CN112542549B - Wide-bandgap perovskite solar cell and preparation and application thereof - Google Patents
Wide-bandgap perovskite solar cell and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a wide-bandgap perovskite solar cell, a preparation method and application thereof, and belongs to the field of photoelectric materials and devices. According to the preparation method, lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide are dissolved in ionic liquid methyl ammonium acetate according to a molar ratio of 3:1:3:1 to prepare a wide band gap perovskite precursor solution, the precursor solution is spin-coated on ITO transparent conductive glass deposited with an electron transport material and an interface material in air by adopting a one-step heating spin-coating method, and a wide band gap perovskite film with compact and smooth surface, high crystallinity, low defect state density and good crystal orientation is formed after annealing treatment. The prepared wide-bandgap 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-bandgap perovskite solar cell, in particular to a simple method for preparing a wide-bandgap 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, and belongs to the technical field of photoelectric materials and devices.
Background
Energy is always an important driving force for the development of human civilization, and the use of fossil energy accelerates the development of science and technology and improves social productivity. However, the modern pace of society is accelerated, and the environmental pollution problem caused by the energy crisis and the fossil energy combustion is also generated, which is also more and more paid attention to. Expanding new renewable and environment-friendly energy is imperative. Accordingly, research and development of renewable energy sources such as water energy, wind energy, solar energy, biomass energy, geothermal energy, tidal energy and the like have been carried out. Among them, "inexhaustible" solar energy is the cleanest energy source and is convenient to obtain, which is important for sustainable development of society. Therefore, solar energy is highly desired as an important energy source for human in the future, and development of a novel solar cell with low cost and high efficiency is also becoming a research hotspot in recent years.
At present, the dominant silicon-based solar cell technology in the market is mature, the photoelectric conversion efficiency is relatively high, but the production cost is high, and the process is complex. The second generation multi-element compound thin film solar cell has higher photoelectric conversion efficiency and stable device performance, but partial elements of materials used by the cell have toxicity or scarce reserves, and the popularization and the use in a large area are limited. Therefore, researchers are continually striving to find alternative materials with high photoelectric conversion efficiency, low cost, simple process and environmental protection. Organic-inorganic hybrid perovskite solar cells have not advanced in the photovoltaic research field, with their unique advantages of excellent photovoltaic properties, low cost, low temperature processing, large area process fabrication, etc., and are considered to be one of the most potential representatives of the "third generation photovoltaic materials". In a short decade, the photoelectric conversion efficiency of the solar cell is rapidly improved from 3.8% to 25.5%, and the solar cell is close to the efficiency record of the dominant crystalline silicon solar cell in the market. The efficiency improvement speed of the perovskite photovoltaic device is far higher than that of the first and second generation photovoltaic materials such as the traditional crystalline silicon, cadmium telluride, copper indium gallium selenide and the like, so that the perovskite photovoltaic device is expected to become a master of the next generation photovoltaic device.
However, its efficiency is also far below the theoretical Shokrill-quinine efficiency limit for a single solar cell. The series photovoltaic structure fabricated by interconnecting the wide bandgap top subcell and the narrow bandgap bottom subcell has proven to be an effective strategy to improve device photovoltaic performance beyond the single solar cell efficiency limit and 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 high-speed development of narrow bandgap solar cells. The continuous adjustability of the band gap of the lead-methyl-ammonium-mixed-halogen perovskite meets the band gap requirement of matching the current and absorption ranges between the top and bottom cells in a series structure, and becomes an ideal candidate of the light absorption material of the wide-band-gap perovskite solar cell. Although significant progress has been made in the investigation of wide band gap perovskite solar cells, under operating conditions, when the bromine content of the perovskite components exceeds 20%, reversible phase segregation, i.e., formation of bromide-rich and iodide-rich regions, is generally observed in mixed halogen perovskite alloys. This so-called "hooke effect" results in a large open circuit voltage loss in a wide bandgap perovskite solar cell and poor long-term operation stability. In addition, perovskite solar cells achieve maximum efficiencies still below 20% in the optimal optical bandgap range of 1.7-1.9eV, which limits the development and application of low cost, solution processed perovskite-based tandem photovoltaic modules.
Researchers now focus on composition tuning, interface control and device structure optimization, and few have focused on the solvents used for perovskite precursor solutions. For solution-processed films, solvent effects can have a significant impact on film quality, such as trap density, crystal size, stability. Ionic liquid methyl ammonium acetate as a solvent for perovskite precursor solutions has been successful in producing perovskite solar cells 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 takes the methyl ammonium acetate as the solvent of perovskite precursor solution in the wide-bandgap perovskite for the first time, and deeply explores the variation of perovskite film and device performance and related mechanism principles. 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 performances and the stability of the wide band gap perovskite film and the perovskite solar cell prepared by adopting the one-step heating spin coating technology are greatly improved.
Disclosure of Invention
Aiming at the technical problems that a wide band gap perovskite film and a perovskite solar cell thereof are easy to generate photoinduced phase separation under illumination conditions, the quality and the device performance of the film are reduced, the invention provides a preparation method of the wide band gap perovskite film and the perovskite solar cell thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the preparation method of the wide-bandgap perovskite solar cell comprises the following steps of:
(1) Dissolving lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide in ionic liquid methyl ammonium acetate according to a molar ratio of 3:1:3:1 to prepare a wide band gap perovskite precursor solution, and stirring for 6-12 hours at 50-70 ℃;
(2) Spin-coating an electron transport 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) On an ITO substrate deposited with an electron transport material and an interface material, preparing a wide band gap perovskite film by adopting a one-step heating spin coating technology, and obtaining the wide band gap perovskite film which is compact and smooth, high in crystallinity, low in defect state density and good in crystal orientation after annealing treatment
(5) Spin-coating a hole transport material on the wide band gap perovskite film;
(6) And vacuum evaporating interface modifying material and metal electrode on the hole transporting material.
Preferably, the concentration of the wide bandgap perovskite precursor solution in the step (1) is 300-600mg/mL.
Preferably, the electron transport layer deposited on the transparent conductive ITO electrode in the step (2) is CPTA, where the CPTA is dissolved in DMF solution at a concentration of 2-6mg/mL, and the specific steps are: after spin coating CPTA, annealing is performed at 140℃for 10-30min.
Preferably, in the step (3), the interface material spin-coated on the ITO transparent conductive glass spin-coated with the electron transport material is BACl, wherein the BACl is dissolved in DMSO solution at a concentration of 10-30 mg/mL.
Preferably, the substrate temperature of the heating spin coating technology for preparing the wide band gap perovskite film in the step (4) is 70-120 ℃, the annealing temperature is 80-120 ℃, and the annealing time is 30s-30min.
Preferably, the hole transport material spin-coated on the wide bandgap perovskite film in the step (5) is a Spiro-ome, and the specific operation is as follows:
(1) 73.2mg of Spiro-OMeTAD were dissolved in 1mL of chlorobenzene;
(2) 520mg of lithium salt was dissolved in 1mL of acetonitrile solution;
(3) 17.6. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution;
(4) 28.8 μ LTBP solution was added to the Spiro-OMeTAD solution;
(5) The mixed solution was stirred at room temperature for 2 hours.
Preferably, in the step (6), the interface modification material vacuum evaporated on the wide-bandgap perovskite film is MoO 3 The metal electrode is Ag, and the specific steps are as follows:
(1) Modification layer MoO 3 Is 5nm thick;
(2) The thickness of the metal Ag electrode was 100nm.
Preferably, the method comprises the following steps:
and (1) sequentially carrying out ultrasonic treatment on the etched ITO conductive glass in ethanol, ultrapure water, cleaning agent, ultrapure water, acetone and ethanol for 20min, drying by nitrogen, and then placing the dried ITO conductive glass in a baking oven at 120 ℃ for baking for 30min to obtain a clean ITO substrate.
Step (2) dissolving 236.93mg of lead iodide, 81.18mg of methyl ammonium iodide, 62.87mg of lead bromide and 19.01mg of methyl ammonium bromide in ionic liquid methyl ammonium acetate, and stirring at 60 ℃ for 12 hours;
step (3) 73.2mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene; 520mg of lithium salt was dissolved in 1mL of acetonitrile solution; 17.6. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution; adding 28.8 μ LTBP solution to the Spiro-OMeTAD solution; the mixed solution is integrally stirred for 2 hours;
step (4), treating the ITO substrate cleaned in the step (1) with ultraviolet ozone for 15 minutes;
step (5) taking 40 mu L of electron transport material CPTA, dripping the CPTA onto 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 CPTA at 140 ℃ for 15 minutes;
step (6), spin-coating BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer after annealing in the step (5), 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 spin-coated with the interface material in the step (6) on a substrate of a heating spin-coating instrument, and preheating for 5min;
and (8) taking 90 mu L of the perovskite precursor solution prepared in the step (2), dripping the solution onto the preheated ITO substrate in the step 7), spin-coating to form a film, and then annealing to obtain the perovskite film. Spin-coating perovskite precursor solution at 4000 rpm for 20 seconds, and annealing at 100deg.C in air for 5min;
step (9) spin-coating the hole transport material prepared in the step (3) on the perovskite film annealed in the step (8), wherein spin-coating of the Spiro-OMeTAD is carried out 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 the step (9) 3 And then evaporating a 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 a molar ratio of 3:1:3:1 as a solvent of a wide band gap perovskite precursor solution, adopting a one-step heating spin coating technology to prepare a wide band gap perovskite film, accelerating the nucleation process of crystals, delaying the growth process of perovskite crystals due to the existence of stronger N-H.Br hydrogen bonds in the precursor solution, and decoupling the crystal nucleation and crystal growth processes to obtain the wide band gap perovskite film with compact and smooth surface, high crystallinity, low defect state density and good crystal orientation;
(2) Compared with an antisolvent method, the one-step heating spin coating technology is simple to operate, is nontoxic, can be prepared in air with high humidity, greatly reduces the preparation cost of the film, and has more advantages in the aspect of industrialization;
(3) The photoelectric conversion efficiency of the wide band gap perovskite solar cell prepared by the method is more than 20%, which is that the efficiency of the wide band gap perovskite solar cell which is more than 1.7eV is reported to be more than 20% for the first time, in sharp contrast to the fact that the photoelectric conversion efficiency of the wide band gap perovskite solar cell prepared by the traditional mixed solvent DMF/DMSO under the nitrogen atmosphere is 15.53%.
(4) The device performance and stability of the wide-bandgap perovskite solar cell prepared by the method are obviously improved.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a graph of the ultraviolet-visible absorption spectrum of a wide band gap perovskite thin film of the invention prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO;
FIG. 2 is a SEM contrast of a wide bandgap perovskite thin film of the invention prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO;
FIG. 3 is an XRD contrast pattern of a wide band gap perovskite thin film of the invention prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO;
FIG. 4 is a GIWAXS comparison of a wide bandgap perovskite thin film of the invention prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO;
FIG. 5 is a proton nuclear magnetic resonance contrast plot of a wide bandgap perovskite precursor solution of the invention prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO;
FIG. 6 is a proton nuclear magnetic resonance spectrum of different precursor solutions of the present invention prepared based on ionic liquid methyl ammonium acetate;
FIG. 7 is a graph comparing the photoelectric conversion efficiency J-V curves of a wide bandgap perovskite solar cell prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO according to the present invention;
FIG. 8 is a graph comparing the photoelectric conversion efficiency of a wide bandgap perovskite solar cell prepared based on ionic liquid methyl ammonium acetate and a traditional mixed solvent DMF/DMSO according to the invention with time under the protection of nitrogen;
FIG. 9 is a graph of the photoelectric conversion efficiency J-V of a wide bandgap perovskite solar cell prepared based on ionic liquid methyl ammonium acetate according to the invention;
fig. 10 is a schematic diagram of a wide bandgap perovskite solar cell according to the invention based on ionic liquid methyl ammonium acetate production.
Detailed Description
Example 1
The embodiment is a preparation method of a wide-bandgap perovskite solar cell and the perovskite solar cell thereof, and the wide-bandgap perovskite solar cell has compact and smooth surface, high crystallinity, low defect state density and good crystal orientation, and mainly comprises the following steps:
step 1), sequentially adding the etched ITO conductive glass into ethanol, ultrapure water, cleaning agent, ultrapure water, acetone and ethanol, and respectively carrying out ultrasonic treatment for 20min. Drying with nitrogen, and baking in an oven at 120deg.C for 30min to obtain clean ITO substrate.
Step 2) 236.93mg of lead iodide, 81.18mg of methyl ammonium iodide, 62.87mg of lead bromide, 19.01mg of methyl ammonium bromide were dissolved in the ionic liquid methyl ammonium acetate and stirred at 60℃for 12 hours.
Step 3) 73.2mg of Spiro-OMeTAD were dissolved in 1mL of chlorobenzene; 520mg of lithium salt was dissolved in 1mL of acetonitrile solution; 17.6. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution; adding 28.8 μ LTBP solution to the Spiro-OMeTAD solution; the mixed solution was stirred for 2 hours as a whole.
Step 4) treating the ITO substrate cleaned in the step 1) with ultraviolet ozone for 15 minutes.
Step 5) taking 40 mu L of CPTA (electron transport material) and dripping the CPTA onto 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 CPTA at 140 ℃ for 15 minutes.
Step 6) spin-coating BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer after annealing in step 5), 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 spin-coated with the interface material in the step 6) on a substrate of a heating spin-coating instrument, and preheating for 5min.
Step 8) taking 90 mu L of the perovskite precursor solution prepared in the step 2), dripping the solution onto the ITO substrate preheated in the step 7), spin-coating to form a film, and then annealing to obtain the perovskite film. The spin-on perovskite precursor solution was spun at 4000 rpm for 20 seconds and annealed in air at 100 ℃ for 5 minutes.
Step 9) spin-coating the hole transport material prepared in the step 3) onto the perovskite film annealed in the step 8), wherein spin-coating of Spiro-OMeTAD is carried out at 3000 rpm for 30 seconds to form a hole transport layer.
Step 10) vapor plating 5nm MoO on the hole transport layer of step 9) by vacuum vapor plating technique 3 And then evaporating a 100nm metal electrode Ag to prepare the perovskite solar cell.
Step 11) under standard test conditions (AM 1.5G illumination), the perovskite battery device performance parameters prepared based on the methyl ammonium acetate prepared in this example are, respectively, energy conversion efficiency of 20.59%, open circuit voltage of 1.22V, and short circuit current of 20.85mA/cm 2 The filling factor is 81.11%;
FIG. 1 is an ultraviolet-visible absorption spectrum diagram of a wide-bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate and a traditional mixed solvent DMF/DMSO, wherein the optical band gap of the wide-bandgap perovskite film prepared by different solvents is 1.71eV;
FIG. 2 is a SEM contrast graph of a wide bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO according to the present invention, wherein the grain size of the wide bandgap perovskite film prepared based on the conventional mixed solvent DMF/DMSO is about 250nm, and the grain size of the wide bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate reaches a micron level and the surface of the film is smooth;
FIG. 3 is an XRD contrast diagram of a wide-bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate and a traditional mixed solvent DMF/DMSO, wherein the wide-bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate has higher peak diffraction intensity and smaller half-width of diffraction peak, and shows that the crystallinity of the film is better;
FIG. 4 is a GIWAXS comparison graph of a wide-bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate and a traditional mixed solvent DMF/DMSO, wherein the wide-bandgap perovskite film prepared based on ionic liquid methyl ammonium acetate has better crystal orientation degree, and the crystal growth degree is higher along the direction perpendicular to a substrate, so that the charge transmission is facilitated;
FIG. 5 is a proton nuclear magnetic resonance contrast plot of a wide bandgap perovskite precursor solution of the invention prepared based on ionic liquid methyl ammonium acetate and conventional mixed solvent DMF/DMSO, where a certain interaction between methyl ammonium acetate and precursor was detected in the wide bandgap perovskite precursor solution prepared based on ionic liquid methyl ammonium acetate, but not observed in the wide bandgap perovskite precursor solution prepared based on conventional mixed solvent DMF/DMSO;
FIG. 6 is a proton nuclear magnetic resonance spectrum of different precursor solutions prepared based on ionic liquid methyl ammonium acetate according to the invention, wherein ionic liquid methyl ammonium acetate, iodine and bromine all form hydrogen bonds, wherein N-H.Br hydrogen bonds are stronger than N-H.I hydrogen bonds, and for a bromine-rich wide bandgap perovskite, the interaction between ionic liquid methyl ammonium acetate and bromine is beneficial to the preparation of a wide bandgap perovskite film;
FIG. 7 is a graph comparing the photoelectric conversion efficiency J-V curves of a wide bandgap perovskite solar cell prepared based on ionic liquid methyl ammonium acetate and a conventional mixed solvent DMF/DMSO according to the present invention, the efficiency of the wide bandgap perovskite solar cell prepared based on ionic liquid methyl ammonium acetate reaches 20.59%, which is reported to be more than 20% for the first time based on a wide bandgap perovskite device efficiency of 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 ionic liquid methyl ammonium acetate and traditional mixed solvent DMF/DMSO according to the invention with time under the protection of nitrogen. Under the nitrogen atmosphere, the wide-bandgap perovskite solar cell prepared based on the ionic liquid methyl ammonium acetate still keeps more than 95% of the initial efficiency after being placed for more than 1200 hours, and the efficiency of the wide-bandgap perovskite solar cell prepared based on the traditional mixed solvent DMF/DMSO is attenuated to 83% of the initial efficiency under the storage of the same condition;
comparative example 1
The embodiment is an inventive wide bandgap perovskite solar cell, and mainly comprises the following steps:
step 1), sequentially adding the etched ITO conductive glass into ethanol, ultrapure water, cleaning agent, ultrapure water, acetone and ethanol, and respectively carrying out ultrasonic treatment for 20min. Drying with nitrogen, and baking in an oven at 120deg.C for 30min to obtain clean ITO substrate.
Step 2) 315.37mg of lead iodide, 27.19mg of methyl ammonium iodide, 57.45mg of methyl ammonium bromide were dissolved in the ionic liquid methyl ammonium acetate and stirred at 60℃for 12 hours.
Step 3) 73.2mg of Spiro-OMeTAD were dissolved in 1mL of chlorobenzene; 520mg of lithium salt was dissolved in 1mL of acetonitrile solution; 17.6. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution; adding 28.8 μ LTBP solution to the Spiro-OMeTAD solution; the mixed solution was stirred for 2 hours as a whole.
Step 4) treating the ITO substrate cleaned in the step 1) with ultraviolet ozone for 15 minutes.
Step 5) taking 40 mu L of CPTA (electron transport material) and dripping the CPTA onto 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 CPTA at 140 ℃ for 15 minutes.
Step 6) spin-coating BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer after annealing in step 5), 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 spin-coated with the interface material in the step 6) on a substrate of a heating spin-coating instrument, and preheating for 5min.
Step 8) taking 90 mu L of the perovskite precursor solution prepared in the step 2), dripping the solution onto the ITO substrate preheated in the step 7), spin-coating to form a film, and then annealing to obtain the perovskite film. The spin-on perovskite precursor solution was spun at 4000 rpm for 20 seconds and annealed in air at 100 ℃ for 5 minutes.
Step 9) spin-coating the hole transport material prepared in the step 3) onto the perovskite film annealed in the step 8), wherein spin-coating of Spiro-OMeTAD is carried out at 3000 rpm for 30 seconds to form a hole transport layer.
Step 10) vapor plating 5nm MoO on the hole transport layer of step 9) by vacuum vapor plating technique 3 And then evaporating a 100nm metal electrode Ag to prepare the perovskite solar cell.
Step 11) under standard test conditions (AM 1.5G illumination), the ionic liquid methyl ammonium acetate is used as a solvent of a wide band gap perovskite precursor solution, the used wide band gap perovskite precursor materials are lead iodide, methyl ammonium iodide and methyl ammonium bromide, and the prepared perovskite battery device performance parameters are respectively that the energy conversion efficiency is 18.81%, the open circuit voltage is 1.17V, and the short circuit current is 19.94mA/cm 2 The fill factor was 80.41%.
Fig. 9 is a graph of the photoelectric conversion efficiency J-V of a wide bandgap perovskite solar cell prepared based on ionic liquid methylammonium acetate of the present invention using lead iodide, methylammonium bromide as the wide bandgap perovskite precursor material. The prepared device has the efficiency of 18.81 percent, which is inferior to a wide band gap perovskite precursor solution prepared by using lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide as wide band gap perovskite precursor materials. In the embodiment 1, the ionic liquid methyl ammonium acetate, iodine and bromine all form hydrogen bonds, wherein N-H.Br hydrogen bonds are stronger than N-H.I hydrogen bonds, and for the wide-bandgap perovskite rich in bromine, 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 scheme described in the above embodiments, and all technical schemes formed by adopting equivalent substitution are the protection scope of the invention.
Claims (3)
1. A preparation method of a wide-bandgap perovskite solar cell is characterized by comprising the following steps: the method comprises the following steps:
sequentially carrying out ultrasonic treatment on the etched ITO conductive glass in ethanol, ultrapure water, cleaning agent, ultrapure water, acetone and ethanol for 20min, drying by nitrogen, and then placing the dried ITO conductive glass in a baking oven at 120 ℃ for baking for 30min to obtain a clean ITO substrate;
step (2) dissolving lead iodide of 236.93mg, ammonium methyl iodide of 81.18mg, lead bromide of 62.87mg and ammonium methyl bromide of 19.01mg in ionic liquid methyl ammonium acetate, and stirring at 60 ℃ for 12 hours;
step (3) the Spiro-ome tad of 73.2mg was dissolved in chlorobenzene of 1 mL; the lithium salt of 520mg was dissolved in acetonitrile solution of 1 mL; 17.6. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution; adding 28.8 μ LTBP solution to the Spiro-OMeTAD solution; the mixed solution is integrally stirred for 2 hours;
step (4), treating the ITO substrate cleaned in the step (1) with ultraviolet ozone for 15 minutes;
step (5) taking 40 mu L of electron transport material CPTA, dripping the CPTA onto 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 CPTA at 140 ℃ for 15 minutes;
step (6), spin-coating BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer after annealing in the step (5), 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 spin-coated with the interface material in the step (6) on a substrate of a heating spin-coating instrument, and preheating for 5min;
and (8) taking 90 mu L of the perovskite precursor solution prepared in the step (2), dripping the solution onto the preheated ITO substrate in the step 7), spin-coating to form a film, and then annealing to obtain the perovskite film. Spin-coating perovskite precursor solution at 4000 rpm for 20 seconds, and annealing at 100deg.C in air for 5min;
step (9) spin-coating the hole transport material prepared in the step (3) on the perovskite film annealed in the step (8), wherein spin-coating of the Spiro-OMeTAD is carried out at 3000 revolutions per minute for 30 seconds 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 technology 3 Then evaporating 100nm metal electrode Ag to prepare a perovskite solar cell;
the ionic liquid methyl ammonium 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 the interaction between the ionic liquid methyl ammonium acetate and the bromine is beneficial to the preparation of the wide band gap perovskite film for the wide band gap perovskite rich in the bromine;
lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide are dissolved in ionic liquid methyl ammonium acetate according to a molar ratio of 3:1:3:1 to be used as a solvent of a wide band gap perovskite precursor solution, and a one-step heating spin coating technology is adopted to prepare the wide band gap perovskite film, so that the nucleation process of crystals is accelerated, the growth process of perovskite crystals is delayed due to the existence of stronger N-H.Br hydrogen bonds in the precursor solution, and the crystal nucleation and crystal growth processes are decoupled, so that the wide band gap perovskite film with compact and smooth surface, high crystallinity, low defect state density and good crystal orientation is obtained.
2. A perovskite solar cell prepared according to the method of preparing a wide bandgap perovskite solar cell according to claim 1.
3. Use of the wide bandgap perovskite solar cell according to claim 2 in the photovoltaic field.
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