CN114899322A - Fullerene di (ethoxycarbonyl) methylene derivative electron transport material, application, solar cell and preparation method thereof - Google Patents
Fullerene di (ethoxycarbonyl) methylene derivative electron transport material, application, solar cell and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
-
- 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
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- 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
-
- 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 provides a fullerene di (ethoxycarbonyl) methylene derivative electron transport material, application thereof, a solar cell and a preparation method thereof, and relates to the technical field of fullerene materials and tin-based perovskite solar cells. The fullerene di (ethoxycarbonyl) methylene derivative electron transport material can be obtained by separating, purifying and drying fullerene di (ethoxycarbonyl) methylene derivatives to obtain four position isomers, namely trans-2, trans-3, trans-4 and e, and then reasonably adjusting the proportion of the four isomers. The film forming property of the electronic transmission material can be improved through reasonable proportioning, energy disorder caused by isomer ratio change is reduced, the energy level matching of the electronic transmission material and tin-based perovskite is better, the electronic extraction and transmission capability of the fullerene thin film are enhanced, meanwhile, the energy barrier of carrier diffusion at an interface can be effectively reduced, the open-circuit voltage loss is reduced, and the tin-based perovskite solar cell with high photoelectric conversion efficiency is realized.
Description
Technical Field
The invention relates to the technical field of fullerene materials and tin-based perovskite solar cells, and particularly relates to a fullerene di (ethoxycarbonyl) methylene derivative electron transport material, application of the fullerene di (ethoxycarbonyl) methylene derivative electron transport material, a solar cell and a preparation method of the fullerene di (ethoxycarbonyl) methylene derivative electron transport material.
Background
In order to solve the energy crisis problem by using solar energy and the environmental problem caused by the combustion of fossil energy, researchers have conducted extensive studies on organic-inorganic hybrid halide lead-based perovskite solar cells (LPSCs). LPSCs are rapidly evolving, with photoelectric conversion efficiencies increasing from the first 3.8% to the present 25.7% only over a decade. However, the toxicity of lead elements and the Shockley-Quetier restriction of lead-based perovskites are also problems that cannot be ignored for preventing further development. To solve these problems, non-lead perovskite solar cells have received much attention in recent years. Among them, tin-based perovskites are the most promising non-lead perovskite materials for development at present due to their narrower band gap, stronger exciton binding energy and higher absorption coefficient.
At present, the Photoelectric Conversion Efficiency (PCE) of tin-based perovskite solar cells (TPSCs) is still a significant difference compared with mainstream LPSCs, and one of the main reasons is that the conduction band bottom of tin-based perovskite is higher than that of lead-based perovskite, so that the energy level matching of fullerene electron transport layer materials (such as C60, PCBM and the like) commonly used in trans-LPSCs is not good, and further a large open-circuit voltage loss is caused. The indene-C60 double adduct (ICBA) which is also a disubstituted fullerene material is prone to cause energy disorder due to too many isomers and large difference of the proportions of isomers in different batches, thereby affecting the photoelectric conversion efficiency of the device. The fullerene di (ethoxycarbonyl) methylene derivative is simple to synthesize, the LUMO energy level position is higher relative to C60, PCBM and the like, and the fullerene di (ethoxycarbonyl) methylene derivative is used as an electron transport layer material and is more matched with the tin-based perovskite energy level. However, the fullerene di (ethoxycarbonyl) methylene derivative contains a series of positional isomers, and the proportions of the isomers in different batches of products are different, so that the fullerene di (ethoxycarbonyl) methylene derivative composed of the isomers in different proportions is difficult to obtain relatively stable photoelectric conversion efficiency when used in TPSCs. Therefore, it is of great interest to researchers how to tailor the ratio of these isomers to obtain a higher PCE.
Disclosure of Invention
The invention aims to provide a fullerene di (ethoxycarbonyl) methylene derivative electron transport material, which can reduce the difference of fullerene isomer ratios in different batches, reduce energy disorder, enhance electron extraction and transport capacity and achieve the purpose of improving the photoelectric conversion efficiency of a corresponding tin-based perovskite solar cell by reasonably adjusting the ratio of different isomers of the fullerene di (ethoxycarbonyl) methylene derivative.
The invention also aims to provide the application of the fullerene bis (ethoxycarbonyl) methylene derivative electron transport material in preparing a tin-based perovskite solar cell.
The third purpose of the invention is to provide a preparation method of the tin-based perovskite solar cell, which is simple, controllable in parameters and suitable for industrial large-scale production.
The fourth purpose of the invention is to provide a tin-based perovskite solar cell, which takes fullerene bis (ethoxycarbonyl) methylene derivative electron transport material as an electron transport layer, thereby improving the photoelectric conversion efficiency of the cell.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a fullerene di (ethoxycarbonyl) methylene derivative electron transport material, which comprises isomers trans-2, trans-3, trans-4 and e, wherein the molecular structures of the isomers trans-2, trans-3, trans-4 and e are respectively as follows:
according to the mass percentage, in the fullerene di (ethoxycarbonyl) methylene derivative electron transmission material, the mass percentage of the isomer trans-2 is 10-30%, the mass percentage of the isomer trans-3 is 25-40%, the mass percentage of the isomer trans-4 is 5-10%, and the mass percentage of the isomer e is 20-60%.
The invention provides an application of a fullerene di (ethoxycarbonyl) methylene derivative electron transport material in preparation of a tin-based perovskite solar cell.
The invention provides a preparation method of a tin-based perovskite solar cell, which comprises the following steps:
s1, preparing an ITO conductive substrate layer, a hole transport layer and a tin-based perovskite light absorption layer, wherein the hole transport layer is located on the ITO conductive substrate layer, and the tin-based perovskite light absorption layer is located on the hole transport layer.
S2, synthesizing the fullerene di (ethoxycarbonyl) methylene derivative, and then separating and purifying to obtain the isomer trans-2, the isomer trans-3, the isomer trans-4 and the isomer e;
s3, weighing the isomers trans-2, trans-3, trans-4 and e according to the mass percent of the fullerene di (ethoxycarbonyl) methylene derivative electron transport material, and dissolving the isomers in chlorobenzene to obtain a fullerene solution;
s4, heating and stirring the fullerene solution, standing, cooling, filtering, spreading on the surface of the tin-based perovskite light absorption layer in a spin coating manner, and annealing at 60-80 ℃ for 5-15 min to obtain a fullerene electron transmission layer film;
s5, spin-coating a BCP hole blocking layer on the fullerene electron transport layer film, and depositing a metal electrode on the BCP hole blocking layer to obtain the tin-based perovskite solar cell.
The invention also provides a tin-based perovskite solar cell which is prepared according to the preparation method, and the tin-based perovskite solar cell sequentially comprises an ITO conductive substrate layer, a hole transport layer, a tin-based perovskite light absorption layer, a fullerene electron transport layer, a BCP hole barrier layer and a metal electrode from bottom to top.
The fullerene di (ethoxycarbonyl) methylene derivative electron transport material and the application thereof, the solar cell and the preparation method thereof have the beneficial effects that:
the invention separates from fullerene di (ethoxycarbonyl) methylene derivative and purifies and dries the fullerene di (ethoxycarbonyl) methylene derivative by methanol to obtain four position isomeric pure bodies, namely trans-2, trans-3, trans-4 and e. By reasonably distributing the proportions of the four isomers, the proportion between fullerene isomers can be controlled, and disorder of energy can be reduced. The photoelectric conversion efficiency of the tin-based perovskite solar cell prepared by adopting the electron transport material as an electron transport layer can reach 13.87%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an interfacial scanning electron micrograph of a tin-based perovskite solar cell of example 1 of the present invention;
FIG. 2 is a J-V curve of tin-based perovskite solar cells of examples 1 to 3 of the present invention and comparative examples 1 to 5;
FIG. 3 is a PCE statistical chart of tin-based perovskite solar cells of examples 1 to 3 of the present invention and comparative examples 1 to 5;
FIG. 4 is a graph showing V of tin-based perovskite solar cells according to examples 1 to 3 and comparative examples 1 to 5 of the present invention OC A statistical chart;
FIG. 5 is a graph showing J of the tin-based perovskite solar cell of examples 1 to 3 and comparative examples 1 to 5 of the present invention SC A statistical chart;
FIG. 6 is a FF statistical chart of tin-based perovskite solar cells of examples 1 to 3 of the present invention and comparative examples 1 to 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following describes the electron transport material of fullerene di (ethoxycarbonyl) methylene derivative, the application thereof, the solar cell and the preparation method thereof.
The fullerene di (ethoxycarbonyl) methylene derivative electron transport material provided by the embodiment of the invention is characterized by comprising isomers trans-2, trans-3, trans-4 and e, wherein the molecular structures of the isomers trans-2, trans-3, trans-4 and e are respectively as follows:
according to the mass percentage, in the fullerene di (ethoxycarbonyl) methylene derivative electron transmission material, the mass percentage of the isomer trans-2 is 10-30%, the mass percentage of the isomer trans-3 is 25-40%, the mass percentage of the isomer trans-4 is 5-10%, and the mass percentage of the isomer e is 20-60%.
The film forming property of the electron transmission material can be improved by reasonably allocating the proportion of the four isomers, the energy disorder caused by the change of the proportion of the isomers is reduced, the energy level matching of the electron transmission material and the tin-based perovskite is better, the electron extraction and transmission capability of the fullerene film are enhanced, the energy barrier of carrier diffusion at the interface can be effectively reduced, the open-circuit voltage loss is reduced, and the photoelectric conversion efficiency of the tin-based perovskite solar cell is improved.
Further, in a preferred embodiment of the present invention, in the electron transport material of fullerene bis (ethoxycarbonyl) methylene derivative, the mass percentage of isomer trans-2 is 30%, the mass percentage of isomer trans-3 is 40%, the mass percentage of isomer trans-4 is 10%, and the mass percentage of isomer e is 20%.
The invention provides an application of the fullerene di (ethoxycarbonyl) methylene derivative electron transport material in preparation of a tin-based perovskite solar cell.
The invention provides a preparation method of a tin-based perovskite solar cell, which comprises the following steps:
s1, preparing an ITO conductive substrate layer, a hole transport layer and a tin-based perovskite light absorption layer, wherein the hole transport layer is located on the ITO conductive substrate layer, and the tin-based perovskite light absorption layer is located on the hole transport layer.
Specifically, the preparation of the ITO conductive substrate layer, the hole transport layer and the tin-based perovskite light absorption layer comprises the following steps:
and sequentially carrying out ultrasonic treatment on Indium Tin Oxide (ITO) glass in acetone, isopropanol and ethanol for 20min, and then treating the ITO glass in ultraviolet ozone for 20min to obtain the ITO conductive substrate layer. And then dripping PEDOT (PEDOT: PSS) on the cleaned ITO conductive substrate layer in the air at the rotating speed of 4000rpm, spin-coating for 40s, and annealing at 150 ℃ for 15min to obtain the hole transport layer. Finally PEAI and SnF 2 FAI and SnI 2 Dissolved in a mixed solvent of DMF and DMSO (DMF: DMSO ═ 4:1V/V), and stirred in a glove box at 70 ℃ for 1h to ensure sufficient dissolution. And then dripping the dissolved tin-based perovskite precursor solution on the surface of a PEDOT (PSS) film, and spin-coating for 10s and 30s at the rotating speeds of 1000rpm and 5000rpm respectively. In this, 600. mu.L of toluene was dropped as an antisolvent at 20 th s of spin coating at 5000 rpm. And finally, annealing for 10min at the temperature of 70 ℃ to obtain the tin-based perovskite light absorption layer.
S2, synthesizing the fullerene di (ethoxycarbonyl) methylene derivative, and separating and purifying to obtain the isomers trans-2, trans-3, trans-4 and e.
The separation and purification steps of the isomer of the invention comprise: separating fullerene di (ethoxycarbonyl) methylene derivative by High Performance Liquid Chromatography (HPLC), and purifying and drying with methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e.
S3, weighing the isomers trans-2, trans-3, trans-4 and e according to the mass percent of the fullerene di (ethoxycarbonyl) methylene derivative electron transport material, and dissolving the isomers in chlorobenzene to obtain a fullerene solution.
Further, in a preferred embodiment of the present invention, the mass concentration of the fullerene solution is 20-30 mg/mL.
And S4, heating and stirring the fullerene solution, standing, cooling, filtering, spreading on the surface of the deposited tin-based perovskite light absorption layer in a spin coating manner, and annealing at 60-80 ℃ for 5-15 min to obtain the fullerene electron transmission layer film. The fullerene solution is filtered, uniformly and fully spread on the surface of the tin-based perovskite light absorption layer by means of spin coating, and the solvent chlorobenzene is removed by annealing. Preferably, the annealing temperature is 70 ℃ and the annealing time is 10 min.
Further, in a preferred embodiment of the present invention, the step of heating and stirring includes: and (3) putting the fullerene solution into a glove box at the temperature of 60-70 ℃ and heating and stirring for 0.5-1.5 h. The isomers can be fully dissolved in chlorobenzene solution by heating and stirring.
Further, in the preferred embodiment of the present invention, the filtering head with a pore size of 0.2-0.45 μm is used for the filtering. Preferably, the fullerene solution is left to cool and filtered with a Polytetrafluoroethylene (PTFE) filter head having a pore size of 0.22 μm 20min before use.
Further, in a preferred embodiment of the present invention, the thickness of the fullerene electron transport layer film is 50 to 70 nm.
S5, spin-coating a BCP hole blocking layer on the fullerene electron transport layer film, and depositing a metal electrode on the BCP hole blocking layer to obtain the tin-based perovskite solar cell.
Further, in a preferred embodiment of the present invention, the metal electrode is a gold electrode or a silver electrode, and the thickness of the metal electrode is 90 to 100 nm. Preferably, the metal electrode is deposited on the hole blocking layer by means of high vacuum metal thermal evaporation.
Referring to fig. 1, the invention also provides a tin-based perovskite solar cell, which is prepared according to the preparation method, and the tin-based perovskite solar cell comprises an ITO conductive substrate layer, a hole transport layer, a tin-based perovskite light absorption layer, a fullerene electron transport layer, a BCP hole blocking layer and a metal electrode from bottom to top.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The tin-based perovskite solar cell provided by the embodiment can be prepared according to the following method:
(1) preparing an ITO conductive substrate layer: and sequentially carrying out ultrasonic treatment on Indium Tin Oxide (ITO) glass in acetone, isopropanol and ethanol for 20min, and then treating the ITO glass in ultraviolet ozone for 20min to obtain the ITO conductive substrate layer.
(2) Preparation of hole transport layer: and dripping PEDOT: PSS on the cleaned ITO conductive substrate layer in the air at the rotation speed of 4000rpm, spin-coating for 40s, and annealing at 15 ℃ for 15 min.
(3) Preparation of perovskite layer: mixing 14.9mg PEAI and 9.4mg SnF 2 116.9mg FAI and 298mg SnI 2 Dissolved in 1mL of a mixed solvent of DMF and DMSO (DMF: DMSO ═ 4:1V/V), and stirred in a glove box at 70 ℃ for 1h to ensure sufficient dissolution. And then dropwise adding the dissolved tin-based perovskite precursor solution to the surface of a PEDOT (PSS) film, and spin-coating for 10s and 30s at the rotating speeds of 1000rpm and 5000rpm respectively. Wherein 600. mu.L of toluene was dropped as an antisolvent at 20s of spin coating at 5000 rpm. And finally annealing at 70 ℃ for 10 min.
(4) Preparing a fullerene electron transport layer: separating fullerene di (ethoxycarbonyl) methylene derivative by using High Performance Liquid Chromatography (HPLC), purifying and drying by using methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e, and mixing according to the mass percentage of trans-2, trans-3, trans-4 and e of 30 percent to 40 percent to 20 percent (namely the mass ratio of the four isomers is 3:4:1: 2). And dissolving the mixture of the four fullerene isomers in a chlorobenzene solvent to prepare a fullerene solution of 20-30 mg/mL. The fullerene solution was then spin coated on the surface of the tin-based perovskite layer at 1500rpm for 30 seconds and annealed at 70 ℃ for 10 min.
(5) Preparation of a hole blocking layer: BCP (0.5mg/mL, isopropanol) was spin coated at 5000rpm for 30 s. Then annealing at 70 deg.C for 10 min.
(6) Preparing a metal electrode: at a pressure of less than 5X 10 -4 And pa, depositing an Ag electrode with the thickness of about 90-100 nm on the hole blocking layer in a metal thermal evaporation mode to obtain the tin-based perovskite battery. The whole preparation process was carried out in a nitrogen glove box except for PEDOT: PSS, and all solutions used were filtered through a Polytetrafluoroethylene (PTFE) filter tip with a pore size of 0.22. mu.m.
Example 2
The present embodiment provides a tin-based perovskite solar cell, which is mainly different from embodiment 1 in that:
(4) preparing a fullerene electron transport layer: separating fullerene di (ethoxycarbonyl) methylene derivative by using High Performance Liquid Chromatography (HPLC), purifying and drying by using methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e, and mixing according to the mass percentage of trans-2, trans-3, trans-4 and e of 20 percent to 40 percent to 30 percent (namely the mass ratio of the four isomers is 2:4:1: 3). And dissolving the mixture of the four fullerene isomers in a chlorobenzene solvent to prepare a fullerene solution of 20-30 mg/mL. The fullerene solution was then spin coated on the surface of the tin-based perovskite layer at 1500rpm for 30 seconds and annealed at 70 ℃ for 10 min.
Example 3
The present embodiment provides a tin-based perovskite solar cell, which is mainly different from embodiment 1 in that:
(4) preparing a fullerene electron transport layer: separating fullerene di (ethoxycarbonyl) methylene derivative by using High Performance Liquid Chromatography (HPLC), purifying and drying by using methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e, and mixing according to the mass percentage of trans-2, trans-3, trans-4 and e of 30 percent to 10 percent to 30 percent (namely the mass ratio of the four isomers is 3:3:1: 3). And dissolving the mixture of the four fullerene isomers in a chlorobenzene solvent to prepare a fullerene solution of 20-30 mg/mL. The fullerene solution was then spin coated on the surface of the tin-based perovskite layer at 1500rpm for 30 seconds and annealed at 70 ℃ for 10 min.
Comparative example 1
This comparative example provides a tin-based perovskite solar cell, which differs from example 1 mainly in that:
(4) preparing a fullerene electron transport layer: separating fullerene di (ethoxycarbonyl) methylene derivative by using High Performance Liquid Chromatography (HPLC), purifying and drying by using methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e, and mixing according to the mass ratio of trans-2, trans-3, trans-4 and e of 1:2:1: 2. And dissolving the mixture of the four fullerene isomers in a chlorobenzene solvent to prepare a fullerene solution of 20-30 mg/mL. The fullerene solution was then spin coated on the surface of the tin-based perovskite layer at 1500rpm for 30 seconds and annealed at 70 ℃ for 10 min.
Comparative example 2
This comparative example provides a tin-based perovskite solar cell, which differs from example 1 mainly in that:
(4) preparing a fullerene electron transport layer: separating fullerene di (ethoxycarbonyl) methylene derivative by using High Performance Liquid Chromatography (HPLC), purifying and drying by using methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e, and mixing according to the mass ratio of trans-2, trans-3, trans-4 and e of 1:1:1: 1. And dissolving the mixture of the four fullerene isomers in a chlorobenzene solvent to prepare a fullerene solution of 20-30 mg/mL. The fullerene solution was then spin coated on the surface of the tin-based perovskite layer at 1500rpm for 30 seconds and annealed at 70 ℃ for 10 min.
Comparative example 3
This comparative example provides a tin-based perovskite solar cell, which differs from example 1 mainly in that:
(4) preparing a fullerene electron transport layer: separating fullerene di (ethoxycarbonyl) methylene derivative by High Performance Liquid Chromatography (HPLC), purifying and drying by using methanol to obtain four position isomeric pure bodies of trans-2, trans-3, trans-4 and e, and mixing according to the mass ratio of trans-2, trans-3, trans-4 and e of 2:1:2: 1. And dissolving the mixture of the four fullerene isomers in a chlorobenzene solvent to prepare a fullerene solution of 20-30 mg/mL. The fullerene solution was then spin coated on the surface of the tin-based perovskite layer at 1500rpm for 30 seconds and annealed at 70 ℃ for 10 min.
Comparative example 4
This comparative example provides a tin-based perovskite solar cell, which differs from example 1 mainly in that:
(4) will [6,6 ]]-phenyl radical C 61 Dissolving methyl butyrate (PCBM) in chlorobenzene to prepare a solution with the concentration of 20-30 mg/mL, rotationally coating the solution on the surface of the tin-based perovskite layer at the rotating speed of 1500rpm for 30s, and annealing at 70 ℃ for 10 min.
Comparative example 5
This comparative example provides a tin-based perovskite solar cell, which differs from example 1 mainly in that:
(4) indene-C 60 Dissolving a bis-adduct (ICBA) in chlorobenzene to prepare a solution with the concentration of 20-30 mg/mL, rotationally coating the solution on the surface of the tin-based perovskite layer at the rotating speed of 1500rpm for 30s, and annealing the solution at 70 ℃ for 10 min.
Test example 1
The test example performs photoelectric performance tests on the tin-based perovskite solar cell of example 1 and the tin-based perovskite solar cells of comparative examples 1 to 5, respectively. The method comprises the following steps:
the current density-voltage characteristic curve of the device was measured under AM 1.5G conditions using an enliech, AAA solar simulator. Wherein, the voltage scanning range is 0-1V, the step length is 0.005V, and the delay time is 40 ms. The light intensity used for the test was 1000w/m 2 Calibrated with standard silicon solar cells. Active area of PSC for testingIs 0.2cm 2 And using an effective area of 0.12cm 2 To reduce light scattering. External Quantum Efficiency (EQE) data were obtained by using an EQE system (enliech, QER666) without any bias light. The duty stability of the device was obtained by a thin film photovoltaic decay test system (Soy DeRui instruments equipment, Suzhou, SQ-1 OOK-SOOQ). Dark J-V curves were obtained using the CHI660E electrochemical workstation in a dark environment. The electroluminescence data of the device are measured by adopting a fluorescence quantum efficiency testing system of the Xipu opto-electronic technology Limited company, and the system is positioned in a glove box and is provided with an integrating sphere.
The test results are shown in fig. 2 to 6, wherein fig. 2 is a J-V curve of the tin-based perovskite solar cells of examples 1 to 3 and the tin-based perovskite solar cells of comparative examples 1 to 5; FIG. 3 is a PCE statistical chart of the tin-based perovskite solar cells of examples 1-3 and the tin-based perovskite solar cells of comparative examples 1-5; FIG. 4 is a graph showing V of the tin-based perovskite solar cell of examples 1 to 3 and the tin-based perovskite solar cell of comparative examples 1 to 5 OC A statistical chart; FIG. 5 is a graph of J for the tin-based perovskite solar cells of examples 1-3 and comparative examples 1-5 SC A statistical chart; FIG. 6 is a FF statistical chart of the tin-based perovskite solar cells of examples 1-3 and the tin-based perovskite solar cells of comparative examples 1-5. The photoelectric performance parameters of each of the tin-based perovskite solar cells in examples 1 to 3 and comparative examples 1 to 5 are shown in table 1:
TABLE 1 photoelectric Performance parameters of the optimum devices for tin-based perovskite solar cells
As can be seen from FIGS. 2 to 6 and Table 1, the open circuit voltage and the short circuit current of the TPSCs optimized device provided in example 1 were 0.83V and 21.71mA/cm 2 The fill factor is 76.88%, and the PCE reaches 13.87%. Each photoelectric property parameter of the single-substituted fullerene PCBM is obviously superior to TPSCs provided in examples 2-3 and comparative examples 1-3 and single-substituted fullerene PCBM used in comparative example 4TPSCs of electron transport materials. In addition, the TPSCs optimized device in comparative example 5 using the disubstituted fullerene material ICBA as the electron transport material had an open circuit voltage of 0.77V and a short circuit current of 19.07mA/cm 2 The fill factor is 72.96%, and the PCE reaches 10.65%. It can be seen that the photoelectric properties of the TPSCs in example 1 are superior to those of the TPSCs in comparative example 5, i.e., the photoelectric properties of the battery obtained by using the fullerene bis (ethoxycarbonyl) methylene derivative electron transport material as the electron transport material are superior to those of the ICBA which is also a disubstituted fullerene.
The fullerene di (ethoxycarbonyl) methylene derivative electron transport material disclosed by the invention can reduce energy disorder caused by the random accumulation of fullerene isomers, promote the extraction and transmission of current carriers, inhibit the oxidation and erosion of water oxygen in the air on a tin-based perovskite luminescent active layer and simultaneously has better energy level matching with a tin-based perovskite by reasonably regulating the proportion of each isomer, thereby effectively reducing the energy barrier of current carrier diffusion at an interface, reducing the loss of open-circuit voltage and improving the photoelectric conversion efficiency of the tin-based perovskite solar cell.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. 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.
Claims (10)
1. A fullerene di (ethoxycarbonyl) methylene derivative electron transport material is characterized by comprising isomers trans-2, trans-3, trans-4 and e, wherein the molecular structures of the isomers trans-2, trans-3, trans-4 and e are respectively as follows:
according to the mass percentage, in the fullerene di (ethoxycarbonyl) methylene derivative electron transmission material, the mass percentage of the isomer trans-2 is 10-30%, the mass percentage of the isomer trans-3 is 25-40%, the mass percentage of the isomer trans-4 is 5-10%, and the mass percentage of the isomer e is 20-60%.
2. A fullerene bis (ethoxycarbonyl) methylene derivative electron transport material according to claim 1, wherein the fullerene bis (ethoxycarbonyl) methylene derivative electron transport material comprises, in terms of mass%, 30% of the isomer trans-2, 40% of the isomer trans-3, 10% of the isomer trans-4 and 20% of the isomer e.
3. Use of a fullerenic di (ethoxycarbonyl) methylene derivative electron transport material according to any of claims 1 to 2 in the preparation of a tin-based perovskite solar cell.
4. A preparation method of a tin-based perovskite solar cell is characterized by comprising the following steps:
s1, preparing an ITO conductive substrate layer, a hole transport layer and a tin-based perovskite light absorption layer, wherein the hole transport layer is positioned on the ITO conductive substrate layer, and the tin-based perovskite light absorption layer is positioned on the hole transport layer;
s2, after synthesizing the fullerene di (ethoxycarbonyl) methylene derivative, separating and purifying to obtain the isomers trans-2, trans-3, trans-4 and e;
s3, weighing the isomers trans-2, trans-3, trans-4 and e according to the mass percentage of the fullerene di (ethoxycarbonyl) methylene derivative electron transport material as defined in any one of claims 1-2, and dissolving the isomers in chlorobenzene to obtain a fullerene solution;
s4, heating and stirring the fullerene solution, standing, cooling, filtering, spreading on the surface of the tin-based perovskite light absorption layer in a spin coating manner, and annealing at 60-80 ℃ for 5-15 min to obtain a fullerene electron transmission layer film;
s5, spin-coating a BCP hole blocking layer on the fullerene electron transport layer film, and depositing a metal electrode on the BCP hole blocking layer to obtain the tin-based perovskite solar cell.
5. The method according to claim 4, wherein the fullerene solution has a mass concentration of 20 to 30 mg/mL.
6. The method according to claim 4, wherein in step S4, the step of heating and stirring includes: and (3) putting the fullerene solution into a glove box at the temperature of 60-70 ℃ and heating and stirring for 0.5-1.5 h.
7. The method according to claim 4, wherein in step S4, the filter head with a pore size of 0.2-0.45 μm is used for the filtration.
8. The method according to claim 4, wherein in step S4, the fullerene electron transport layer thin film has a thickness of 50 to 70 nm.
9. The method according to claim 4, wherein in step S5, the metal electrode is a gold electrode or a silver electrode, and the thickness of the metal electrode is 90-100 nm.
10. The tin-based perovskite solar cell is characterized by comprising an ITO conductive substrate layer, a hole transport layer, a tin-based perovskite light absorption layer, a fullerene electron transport layer, a BCP hole blocking layer and a metal electrode from bottom to top in sequence.
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