pentoxide (Nb)2O5) By adjusting the electron transport layer Nb2O5The thickness of the perovskite solar cell is 40-100 nanometers, so that the performance of the perovskite photovoltaic cell device is optimized, and an electron transport layer Nb is prepared by using electron beam evaporation equipment2O5The low-temperature large-area flexible battery device can be prepared by using different masks; and using electron beam to evaporate metal silver as the cathode of the device. The evaporation rate and the thickness of each evaporated functional layer are monitored in real time by a quartz crystal oscillator film thickness detector, and the thickness of the electron transmission layer is controlled to be 70 nanometers, and the thickness of the cathode layer material metal silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device is as follows: glass substrate/ITO/PEDOT PSS/PffBT4T-2 DT/perovskite layer/IEIC/Nb2O5Silver.
The perovskite photovoltaic cell device obtained in the example is subjected to a photoelectric performance test:
and after the device is prepared, taking out the device from the evaporation cavity. The test was then conducted in air and the device current-voltage information was determined from a 2400 power supply meter manufactured by giemley (Keithley). The performances of the device such as current density, filling factor, power conversion efficiency and the like can be respectively calculated through information such as current, voltage, light intensity and the like.
The perovskite photovoltaic cell device obtained by the implementation comprises the following components: glass substrate/ITO/PEDOT PSS/PffBT4T-2 DT/perovskite layer/IEIC/Nb2O5The current density-voltage characteristic curve for silver is shown in fig. 4.
The result of this example is a highly efficient perovskite photovoltaic cell device.
Example 11:
the preparation process was the same as example 10, and several ITO conductive glass substrates of the same lot number were used, the specification was 25 mm × 25 mm, the thickness of ITO was about 90 nm, and the sheet resistance was about 20 ohm/square. And ultrasonically cleaning the substrate for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into an oven to be dried at 80 ℃. Then NiO is prepared on the ITO substrate by using an electron beam evaporation methodxAs the hole transport layer 1, the NiO was coated by spin coatingxThe high molecular conductive polymer PffBT4T-2DT is spin-coated to form a hole transport layer 2, and then the hole transport layer is transferred into a glove box filled with low-water-oxygen and high-purity nitrogen. In the glove box, a perovskite light absorption layer with the components of CsPbIBr is prepared by one-step spin coating, then the perovskite light absorption layer is heated on a heating table for 2 minutes at 40 ℃ and 30 minutes at 100 ℃, then a conductive organic compound IEIC is prepared by spin coating on the perovskite light absorption layer, then the device is arranged in an electron beam evaporation equipment, a cooling pump is started, 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. Using a specific mask plate to sequentially evaporate an electron transport layer niobium pentoxide (Nb)2O5) By adjusting the electron transport layer Nb2O5The thickness of the perovskite cell is 40-100 nanometers, so that the performance of the perovskite cell device is optimized, and an electron transport layer Nb is prepared by using electron beam evaporation equipment2O5The low-temperature large-area solar cell can be realized, so that a large-area cell device can be prepared by using different masks; gold is deposited by electron beam evaporationSilver is used as the cathode of the device. The evaporation rate and the thickness of each evaporated functional layer are monitored in real time by a quartz crystal oscillator film thickness detector, and the thickness of the electron transmission layer is controlled to be 70 nanometers, and the thickness of the cathode layer material metal silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite photovoltaic cell device is as follows: glass substrate/ITO/NiOxPffBT4T-2 DT/perovskite layer/IEIC/Nb2O5Silver.
The perovskite photovoltaic cell device obtained by the implementation comprises the following components: glass substrate/ITO/NiOxPffBT4T-2 DT/perovskite layer/IEIC/Nb2O5The current density-voltage characteristic curve for silver is shown in fig. 5.
The result of this example is a highly efficient perovskite photovoltaic cell device.
Example 12:
the preparation process was the same as example 10, and several ITO conductive glass substrates of the same lot number were used, the specification was 25 mm × 25 mm, the thickness of ITO was about 90 nm, and the sheet resistance was about 20 ohm/square. And ultrasonically cleaning the substrate for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into an oven to be dried at 80 ℃. Then preparing nickel oxide (NiO) on the ITO substrate by using a spin coating methodx) The preparation method of the precursor solution of the layer and the nickel oxide comprises the following steps: dissolving nickel acetate tetrahydrate in ethylene glycol at 0.5M concentration, adding ethylenediamine solution at molar ratio to Ni2+1:1, heating at 160 ℃ for 10 minutes on a heating table after spin coating, then heating at 300 ℃ for 60 minutes on the heating table, and then spin coating on NiOxSpin-coating a high-molecular conductive polymer FTAZ as a hole transport layer 2, and then transferring the hole transport layer into a glove box filled with low-water oxygen and high-purity nitrogen. In the glove box, a perovskite light absorption layer with the component CsPbIBr is prepared by one-step spin coating, then the perovskite light absorption layer is heated on a heating table for 2 minutes at 40 ℃ and 30 minutes at 100 ℃, then a conductive organic compound hPDI4 is prepared by spin coating on the perovskite light active layer, then the device is arranged in an electron beam evaporation equipment, a cooling pump is started, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10-4 Starting electron beam evaporation after PaA film. Using a specific mask plate to sequentially evaporate an electron transport layer niobium pentoxide (Nb)2O5) By adjusting the electron transport layer Nb2O5The thickness of the perovskite solar cell is 40-100 nanometers, so that the performance of the perovskite photovoltaic cell device is optimized, and an electron transport layer Nb is prepared by using electron beam evaporation equipment2O5The low-temperature large-area solar cell can be realized, so that a large-area cell device can be prepared by using different masks; and evaporating a metal silver material by using an electron beam to serve as a cathode of the device. The evaporation rate and the thickness of each functional layer of evaporation are monitored in real time by a quartz crystal oscillator film thickness detector, and the thickness of the electron transmission layer is controlled to be 70 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 photovoltaic cell device is as follows: glass substrate/ITO/NiOxFTAZ/perovskite layer/hPDI 4/Nb2O5Silver.
The perovskite photovoltaic cell device obtained by the implementation comprises the following components: glass substrate/ITO/NiOxFTAZ/perovskite layer/hPDI 4/Nb2O5The current density-voltage characteristic curve for silver is shown in fig. 6.
The result of this example is a highly efficient perovskite photovoltaic cell device.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.

Claims (10)

1. A perovskite photovoltaic cell device characterized by: PSS or nickel oxide, a second hole transport layer formed on the first hole transport layer, a perovskite light absorption layer formed on the second hole transport layer and composed of CsPbIBr, a first electron transport layer formed on the perovskite light absorption layer, a second electron transport layer formed on the first electron transport layer and composed of niobium pentoxide, and a cathode layer formed on the second electron transport layer;
Figure FDF0000012942870000011
Figure FDF0000012942870000021
the second hole transport layer is a compound PffBT-T3(1,2) -2 or P3TEA or FTAZ or PvBDTTAZ or PffBT4T-2 DT;
the first electron transport layer is a compound hPDI4 or IEIC or IT-4F.
2. The perovskite photovoltaic cell device of claim 1, wherein:
the first hole transport layer further comprises an electron blocking layer and/or an exciton blocking layer;
and/or
The second hole transport layer further comprises an electron blocking layer and/or an exciton blocking layer;
and/or
The first electron transport layer further comprises a hole blocking layer and/or an exciton blocking layer;
and/or
The second electron transport layer further comprises a hole blocking layer and/or an exciton blocking layer;
and/or
An anode buffer layer is also arranged between the anode layer and the first hole transport layer;
and/or
And a cathode buffer layer is arranged between the cathode layer and the second electron transport layer.
3. A method of manufacturing a perovskite photovoltaic cell device as claimed in claim 1 or 2, wherein: the method comprises the following steps:
(1) obtaining a substrate;
(2) ultrasonically cleaning the substrate by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence and drying;
(3) forming an anode layer on the substrate;
(4) forming PEDOT on the anode layer, wherein a PSS layer or a nickel oxide layer is used as a first hole transport layer;
(5) forming a conductive organic compound as a second hole transport layer on the first hole transport layer;
(6) spin coating a perovskite light absorption layer having a composition comprising CsPbIBr on the second hole transport layer;
(7) carrying out heat treatment on the product obtained in the step (6) at 40-100 ℃;
(8) spin-coating a conductive organic compound as a first electron transport layer on the perovskite light absorption layer through step (7);
(9) evaporating a niobium pentoxide layer on the first electron transport layer to form a second electron transport layer;
(10) and forming a cathode layer on the second electron transport layer.
4. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 3, characterized in that: the substrate is glass, quartz, sapphire, polyimide, polyethylene terephthalate, polyethylene naphthalate, metal or alloy film.
5. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 3 or 4, characterized in that: the anode layer and the cathode layer are metals, metal oxides or poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) and modified products thereof.
6. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 5, characterized in that: the metal is aluminum, silver-magnesium alloy, silver or gold; the metal oxide is one or the combination of more than two of indium tin oxide, fluorine-doped tin dioxide, zinc oxide and indium gallium zinc oxide.
7. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 3 or 4 or 6, characterized in that: further comprising forming an electron blocking layer and/or an exciton blocking layer on the first hole transport layer and forming an electron blocking layer and/or an exciton blocking layer on the second hole transport layer.
8. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 3 or 4 or 6, characterized in that: further comprising forming a hole blocking layer and/or an exciton blocking layer on the perovskite light absorbing layer and forming a hole blocking layer and/or an exciton blocking layer on the first electron transporting layer.
9. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 3 or 4 or 6, characterized in that: further comprising forming an anode buffer layer between the anode layer and the hole transport layer.
10. The method of manufacturing a perovskite photovoltaic cell device as claimed in claim 3 or 4 or 6, characterized in that: further comprising forming a cathode buffer layer between the cathode layer and the second electron transport layer.
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