CN112542549A - Wide-band-gap perovskite solar cell and preparation and application thereof - Google Patents
Wide-band-gap perovskite solar cell and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a wide-band-gap perovskite solar cell and a preparation method and application thereof, belonging to the field of photoelectric materials and devices. The method comprises the steps of dissolving lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide in ionic liquid methyl ammonium acetate according to the molar ratio of 3:1:3:1 to prepare a wide-band-gap perovskite precursor solution, coating the precursor solution on ITO transparent conductive glass deposited with an electron transport material and an interface material in air by a one-step heating spin-coating method, and annealing to form the wide-band-gap perovskite thin film with a compact and smooth surface, high crystallinity, low defect state density and good crystal orientation. The prepared wide-band gap perovskite solar cell has excellent photoelectric conversion efficiency and excellent device stability.
Description
Technical Field
The invention relates to a preparation method and application of a wide-band-gap perovskite solar cell, in particular to a simple method for preparing a wide-band-gap perovskite thin film with compact and smooth surface, high crystallinity, low defect state density and good crystal orientation and a perovskite solar cell device thereof, belonging to the technical field of photoelectric materials and devices.
Background
Energy has been an important driving force for the civilized development of human beings, and the use of fossil energy accelerates the development of science and technology and improves the social productivity. However, the modernization pace of society is accelerated, and simultaneously, the problem of environmental pollution caused by 'energy crisis' and fossil energy combustion is also generated, which is more and more paid attention by people. The development of renewable and environment-friendly new energy sources is imperative. Therefore, research and development of renewable energy sources such as water energy, wind energy, solar energy, biomass energy, geothermal energy, tidal energy and the like are carried forward. Among them, "inexhaustible" solar energy is the cleanest energy and is convenient, which is crucial to the sustainable development of society. Therefore, solar energy is expected as an important energy supply for human beings in the future, and development of a novel solar cell having low cost and high efficiency has become a research hotspot in recent years.
At present, the silicon-based solar cell which is dominant in the market is mature in technology, relatively high in photoelectric conversion efficiency, high in production cost and complex in process. The second generation multi-component compound thin film solar cell has high photoelectric conversion efficiency and stable device performance, but part of elements of materials used by the cell have toxicity or scarce reserves, so that the popularization and the use of large areas are limited. Therefore, researchers are constantly working on finding alternative materials with high photoelectric conversion efficiency, low cost, simple process and environmental protection. Organic-inorganic hybrid perovskite solar cells have made unprecedented progress in the field of photovoltaic research with their excellent photovoltaic properties and unique advantages of low cost, low temperature processing, large area process fabrication, etc., and are considered to be one of the most promising "third generation photovoltaic materials". The photoelectric conversion efficiency of the solar cell is rapidly improved from 3.8% to 25.5% in short ten years, and the solar cell is close to the efficiency record of the crystal silicon solar cell which is dominant in the market. The efficiency improvement speed of the perovskite-type photovoltaic device far exceeds that of the first and second generation photovoltaic materials such as traditional crystalline silicon, cadmium telluride, copper indium gallium selenide and the like, so that the perovskite-type photovoltaic device is expected to become a leader of the next generation photovoltaic device.
However, its efficiency is still far below the theoretical schottky-queetier efficiency limit of single junction solar cells. A tandem photovoltaic structure fabricated by interconnecting a wide bandgap top subcell and a narrow bandgap bottom subcell has proven to be an effective strategy to improve device photovoltaic performance beyond the efficiency limit of a single-junction solar cell and to reduce the average cost of photovoltaic power generation. Wide bandgap solar cells are highly limited by the choice of suitable materials and research methods relative to the rapidly developing narrow bandgap solar cells. The band gap continuity adjustability of the ammonium-lead mixed halogen perovskite meets the band gap requirement of matching current and absorption range between the top cell and the bottom cell in the series structure, and becomes an ideal candidate of a light absorption material of a wide band gap perovskite solar cell. Although significant progress has been made in the development of wide bandgap perovskite solar cells, under operating conditions, reversible phase segregation, i.e., the formation of bromide-rich and iodide-rich regions, is typically observed in mixed-halogen perovskite alloys when the bromine content in the components of the perovskite exceeds 20%. This so-called "hooke effect" can lead to large open circuit voltage losses and poor long-term operational stability in wide bandgap perovskite solar cells. Furthermore, the maximum efficiencies achieved by perovskite solar cells in the optimal optical bandgap range of 1.7-1.9eV are still below 20%, which limits the development and application of low cost, solution processed perovskite-based tandem photovoltaic modules.
Researchers now focus on composition adjustment, interface control, and device structure optimization, and few focus on solvents used in perovskite precursor solutions. For solution processed films, solvent effects can have a significant impact on film quality, such as trap density, crystal size, stability. The ionic liquid methylammonium acetate is used as a solvent of a perovskite precursor solution to successfully prepare a perovskite solar cell with high device efficiency and excellent stability in an air environment. However, little is known about how the use of such ionic liquid solvents in wide-bandgap perovskites translates into the overall quality of the perovskite thin film and device performance. The invention researches and uses the methyl ammonium acetate as the solvent of the perovskite precursor solution in the wide-band gap perovskite for the first time, and deeply explores the performance change and the related mechanism principle of the perovskite film and the device. Compared with the traditional mixed solvent DMF/DMSO, the ionic liquid methyl ammonium acetate is used as a wide-band-gap perovskite precursor solvent, and the performance and stability of the wide-band-gap perovskite thin film and the perovskite solar cell prepared by adopting the one-step heating spin coating technology are greatly improved.
Disclosure of Invention
The invention provides a wide-band-gap perovskite thin film and a preparation method of a perovskite solar cell thereof, aiming at solving the technical problems that the wide-band-gap perovskite thin film and the perovskite solar cell thereof are easy to undergo light-induced phase separation under the illumination condition, and the quality and the device performance of the thin film are reduced.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a wide-bandgap perovskite solar cell comprises the following steps:
(1) dissolving lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide in ionic liquid methyl ammonium acetate according to the molar ratio of 3:1:3:1 to prepare a wide-band gap perovskite precursor solution, and stirring at 50-70 ℃ for 6-12 hours;
(2) spin-coating an electron transmission material on the cleaned and processed ITO transparent conductive glass;
(3) spin-coating an interface material on the ITO transparent conductive glass spin-coated with the electron transport material;
(4) preparing a wide-band-gap perovskite thin film on an ITO substrate deposited with an electron transmission material and an interface material by adopting a one-step heating spin coating technology, and annealing to obtain the dense and smooth wide-band-gap perovskite thin film with high crystallinity, low defect state density and good crystal orientation
(5) Coating a hole transport material on the wide-band gap perovskite film in a spinning way;
(6) and (3) evaporating an interface modification material and a metal electrode on the hole transport material in vacuum.
Preferably, the concentration of the wide band gap perovskite precursor solution in the step (1) is 300-600 mg/mL.
Preferably, the electron transport layer deposited on the transparent conductive ITO electrode in step (2) is CPTA, wherein the CPTA is dissolved in DMF solution at a concentration of 2-6mg/mL, and the specific steps are as follows: after CPTA is spin-coated, annealing is carried out for 10-30min at 140 ℃.
Preferably, the interface material spin-coated on the ITO transparent conductive glass spin-coated with the electron transport material in the step (3) is BACl, wherein the BACl is dissolved in a DMSO solution at a concentration of 10-30 mg/mL.
Preferably, the substrate temperature of the heating spin coating technology for preparing the wide-bandgap perovskite thin film in the step (4) is 70-120 ℃, the annealing temperature is 80-120 ℃, and the annealing time is 30s-30 min.
Preferably, the hole transport material spin-coated on the wide-bandgap perovskite thin film in step (5) is Spiro-OMeTAD, and the specific operation is as follows:
(1) 73.2mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene;
(2) dissolving 520mg of lithium salt in 1mL of acetonitrile solution;
(3) add 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution;
(4) adding 28.8 mu LTBP solution to the Spiro-OMeTAD solution;
(5) the mixed solution was stirred at room temperature for 2 hours.
Preferably, the interface modification material vacuum-evaporated on the wide-bandgap perovskite thin film in the step (6) is MoO3The metal electrode is Ag, and the specific steps are as follows:
(1) modification layer MoO3Is 5 nm;
(2) the thickness of the metal Ag electrode is 100 nm.
Preferably, the method comprises the following steps:
and (1) sequentially performing ultrasonic treatment on the etched ITO conductive glass in ethanol, ultrapure water, a cleaning agent, ultrapure water, acetone and ethanol for 20min, drying by using nitrogen, and baking in a 120-DEG C oven for 30min to obtain a clean ITO substrate.
Step (2) 236.93mg of lead iodide, 81.18mg of methylammonium iodide, 62.87mg of lead bromide and 19.01mg of methylammonium bromide are dissolved in ionic liquid methylammonium acetate and stirred at 60 ℃ for 12 hours;
step (3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; dissolving 520mg of lithium salt in 1mL of acetonitrile solution; add 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution; add 28.8 μ LTBP solution to Spiro-OMeTAD solution; stirring the whole mixed solution for 2 hours;
step (4) carrying out ultraviolet ozone treatment on the ITO substrate cleaned in the step (1) for 15 minutes;
dripping 40 mu L of electron transport material CPTA on the ITO substrate processed in the step (4), spin-coating for 30 seconds at the rotating speed of 4000 revolutions per minute, and annealing the ITO spin-coated with the CPTA at 140 ℃ for 15 minutes;
step (6) spin-coating a BACl interface material on the ITO conductive substrate which is subjected to annealing in the step (5) and is spin-coated with the electronic transmission layer, wherein the spin-coating condition is 4000 revolutions per minute, and the spin-coating time is 30 seconds;
step (7) placing the ITO conductive substrate which is spin-coated with the interface material in the step (6) on a heating spin-coating instrument substrate, and preheating for 5 min;
and (8) dripping 90 mu L of the perovskite precursor solution prepared in the step (2) onto the ITO substrate preheated in the step (7), spin-coating to form a film, and then annealing to obtain the perovskite thin film. The rotation speed of the perovskite precursor solution is 4000 revolutions per minute, the spin coating time is 20 seconds, and the perovskite precursor solution is annealed for 5min at the temperature of 100 ℃ in the air;
step (9) spin-coating the hole transport material prepared in the step (3) on the annealed perovskite thin film in the step (8), wherein the spin-coating Spiro-OMeTAD is performed at 3000 revolutions per minute for 30 seconds to form a hole transport layer;
step (10) adopts a vacuum evaporation technology to evaporate 5nm MoO on the hole transport layer in step (9)3And then evaporating 100nm metal electrode Ag to prepare the perovskite solar cell.
In order to solve the above problems, another technical solution proposed by the present invention is: the perovskite solar cell prepared by the preparation method of the wide-band-gap perovskite solar cell.
In order to solve the above problems, another technical solution proposed by the present invention is: the wide band gap perovskite solar cell is applied to the photoelectric field.
The invention has the beneficial effects that:
(1) dissolving lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide in ionic liquid methyl ammonium acetate according to the molar ratio of 3:1:3:1 as a solvent of a wide-bandgap perovskite precursor solution, and preparing the wide-bandgap perovskite thin film by adopting a one-step heating spin coating technology, so that the nucleation process of the crystal is accelerated, the existence of stronger N-H & Br hydrogen bonds in the precursor solution delays the growth process of the perovskite crystal, the crystal nucleation and crystal growth processes are decoupled, and the wide-bandgap perovskite thin film with compact and smooth surface, high crystallinity, low defect state density and good crystal orientation is obtained;
(2) compared with an anti-solvent method, the method has the advantages that the one-step heating spin coating technology is adopted in the air, the operation is simple, the non-toxic and high-humidity air preparation can be realized, the preparation cost of the film is greatly reduced, and the industrialization is more advantageous;
(3) the photoelectric conversion efficiency of the wide-bandgap perovskite solar cell prepared by the method is more than 20%, which is the first report that the efficiency of the wide-bandgap perovskite solar cell is more than 20% and is more than 1.7eV, in contrast, the photoelectric conversion efficiency of the wide-bandgap perovskite solar cell prepared by the traditional mixed solvent DMF/DMSO under the nitrogen atmosphere is 15.53%.
(4) The performance and stability of the wide-bandgap perovskite solar cell prepared by the method are obviously improved.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is a graph of the UV-VIS absorption spectrum of a wide band gap perovskite thin film of the present invention prepared based on the ionic liquid methylammonium acetate and the conventional mixed solvent DMF/DMSO;
FIG. 2 is a SEM comparison of a wide band gap perovskite thin film prepared based on an ionic liquid, namely methyl ammonium acetate, and a traditional mixed solvent, namely DMF/DMSO;
FIG. 3 is a comparative XRD plot of a wide band gap perovskite thin film of the present invention prepared based on the ionic liquid methylammonium acetate and the conventional mixed solvent DMF/DMSO;
FIG. 4 is a graph comparing GIWAXS for wide band gap perovskite thin films prepared based on the ionic liquid methylammonium acetate and the conventional mixed solvent DMF/DMSO in accordance with the present invention;
FIG. 5 is a comparison of proton nuclear magnetic resonance of a wide band gap perovskite precursor solution prepared based on an ionic liquid, methylammonium acetate, and a conventional mixed solvent, DMF/DMSO, in accordance with the present invention;
FIG. 6 is a proton NMR spectrum of different precursor solutions prepared based on ionic liquid methylammonium acetate of the present invention;
FIG. 7 is a graph comparing the photoelectric conversion efficiency J-V curves of wide band gap perovskite solar cells prepared based on the ionic liquid methylammonium acetate and the conventional mixed solvent DMF/DMSO in accordance with the present invention;
FIG. 8 is a graph comparing the photoelectric conversion efficiency of the wide band gap perovskite solar cell prepared based on the ionic liquid methyl ammonium acetate and the traditional mixed solvent DMF/DMSO, under the protection of nitrogen, with the time;
FIG. 9 is a J-V plot of the photoelectric conversion efficiency of a wide band gap perovskite solar cell of the present invention prepared based on an ionic liquid methylammonium acetate;
figure 10 is a schematic representation of a wide band gap perovskite solar cell based on ionic liquid methylammonium acetate fabrication of the present invention.
Detailed Description
Example 1
The embodiment is a preparation method of a wide-bandgap perovskite solar cell and the perovskite solar cell, the wide-bandgap perovskite solar cell has a compact and smooth surface, high crystallinity, low defect state density and good crystal orientation, and mainly comprises the following steps:
and step 1) sequentially carrying out ultrasonic treatment on the etched ITO conductive glass in ethanol, ultrapure water, a cleaning agent, ultrapure water, acetone and ethanol for 20min respectively. And drying by nitrogen, and then baking in an oven at 120 ℃ for 30min to obtain a clean ITO substrate.
Step 2) 236.93mg of lead iodide, 81.18mg of methylammonium iodide, 62.87mg of lead bromide and 19.01mg of methylammonium bromide were dissolved in the ionic liquid methylammonium acetate and stirred at 60 ℃ for 12 hours.
Step 3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; dissolving 520mg of lithium salt in 1mL of acetonitrile solution; add 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution; add 28.8 μ LTBP solution to Spiro-OMeTAD solution; the mixed solution was stirred for 2 hours as a whole.
And 4) carrying out ultraviolet ozone treatment on the ITO substrate cleaned in the step 1) for 15 minutes.
And 5) dripping 40 mu L of electron transport material CPTA on the ITO substrate processed in the step 4), spin-coating for 30 seconds at the rotating speed of 4000 revolutions per minute, and annealing the ITO spin-coated with the CPTA at 140 ℃ for 15 minutes.
And 6) spin-coating a BACl interface material on the ITO conductive substrate which is subjected to annealing in the step 5) and is spin-coated with the electron transmission layer, wherein the spin-coating condition is 4000 revolutions per minute, and the spin-coating time is 30 seconds.
And 7) placing the ITO conductive substrate which is spin-coated with the interface material in the step 6) on a heating spin-coating instrument substrate, and preheating for 5 min.
And 8) dripping 90 mu L of the perovskite precursor solution prepared in the step 2) onto the ITO substrate preheated in the step 7), spin-coating to form a film, and then annealing to obtain the perovskite thin film. The rotation speed of the perovskite precursor solution is 4000 revolutions per minute, the spin coating time is 20 seconds, and the perovskite precursor solution is annealed for 5min at the temperature of 100 ℃ in the air.
And 9) spin-coating the hole transport material prepared in the step 3) on the annealed perovskite thin film in the step 8), wherein the spin-coating is carried out at 3000 revolutions per minute for 30 seconds, so as to form a hole transport layer.
Step 10) evaporating 5nm MoO on the hole transport layer in the step 9) by adopting a vacuum evaporation technology3And then evaporating 100nm metal electrode Ag to prepare the perovskite solar cell.
Step 11) under standard test conditions (AM 1.5G illumination), the performance parameters of the perovskite battery device prepared based on the ammonium methyl acetate prepared in this example were, respectively, an energy conversion efficiency of 20.59%, an open-circuit voltage of 1.22V, and a short-circuit current of 20.85mA/cm2The fill factor is 81.11%;
FIG. 1 is a UV-visible absorption spectrum of a wide band gap perovskite thin film prepared based on an ionic liquid of methyl ammonium acetate and a traditional mixed solvent of DMF/DMSO, wherein optical band gaps of the wide band gap perovskite thin films prepared by different solvents are all 1.71 eV;
FIG. 2 is a SEM comparison of the wide band gap perovskite thin film prepared based on the ionic liquid methyl ammonium acetate and the traditional mixed solvent DMF/DMSO, the grain size of the wide band gap perovskite thin film prepared based on the traditional mixed solvent DMF/DMSO is about 250nm, and the grain size of the wide band gap perovskite thin film prepared based on the ionic liquid methyl ammonium acetate reaches micron level and the surface of the thin film is smooth;
FIG. 3 is an XRD contrast diagram of a wide-band-gap perovskite thin film prepared based on ionic liquid methylammonium acetate and a traditional mixed solvent DMF/DMSO, wherein the wide-band-gap perovskite thin film prepared based on the ionic liquid methylammonium acetate has higher peak diffraction intensity and smaller full width at half maximum of a diffraction peak, and shows that the crystallinity of the thin film is better;
FIG. 4 is a graph comparing GIWAXS of wide band gap perovskite thin films prepared based on ionic liquid methylammonium acetate and a conventional mixed solvent DMF/DMSO, wherein the wide band gap perovskite thin films prepared based on the ionic liquid methylammonium acetate have better crystal orientation degree and higher crystal growth degree along the direction vertical to the substrate, which is beneficial to charge transmission;
FIG. 5 is a comparison of proton Nuclear Magnetic Resonance (NMR) of a wide band gap perovskite precursor solution prepared based on ionic liquid methylammonium acetate and a conventional mixed solvent DMF/DMSO, where certain interactions between the methylammonium acetate and the precursor were detected in the wide band gap perovskite precursor solution prepared based on the ionic liquid methylammonium acetate, but were not observed in the wide band gap perovskite precursor solution prepared by the conventional mixed solvent DMF/DMSO;
FIG. 6 is a proton NMR spectrum of different precursor solutions prepared based on ionic liquid methylammonium acetate of the present invention, wherein the ionic liquid methylammonium acetate, iodine, and bromine all form hydrogen bonds, wherein the N-H-Br hydrogen bonds are stronger than the N-H-I hydrogen bonds, and for bromine-rich wide-bandgap perovskites, the interaction between the ionic liquid methylammonium acetate and bromine is beneficial for the preparation of wide-bandgap perovskite thin films;
FIG. 7 is a comparison of the J-V curves for photoelectric conversion efficiency of wide bandgap perovskite solar cells of the present invention based on ionic liquid methylammonium acetate and conventional mixed solvent DMF/DMSO, with efficiencies of 20.59% for wide bandgap perovskite solar cells based on ionic liquid methylammonium acetate, which are first reported to exceed 20% for wide bandgap perovskite device efficiencies greater than 1.7 eV;
FIG. 8 is a graph comparing the photoelectric conversion efficiency of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methyl ammonium acetate and the conventional mixed solvent DMF/DMSO, under the protection of nitrogen, with the time. Under the nitrogen atmosphere, the wide-band gap perovskite solar cell prepared based on the ionic liquid methylammonium acetate still keeps more than 95% of the initial efficiency after being placed for more than 1200 hours, while the efficiency of the wide-band gap perovskite solar cell prepared based on the traditional mixed solvent DMF/DMSO is reduced to 83% of the initial efficiency under the storage under the same condition;
comparative example 1
The embodiment of the invention relates to a wide-bandgap perovskite solar cell, which mainly comprises the following steps:
and step 1) sequentially carrying out ultrasonic treatment on the etched ITO conductive glass in ethanol, ultrapure water, a cleaning agent, ultrapure water, acetone and ethanol for 20min respectively. And drying by nitrogen, and then baking in an oven at 120 ℃ for 30min to obtain a clean ITO substrate.
Step 2) 315.37mg of lead iodide, 27.19mg of methylammonium iodide, and 57.45mg of methylammonium bromide were dissolved in the ionic liquid methylammonium acetate, and stirred at 60 ℃ for 12 hours.
Step 3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; dissolving 520mg of lithium salt in 1mL of acetonitrile solution; add 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution; add 28.8 μ LTBP solution to Spiro-OMeTAD solution; the mixed solution was stirred for 2 hours as a whole.
And 4) carrying out ultraviolet ozone treatment on the ITO substrate cleaned in the step 1) for 15 minutes.
And 5) dripping 40 mu L of electron transport material CPTA on the ITO substrate processed in the step 4), spin-coating for 30 seconds at the rotating speed of 4000 revolutions per minute, and annealing the ITO spin-coated with the CPTA at 140 ℃ for 15 minutes.
And 6) spin-coating a BACl interface material on the ITO conductive substrate which is subjected to annealing in the step 5) and is spin-coated with the electron transmission layer, wherein the spin-coating condition is 4000 revolutions per minute, and the spin-coating time is 30 seconds.
And 7) placing the ITO conductive substrate which is spin-coated with the interface material in the step 6) on a heating spin-coating instrument substrate, and preheating for 5 min.
And 8) dripping 90 mu L of the perovskite precursor solution prepared in the step 2) onto the ITO substrate preheated in the step 7), spin-coating to form a film, and then annealing to obtain the perovskite thin film. The rotation speed of the perovskite precursor solution is 4000 revolutions per minute, the spin coating time is 20 seconds, and the perovskite precursor solution is annealed for 5min at the temperature of 100 ℃ in the air.
And 9) spin-coating the hole transport material prepared in the step 3) on the annealed perovskite thin film in the step 8), wherein the spin-coating is carried out at 3000 revolutions per minute for 30 seconds, so as to form a hole transport layer.
Step 10) evaporating 5nm MoO on the hole transport layer in the step 9) by adopting a vacuum evaporation technology3And then evaporating 100nm metal electrode Ag to prepare the perovskite solar cell.
Step 11) under standard test conditions (AM 1.5G illumination), this comparative example used ionic liquid methylammonium acetate as the solvent for the wide-bandgap perovskite precursor solution, the wide-bandgap perovskite precursor materials used were lead iodide, methylammonium bromide, and the performance parameters of the prepared perovskite battery devices were, respectively, 18.81% energy conversion efficiency, 1.17V open-circuit voltage, and 19.94mA/cm short-circuit current2The fill factor was 80.41%.
Fig. 9 is a J-V plot of the photoelectric conversion efficiency of the wide bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate of the present invention, wherein the wide bandgap perovskite precursor materials used are lead iodide, methylammonium iodide, and methylammonium bromide. The prepared device has the efficiency of 18.81 percent, which is inferior to that of a wide-band gap perovskite precursor solution prepared by taking lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide as wide-band gap perovskite precursor materials. In example 1, hydrogen bonds are formed by the ionic liquid methyl ammonium acetate, iodine and bromine, wherein the hydrogen bonds N-H.Br are stronger than the hydrogen bonds N-H.I, and for the bromine-rich wide-bandgap perovskite, the interaction between the ionic liquid methyl ammonium acetate and the bromine is beneficial to the preparation of the wide-bandgap perovskite film.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a wide-bandgap perovskite solar cell is characterized by comprising the following steps:
(1) dissolving lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide in ionic liquid methyl ammonium acetate according to the molar ratio of 3:1:3:1 to prepare a wide-band gap perovskite precursor solution, and stirring at 50-70 ℃ for 6-12 hours;
(2) spin-coating an electron transmission material on the cleaned and processed ITO transparent conductive glass;
(3) spin-coating an interface material on the ITO transparent conductive glass spin-coated with the electron transport material;
(4) preparing a wide-band-gap perovskite thin film on an ITO substrate deposited with an electron transport material and an interface material by adopting a one-step heating spin coating technology, and annealing to obtain the wide-band-gap perovskite thin film which is compact and smooth, high in crystallinity, low in defect state density and good in crystal orientation;
(5) coating a hole transport material on the wide-band gap perovskite film in a spinning way;
(6) and (3) evaporating an interface modification material and a metal electrode on the hole transport material in vacuum.
2. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the concentration of the wide band gap perovskite precursor solution in the step (1) is 300-600 mg/mL.
3. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the electron transport layer deposited on the transparent conductive ITO electrode in the step (2) is CPTA, wherein the CPTA is dissolved in DMF solution at the concentration of 2-6mg/mL, and the specific steps are as follows: after CPTA is spin-coated, annealing is carried out for 10-30min at 140 ℃.
4. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the interface material spin-coated on the ITO transparent conductive glass spin-coated with the electron transport material in the step (3) is BACl, wherein the BACl is dissolved in DMSO solution at the concentration of 10-30 mg/mL.
5. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the substrate temperature of the heating spin coating technology for preparing the wide band gap perovskite thin film in the step (4) is 70-120 ℃, the annealing temperature is 80-120 ℃, and the annealing time is 30s-30 min.
6. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the hole transport material spin-coated on the wide-bandgap perovskite thin film in the step (5) is Spiro-OMeTAD, and the specific operation is as follows:
(1) 73.2mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene;
(2) dissolving 520mg of lithium salt in 1mL of acetonitrile solution;
(3) add 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution;
(4) adding 28.8 mu LTBP solution to the Spiro-OMeTAD solution;
(5) the mixed solution was stirred at room temperature for 2 hours.
7. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the interface modification material vacuum-evaporated on the wide-band-gap perovskite film in the step (6) is MoO3The metal electrode is Ag, and the specific steps are as follows:
(1) modification layer MoO3Is 5 nm;
(2) the thickness of the metal Ag electrode is 100 nm.
8. The method of fabricating a wide bandgap perovskite solar cell of claim 1, wherein: the method comprises the following steps:
and (1) sequentially performing ultrasonic treatment on the etched ITO conductive glass in ethanol, ultrapure water, a cleaning agent, ultrapure water, acetone and ethanol for 20min, drying by using nitrogen, and baking in a 120-DEG C oven for 30min to obtain a clean ITO substrate.
Step (2) 236.93mg of lead iodide, 81.18mg of methylammonium iodide, 62.87mg of lead bromide and 19.01mg of methylammonium bromide are dissolved in ionic liquid methylammonium acetate and stirred at 60 ℃ for 12 hours;
step (3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; dissolving 520mg of lithium salt in 1mL of acetonitrile solution; add 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution; add 28.8 μ LTBP solution to Spiro-OMeTAD solution; stirring the whole mixed solution for 2 hours;
step (4) carrying out ultraviolet ozone treatment on the ITO substrate cleaned in the step (1) for 15 minutes;
dripping 40 mu L of electron transport material CPTA on the ITO substrate processed in the step (4), spin-coating for 30 seconds at the rotating speed of 4000 revolutions per minute, and annealing the ITO spin-coated with the CPTA at 140 ℃ for 15 minutes;
step (6) spin-coating a BACl interface material on the ITO conductive substrate which is subjected to annealing in the step (5) and is spin-coated with the electronic transmission layer, wherein the spin-coating condition is 4000 revolutions per minute, and the spin-coating time is 30 seconds;
step (7) placing the ITO conductive substrate which is spin-coated with the interface material in the step (6) on a heating spin-coating instrument substrate, and preheating for 5 min;
and (8) dripping 90 mu L of the perovskite precursor solution prepared in the step (2) onto the ITO substrate preheated in the step (7), spin-coating to form a film, and then annealing to obtain the perovskite thin film. The rotation speed of the perovskite precursor solution is 4000 revolutions per minute, the spin coating time is 20 seconds, and the perovskite precursor solution is annealed for 5min at the temperature of 100 ℃ in the air;
step (9) spin-coating the hole transport material prepared in the step (3) on the annealed perovskite thin film in the step (8), wherein the spin-coating Spiro-OMeTAD is performed at 3000 revolutions per minute for 30 seconds to form a hole transport layer;
step (10) adopts a vacuum evaporation technology to evaporate 5nm MoO on the hole transport layer in step (9)3And then evaporating 100nm metal electrode Ag to prepare the perovskite solar cell.
9. A perovskite solar cell manufactured by the method for manufacturing a wide bandgap perovskite solar cell according to any one of claims 1 to 8.
10. Use of the wide bandgap perovskite solar cell according to claim 9 in the field of photovoltaics.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114551742A (en) * | 2022-02-23 | 2022-05-27 | 电子科技大学 | Silicon-based high-speed perovskite light source and preparation method thereof |
| CN114843406A (en) * | 2022-04-02 | 2022-08-02 | 湖北文理学院 | Preparation method of organic-inorganic hybrid perovskite thin film and preparation method of semitransparent solar cell |
| WO2023051494A1 (en) * | 2021-09-28 | 2023-04-06 | 天合光能股份有限公司 | Large-area perovskite layer and preparation method therefor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140332078A1 (en) * | 2013-05-09 | 2014-11-13 | National Cheng Kung University | Hybrid organic solar cell with perovskite structure as absorption material and manufacturing method thereof |
| CN108321299A (en) * | 2018-02-22 | 2018-07-24 | 南京工业大学 | A kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery |
| CN108336249A (en) * | 2018-02-22 | 2018-07-27 | 南京工业大学 | One kind is based on straight chain organic diamine low-dimensional perovskite solar cell and its preparation method and application |
| CN108365102A (en) * | 2018-02-22 | 2018-08-03 | 南京工业大学 | A kind of stability and high efficiency two-dimensional layer perovskite solar cell and preparation method thereof |
| CN108666424A (en) * | 2018-01-05 | 2018-10-16 | 南京工业大学 | One kind preparing perovskite solar cell and its methods and applications based on acetic acid methylamine room temperature fused salt as green solvent |
| CN111710780A (en) * | 2020-06-18 | 2020-09-25 | 西北工业大学 | Preparation method of cathode in-situ modified perovskite solar cell without electron transport layer |
-
2020
- 2020-12-08 CN CN202011423449.0A patent/CN112542549B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140332078A1 (en) * | 2013-05-09 | 2014-11-13 | National Cheng Kung University | Hybrid organic solar cell with perovskite structure as absorption material and manufacturing method thereof |
| CN108666424A (en) * | 2018-01-05 | 2018-10-16 | 南京工业大学 | One kind preparing perovskite solar cell and its methods and applications based on acetic acid methylamine room temperature fused salt as green solvent |
| CN108321299A (en) * | 2018-02-22 | 2018-07-24 | 南京工业大学 | A kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery |
| CN108336249A (en) * | 2018-02-22 | 2018-07-27 | 南京工业大学 | One kind is based on straight chain organic diamine low-dimensional perovskite solar cell and its preparation method and application |
| CN108365102A (en) * | 2018-02-22 | 2018-08-03 | 南京工业大学 | A kind of stability and high efficiency two-dimensional layer perovskite solar cell and preparation method thereof |
| CN111710780A (en) * | 2020-06-18 | 2020-09-25 | 西北工业大学 | Preparation method of cathode in-situ modified perovskite solar cell without electron transport layer |
Non-Patent Citations (2)
| Title |
|---|
| LINGFENG CHAO等: "Room-Temperature Molten Salt for Facile Fabrication of Efficient and Stable Perovskite Solar Cells in Ambient Air", 《CHEM》, vol. 5, pages 995 - 1006 * |
| ZHOU, YANG等: "Distribution of bromine in mixed iodide-bromide organolead perovskites and its impact on photovoltaic performance", 《JOURNAL OF MATERIALS CHEMISTRY A》, vol. 4, pages 16191 - 16197 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023051494A1 (en) * | 2021-09-28 | 2023-04-06 | 天合光能股份有限公司 | Large-area perovskite layer and preparation method therefor |
| CN114551742A (en) * | 2022-02-23 | 2022-05-27 | 电子科技大学 | Silicon-based high-speed perovskite light source and preparation method thereof |
| CN114551742B (en) * | 2022-02-23 | 2023-11-17 | 电子科技大学 | Silicon-based high-speed perovskite light source and preparation method thereof |
| CN114843406A (en) * | 2022-04-02 | 2022-08-02 | 湖北文理学院 | Preparation method of organic-inorganic hybrid perovskite thin film and preparation method of semitransparent solar cell |
| WO2023184626A1 (en) * | 2022-04-02 | 2023-10-05 | 湖北文理学院 | Preparation method for organic-inorganic hybrid perovskite thin film and preparation method for semi-transparent solar cell |
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