CN114784192A - High-stability wide-band-gap perovskite solar cell and preparation method thereof - Google Patents
High-stability wide-band-gap perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-stability wide-band-gap perovskite solar cell and a preparation method thereof. According to the invention, the PTAA film is heated and washed by adopting the DMF solution, the problem of holes of the perovskite film is solved on the premise of not influencing hole transmission, and the high efficiency and repeatability of PSCs are realized. The method is simple, convenient, economical and efficient, and realizes the optimization of the PTAA film. The wide-band-gap perovskite precursor solution is deposited on the PTAA thin film after DMF optimized washing, the two solutions are in good contact, and holes on the surface of the deposited perovskite thin film disappear. Meanwhile, halogen ions are partially replaced by halogen-like anions, so that the common halogen separation in the wide-band-gap perovskite is improved while higher conversion efficiency is obtained, and the stability of the perovskite is increased; and tensile strain generated by unstable thermal expansion coefficients of the perovskite and the lower layer is improved, and the carrier transmission rate of the perovskite is increased.
Description
Technical Field
The invention relates to a silicon-perovskite laminated solar cell, in particular to a high-stability wide-band-gap perovskite solar cell and a preparation method thereof.
Background
Currently, the conversion efficiency of single-junction perovskite solar cells has reached 25.7%. The perovskite material becomes an ideal candidate material for manufacturing a multi-junction tandem solar cell due to the flexible and adjustable forbidden band width and the simple low-temperature solution preparation process. The development of wide bandgap Perovskite Solar Cells (PSCs) is imperative.
The problems of large deviation between open-circuit voltage (Voc) and band gap (Eg), low photoelectric conversion efficiency and the like of the conventional wide-band gap perovskite battery generally exist. In addition, perovskite cells also face stability challenges, and halogen separation is prone to occur under conditions of light, heat, water, oxygen, and the like, and particularly the phase instability of wide-bandgap perovskite cells is prominent. Perovskite materials have ionic defects that can migrate to the interface of the perovskite and other contact layers, inhibiting efficient extraction of charge, and are also very moisture sensitive, with rapid decay of PSCs performance in a humid environment.
In inverted PSCs, the Hole Transport Layer (HTL) not only acts as a charge carrier extraction layer but also significantly affects the crystallization and film formation of perovskite. It is important to optimize the HTL to improve its contact with the perovskite layer. At present, poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ] (PTAA) is one of the most widely used Hole Transport Materials (HTM) in an inversion device due to its high hole mobility, good resistance to etching by precursor solvents such as N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and level matching with a perovskite layer.
Due to the non-wettability of the surface of the PTAA film, the adhesion of the perovskite precursor solution in the deposition process is small, the contact between the PTAA film and the perovskite precursor solution is poor, the PTAA film cannot be completely covered by the perovskite precursor solution in the spin coating process, meanwhile, the perovskite film generates more holes, a large amount of perovskite precursor solution is wasted, and the factors directly influence the conversion efficiency and the stability of the perovskite solar device. To solve this problem, researchers have adopted various approaches. It is currently known to subject PTAA films directly to ultraviolet ozone (UVO) treatment to change their chemical structure. However, this method has a large number of factors (e.g., plasma power and processing time), which reduces the reproducibility of the device and increases the manufacturing difficulty of the perovskite solar cell industry. In addition, the method for reducing the non-wettability of the PTAA by washing the PTAA thin film with Chlorobenzene (CB) solution solves the problem of pores of the perovskite thin film, but the PTAA solution is dissolved by using CB as a solvent, and the effective adhesion of the PTAA on the ITO conductive glass is reduced by washing with CB, so that the hole mobility of the PTAA is influenced.
Therefore, there is a strong need to explore a simple and cost-effective method to optimize PTAA to achieve both high efficiency and reproducibility of PSCs. And a highly effective and feasible additive is sought to reduce halogen decomposition of perovskite and increase device efficiency.
Disclosure of Invention
The invention aims to provide a high-stability wide-band-gap perovskite solar cell and a preparation method thereof, which are used for optimizing PTAA (Polybutylece terephthalate) and improving the problem of pores of a perovskite film; meanwhile, the decomposition of perovskite halogen can be effectively reduced, and the conversion efficiency of the battery is improved.
The invention is realized by the following steps: according to the invention, the problem of poor contact between the PTAA layer and the perovskite precursor solution is solved by heating the DMF solvent to wash the PTAA film, and the situations of unstable halogen in the wide-bandgap perovskite and the like are solved by adding the halogen-like additive, so that the perovskite solar cell device which is efficient, stable and easy to repeat is prepared.
DMF is used for washing when the PTAA layer is optimized, and the PTAA thin film is washed at normal temperature due to the fact that DMF solution is high in polarity, and the perovskite thin film obtained by spin coating of the perovskite thin film still has more problems. Therefore, the invention utilizes a heating method to improve the polarity of the DMF solution, thereby solving the problems of wettability of the PTAA film and pores on the surface of the perovskite film.
The halide-like elements have chemical properties and ionic radii similar to those of halides, and can effectively replace partial halogen ions, so that the stability of the wide-band-gap perovskite thin film is improved, the halogen separation of the perovskite device is effectively reduced, the performance and the stability of the device are greatly improved, and a more ideal upper-layer absorbing material is provided for the perovskite-silicon laminated solar cell.
The finally manufactured device sequentially comprises ITO conductive glass, a washed hole transport layer (namely, the hole transport layer is washed by DMF), a perovskite film, an electron transport layer, a barrier layer and a metal electrode from bottom to top.
The hole transport layer, the DMF flushing layer, the perovskite film, the electron transport layer and the barrier layer are all prepared by adopting a spin coating method.
The metal electrode is prepared by a thermal evaporation method.
The selected system is FA with a band gap of 1.67eV0.65MA0.20Cs0.15Pb(I0.8Br0.2)3The preparation process of each layer of the wide-bandgap perovskite is as follows:
a. hole transport layer: poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ] (PTAA) powder was dissolved in chlorobenzene solution, the dissolved PTAA solution was spin-coated on conductive glass ITO by a spin coating method, and annealing was performed on a heating stage. The hole transport layer material is selected to match the band gap of the perovskite thin film.
b. DMF washing: the DMF solution was heated on a heating table due to its greater polarity. And c, placing the sample obtained in the step a on a spin coater, and dynamically spin-coating in one step.
c. Perovskite thin film: and (c) spin-coating the wide-band gap perovskite precursor solution on the sample obtained in the step (b) by using a spin-coating method. During spin coating: 1100rpm at low speed, 2s of spin coating time and 1000rpm/s of acceleration; high speed 6000rpm, spin time 30s, acceleration 2000 rpm/s. And (3) dropwise adding an anti-solvent chlorobenzene solution at a high speed of 20-25s, and annealing the perovskite thin film obtained by spin coating. Annealing to obtain the perovskite thin film with the thickness of about 400 nm.
d. Electron transport layer: 3' -phenyl-3 ' H-cyclopropa [1,9] [5,6] fullerene-C60-Ih-3 ' -butyric acid methyl ester (PCBM) powder was dissolved in a chlorobenzene solution, and the solution was thoroughly dissolved and then filtered through a 0.22 μm filter head. And c, placing the perovskite thin film sample obtained in the step c on a spin coater, and statically spin-coating PCBM solution under the conditions of the rotating speed of 1500rpm, the spin-coating time of 30s and the acceleration of 1000 rpm/s.
e. Barrier layer: BCP powder was dissolved in anhydrous ethanol. And d, standing the sample obtained in the step d for about 10min, and spin-coating BCP by using a spin-coating method to avoid the metal electrode and the lower perovskite film from reacting to influence the performance of the device.
f. Metal electrode: the silver metal electrode with the thickness of about 150nm is prepared by a thermal evaporation method.
The problems of PTAA wettability and perovskite film holes are solved by heating and washing with a DMF solution. Has the advantages of simple and easy implementation, high conversion efficiency, good contact of perovskite precursor solution and the like.
Halogen-like anions BF4 -、PF6 -The conversion efficiency of the basic device of the system can be greatly improved by acting on the system. In addition, the perovskite has improved halogen separation, tensile strain, and the like.
The invention relates to a light absorption layer of a top battery in a silicon-perovskite laminated solar battery, and firstly solves the problem of non-wettability of a hole transmission layer in a perovskite device. According to the invention, the PTAA film is heated and washed by selecting the N, N-Dimethylformamide (DMF) solution, the problem of holes of the perovskite film is solved on the premise of not influencing the hole transmission of the PTAA film, and the high efficiency and the repeatability of PSCs are realized. The method is simple, convenient, economical and efficient, and realizes the optimization of the PTAA film. The wide-band-gap perovskite precursor solution is deposited on the PTAA thin film after DMF optimized washing, the two solutions are in good contact, and holes on the surface of the deposited perovskite thin film disappear.
Meanwhile, in the formed wide-band-gap perovskite solar cell device, halogen-like elements with chemical properties and ionic radii similar to those of halogen elements are searched for to partially replace the halogen elements so as to solve the problems of halogen separation, tensile strain inside a thin film, low conversion efficiency and the like of the existing wide-band-gap perovskite solar cell and provide an ideal upper-layer absorbing material for the laminated solar cell.
The invention effectively solves the non-wetting property of the hole transport layer PTAA thin film and improves the hole problem of the perovskite thin film; in addition, the problems of easy decomposition of perovskite halogen, tensile strain in the film, low conversion efficiency, and the like due to the use of the halogen-like additive are solved by the effective action of the halogen-like additive.
Drawings
Fig. 1 is a schematic view of the device structure of the present invention.
FIG. 2 shows a halogen-like anion BF4 -、PF6 -The structure and the action process of the method.
FIG. 3 is a comparison of the surface topography and cross-section of the base perovskite thin film of comparative example 1 and the modified thin films of examples 1 and 2 after addition of the halogen-like additive.
FIG. 4 is an Atomic Force Microscope (AFM) image of the base perovskite thin film of comparative example 1 and the modified thin film of examples 1 and 2 after addition of the halogen-like additive.
FIG. 5 is a graph comparing the change in PL profile measured under continuous sunlight for the base perovskite thin film of comparative example 1 and the modified thin films of examples 1 and 2, respectively, after the halogen-like additive was added.
Fig. 6 shows (a) J-V curves for the base device and the device with the halogen-like additive added, and (b) EQE curves for the base device and the device with the halogen-like additive added.
FIG. 7 is a graph of the measured water contact angle of a base perovskite thin film and a perovskite thin film after addition of a halogen-like additive.
Detailed Description
The invention is further described below with reference to the figures and the specific embodiments.
Example 1 use of a halogen-like anion BF4 -Partially replacing the halide ion.
This example prepares a highly efficient and stable wide band gap perovskite solar cell device according to the following procedure, and the selected system is FA with a band gap of 1.67eV0.65MA0.20Cs0.15Pb(I0.8Br0.2)3A wide band gap perovskite.
(1) Cleaning a substrate: the ITO conductive glass is sequentially placed into cleaning solution (commercially available, preferably produced by New energy science and technology Co., Ltd.), deionized water, acetone, isopropanol and absolute ethyl alcohol for ultrasonic cleaning for 20min, then dried by nitrogen, and then placed into an ultraviolet ozone (UVO) instrument for ultraviolet ozone treatment for 30 min.
(2) The ITO conductive glass subjected to the ultraviolet ozone treatment is transferred into a glove box filled with nitrogen. A PTAA solution having a concentration of 5mg/mL was spin-coated at 5000rpm (accelerated at 2500 rpm/s) for 25s (the 25s includes acceleration time, the same applies hereinafter), statically spin-coated, and the spin-coated film was annealed on a heating stage at 100 ℃ for 10 min. After the annealing is finished, the wafer is allowed to stand to room temperature, and the next operation is started.
(3) Since PTAA films are relatively hydrophobic and not conducive to perovskite spin coating, the samples obtained in step (2) were DMF washed: heating the DMF solution on a heating table at 100 ℃ for 5min, sucking 40 mu L of the heated DMF solution by using a pipette, spin-coating for 25s at the rotating speed of 4000rpm (accelerated at the acceleration of 2000 rpm/s), and dripping the DMF solution at 8s to realize the dynamic spin-coating of the DMF solution, wherein the dynamic spin-coating process is DMF flushing.
(4) Cleaning glove box before starting spin coating of perovskite, and prepared MABF4And fully dissolving the wide-band gap perovskite precursor solution for 12 h.
MABF4The preparation process of the wide-band gap perovskite precursor solution comprises the following steps: 167.7mg of FAI and 553.2mg of PbI2、33.6mg MABr、110.1mg PbBr2、58.5mg CsI、24mg MACl、2mg MABF4Dissolved in 1mL of a 4:1 volume ratio mixture of DMF and DMSO.
The prepared MABF with the concentration of 2mg/mL4The wide band gap perovskite precursor solution is placed in a glove box. Sucking 30 mu L of precursor solution, paving the precursor solution on the sample obtained in the step (3), and spin-coating for 2s at low speed of 1100rpm (accelerated at accelerated speed of 1000 rpm/s); followed by spin coating at high speed 6000rpm (accelerated at an acceleration of 2000 rpm/s) for 30 s. And (3) dropwise adding 110 mu L of an anti-solvent chlorobenzene solution at a high speed of 20-25s, immediately placing the perovskite thin film obtained by spin coating on a heating table at 100 ℃ for annealing for 45min, and obtaining the crystallized perovskite thin film. And standing to room temperature after the annealing is finished, and starting the next operation.
(5) And (5) spin-coating the filtered PCBM solution on the sample obtained in the step (4), wherein the concentration of the solution is 20mg/mL, spin-coating for 30s at a rotation speed of 1500rpm (accelerated at an acceleration of 1000 rpm/s), performing static spin-coating, and standing for about 15 min.
(6) And (3) spinning 40 mu L of BCP solution with absolute ethyl alcohol as a solvent at the rotating speed of 5000rpm (accelerated at the accelerated speed of 2000 rpm/s) for 30s on the sample obtained in the step (5), and dynamically spinning at 8s, wherein the concentration of the BCP solution is 0.5 mg/mL.
(7) Placing the sample obtained in the step (6) in an evaporation coating die, carrying out thermal evaporation on a metal electrode Ag in an evaporation coating bin, placing Ag particles on a thermal evaporation boat, tightly closing a cabin door, and pumping the vacuum degree of a cavity to 6 multiplied by 10-4Pa. The current is adjusted to 120A, and the evaporation rate is
When the rate drops to 0, evaporation is complete and a 150nm thick Ag electrode is obtained.
The structure of the finally prepared sample is shown in fig. 1.
Example 2 Using halogen-like anion PF6 -Partially replacing the halide ion.
In this example, a highly efficient and stable wide band gap perovskite solar cell device was prepared according to the following steps, and the selected system was FA with a band gap of 1.67eV0.65MA0.20Cs0.15Pb(I0.8Br0.2)3A wide band gap perovskite.
(1) Cleaning a substrate: the ITO conductive glass is sequentially placed into cleaning solution (sold in the market), deionized water, acetone, isopropanol and absolute ethyl alcohol to be ultrasonically cleaned for 20min, then is dried by nitrogen, and is placed into an ultraviolet ozone (UVO) instrument to be subjected to ultraviolet ozone treatment for 30 min.
(2) And transferring the ITO conductive glass subjected to the ultraviolet ozone treatment into a glove box filled with nitrogen. A PTAA solution having a concentration of 5mg/mL was spin-coated at 5000rpm (accelerated at 2500 rpm/s) for 25s (the 25s includes acceleration time, the same applies hereinafter), statically spin-coated, and the spin-coated film was annealed on a heating stage at 100 ℃ for 10 min. After the annealing is finished, the wafer is allowed to stand to room temperature, and the next operation is started.
(3) Performing DMF washing on the sample obtained in the step (2): heating the DMF solution on a heating table at 100 ℃ for 5min, sucking 40 mu L of the heated DMF solution by using a pipette, spin-coating for 25s at the rotating speed of 4000rpm (accelerated at the acceleration of 2000 rpm/s), and dripping the DMF solution at 8s to realize the dynamic spin-coating of the DMF solution, wherein the dynamic spin-coating process is DMF flushing.
(4) MAPF prepared by cleaning glove box before starting spin coating perovskite6And fully dissolving the wide-band gap perovskite precursor solution for 12 hours.
MAPF6The preparation steps of the wide-band gap perovskite precursor solution are as follows: 167.7mg of FAI and 553.2mg of PbI2、33.6mg MABr、110.1mg PbBr2、58.5mg CsI、24mg MACl、2mg MAPF6Dissolved in 1mL of a 4:1 mixture of DMF and DMSO.
FIG. 2 shows a halogen-like anion BF4 -、PF6 -The structure and the action process of the method. Shown as BF4 -、PF6 -Ionic substitution of I-The process of (1).
Preparing MAPF with the concentration of 2mg/mL6The wide band gap perovskite precursor solution is placed in a glove box. Sucking 30 mu L of precursor solution, paving the precursor solution on the sample obtained in the step (3), and spin-coating for 2s at low speed of 1100rpm (accelerated at accelerated speed of 1000 rpm/s); followed by spin coating at high speed 6000rpm (accelerated at an acceleration of 2000 rpm/s) for 30 s. And (3) dropwise adding 110 mu L of an anti-solvent chlorobenzene solution at a high speed of 20-25s, immediately placing the perovskite thin film obtained by spin coating on a heating table at 100 ℃ for annealing for 45min, and obtaining the crystallized perovskite thin film. And standing to room temperature after the annealing is finished, and starting the next operation.
(5) And (3) spin-coating the filtered PCBM solution on the sample obtained in the step (4), wherein the concentration of the solution is 20mg/mL, spin-coating at a rotation speed of 1500rpm (accelerated at an acceleration of 1000 rpm/s) for 30s, statically spin-coating, and standing for about 15 min.
(6) And (3) spinning 40 mu L of BCP solution with absolute ethyl alcohol as a solvent at the rotating speed of 5000rpm (accelerated at the accelerated speed of 2000 rpm/s) for 30s on the sample obtained in the step (5), and dynamically spinning at 8s, wherein the concentration of the BCP solution is 0.5 mg/mL.
(7) Placing the sample obtained in the step (6) in an evaporation coating die, carrying out thermal evaporation on a metal electrode Ag in an evaporation coating bin, placing Ag particles on a thermal evaporation boat, tightly closing a cabin door, and pumping the vacuum degree of a cavity to 6 multiplied by 10-4Pa. Regulating current to 120A, and evaporating at a rate of
When the rate drops to 0, evaporation is complete and a 150nm thick Ag electrode is obtained.
Comparative example 1, a base perovskite thin film.
In this example, a highly efficient and stable wide band gap perovskite solar cell device was prepared according to the following steps, and the selected system was FA with a band gap of 1.67eV0.65MA0.20Cs0.15Pb(I0.8Br0.2)3A wide band gap perovskite.
(1) Cleaning the substrate: the ITO conductive glass is sequentially placed into cleaning solution (sold in the market), deionized water, acetone, isopropanol and absolute ethyl alcohol to be ultrasonically cleaned for 20min, then is dried by nitrogen, and is placed into an ultraviolet ozone (UVO) instrument to be subjected to ultraviolet ozone treatment for 30 min.
(2) The ITO conductive glass subjected to the ultraviolet ozone treatment is transferred into a glove box filled with nitrogen. A PTAA solution having a concentration of 5mg/mL was spin-coated at 5000rpm (accelerated at 2500 rpm/s) for 25s (the 25s included the acceleration time, the same applies hereinafter), and statically spin-coated, and the spin-coated film was annealed on a heating stage at 100 ℃ for 10 min. After the annealing is finished, the wafer is allowed to stand to room temperature, and the next operation is started.
(3) Performing DMF washing on the sample obtained in the step (2): heating the DMF solution on a heating table at 100 ℃ for 5min, sucking 40 mu L of the heated DMF solution by using a pipette, spin-coating for 25s at the rotating speed of 4000rpm (accelerated at the acceleration of 2000 rpm/s), and dripping the DMF solution at 8s to realize the dynamic spin-coating of the DMF solution, wherein the dynamic spin-coating process is DMF flushing.
(4) Glove box cleaning before starting spin coating of perovskiteWashing, preparation of FA0.65MA0.20Cs0.15Pb(I0.8Br0.2)3And fully dissolving the wide-band gap perovskite precursor solution for 12 hours.
FA0.65MA0.20Cs0.15Pb(I0.8Br0.2)3The preparation process of the wide-band gap perovskite precursor solution is as follows: 167.7mg of FAI and 553.2mg of PbI2、33.6mg MABr、110.1mg PbBr258.5mg CsI, 24mg MACl, dissolved in 1mL of a 4:1 volume ratio mixture of DMF and DMSO.
Prepared FA with the concentration of 2mg/mL0.65MA0.20Cs0.15Pb(I0.8Br0.2)3The wide band gap perovskite precursor solution was placed in a glove box. Sucking 30 mu L of precursor solution, paving the precursor solution on the sample obtained in the step (3), and spin-coating for 2s at low speed of 1100rpm (accelerated at acceleration of 1000 rpm/s); followed by spin coating at high speed 6000rpm (acceleration at 2000 rpm/s) for 30 s. And (3) dripping 110 mu L of anti-solvent chlorobenzene solution at a high speed of 20-25s, immediately placing the perovskite thin film obtained by spin coating on a heating table at 100 ℃ for annealing for 45min to obtain the perovskite thin film (namely the basic perovskite thin film) finished by crystallization. And standing to room temperature after the annealing is finished, and starting the next operation.
SEM tests were conducted on the base perovskite thin film prepared herein and the modified thin films of examples 1 and 2 after addition of the halogen-like additive, and the SEM and cross-sectional views are shown in FIG. 3. It can be seen from FIG. 3 that the perovskite thin film added with the additive has larger grain size, and the surface of the thin film becomes smoother. And a halogen-like anion (BF) is added4 -Or PF6 -) The grain boundary of the perovskite thin film is obviously reduced compared with the grain boundary of the basic perovskite thin film.
The obtained basic perovskite thin film and the modified thin films obtained in examples 1 and 2 after adding the halogen-like additive were respectively subjected to an AFM test, and the results are shown in fig. 4. It can be seen from fig. 4 that the roughness of the perovskite thin film is significantly reduced after the halogen-like additive is added.
The prepared basic perovskite thin film and the improved thin film added with the halogen-like additive are subjected to a light stability test, Photoluminescence (PL) measurement is carried out every 30min after one sunlight is continuously irradiated for 1h, and the obtained PL spectrum is shown in figure 5. As can be seen from FIG. 5, the PL peak position of the halogen-like additive was 741nm, and the peak position was not shifted by light irradiation, and the halogen in the perovskite was not separated; and the peak position of the basic perovskite thin film is shifted from 741nm to 744nm through continuous irradiation of sunlight, which indicates that halogen separation occurs under the illumination condition. This indicates that halogen segregation in the perovskite is effectively reduced after treatment with the halogen-like additive.
FIG. 7 is a graph of the measured water contact angle of a base perovskite thin film and a perovskite thin film after addition of a halogen-like additive. It is clearly seen that the films after the addition of the additive are more hydrophobic with contact angles from 46.3 ° to 57.8 ° and 70.4 °.
(5) And (5) spin-coating the filtered PCBM solution on the sample obtained in the step (4), wherein the concentration of the solution is 20mg/mL, spin-coating for 30s at a rotation speed of 1500rpm (accelerated at an acceleration of 1000 rpm/s), performing static spin-coating, and standing for about 15 min.
(6) And (4) spinning 40 mu L of BCP solution with absolute ethyl alcohol as a solvent at the speed of 5000rpm (accelerated at the acceleration of 2000 rpm/s) for 30s on the sample obtained in the step (5), and dynamically spinning at the time of 8s, wherein the concentration of the BCP solution is 0.5 mg/mL.
(7) Placing the sample obtained in the step (6) in an evaporation coating die, carrying out thermal evaporation on a metal electrode Ag in an evaporation coating bin, placing Ag particles on a thermal evaporation boat, tightly closing a cabin door, and pumping the vacuum degree of a cavity to 6 multiplied by 10-4Pa. The current is adjusted to 120A, and the evaporation rate is
Evaporation was terminated when the rate dropped to 0, resulting in a 150nm thick Ag electrode.
The solar cell device prepared in this comparative example was a base device.
FIG. 6 (a) is a J-V curve (F for forward scan and R for reverse scan) of a base device and a halogen-additive-added device, with the halogen-additive-added device open-circuit compared to the base deviceThe voltage is increased from 1.130V to 1.195V, and the current density is increased from 20.3mA/cm2The lift is increased to 21.1mA/cm2The fill factor increased from 77% to 81.88%, and the conversion efficiency of devices with halogen-like additives was 20.643%, approaching world efficiency. Fig. 6 (b) is an External Quantum Efficiency (EQE) curve of the basic device and the device added with the halogen-like additive, and it can be seen that the current density measured by the J-V curve and the current density measured by the EQE are within 5%.
The preparation method has the advantages that the wettability of the F-type halogen-containing perovskite precursor solution is poor, and the wettability of the surface of the PTAA film is poor. Meanwhile, the non-wettability of the PTAA film and the hydrophobicity of the F-containing halogen perovskite precursor solution are improved, and the efficient and stable wide-bandgap perovskite solar cell is finally prepared.
According to the invention, halogen-like anions are used for partially replacing halogen ions, so that the common halogen separation in the wide-band-gap perovskite is improved while higher conversion efficiency is obtained, and the stability of the perovskite is increased; meanwhile, tensile strain generated by unstable thermal expansion coefficients of the perovskite and the lower layer is improved, and the carrier transmission rate of the perovskite is increased.
Claims (7)
1. A high-stability wide-band-gap perovskite solar cell comprises ITO conductive glass, a hole transport layer, a perovskite thin film, an electron transport layer, a barrier layer and a metal electrode from bottom to top in sequence; characterized in that the perovskite thin film is formed by halogen-like anions BF4 -Or PF6 -Partially replacing the halide ion.
2. The perovskite solar cell with high stability according to claim 1, wherein the hole transport layer is a PTAA layer and the PTAA layer is washed with a heated DMF solution.
3. The wide bandgap perovskite solar cell with high stability of claim 1The perovskite thin film is characterized in that FA with the band gap of 1.67eV is selected for the perovskite thin film0.65MA0.20Cs0.15Pb(I0.8Br0.2)3A wide band gap perovskite.
4. A preparation method of a high-stability wide-band-gap perovskite solar cell is characterized by comprising the following steps:
a. cleaning a substrate: sequentially putting the ITO conductive glass into a cleaning solution, deionized water, acetone, isopropanol and absolute ethyl alcohol for ultrasonic cleaning, then blowing to dry by using nitrogen, and then putting into an ultraviolet ozone instrument for ultraviolet ozone treatment;
b. preparing a hole transport layer: spin-coating the PTAA solution on ITO conductive glass by static spin coating in a glove box filled with nitrogen, followed by annealing;
c. and (3) washing the hole transport layer: heating the DMF solution, then sucking the heated DMF solution by using a pipette, and spin-coating the heated DMF solution on the hole transport layer in a dynamic spin coating manner to realize the flushing of the hole transport layer;
d. preparing a perovskite thin film: spin-coating a wide-bandgap perovskite precursor solution on the washed hole transport layer by adopting a static spin-coating mode;
e. preparing an electron transport layer: spin-coating PCBM solution on the perovskite thin film in a static spin-coating mode;
f. preparing a barrier layer: spin-coating a BCP solution on the electron transport layer in a dynamic spin-coating manner;
g. preparing a metal electrode: the metal electrode is prepared by a thermal evaporation method.
5. The method of claim 4, wherein in step d, the wide band gap perovskite precursor solution is MABF4Wide band gap perovskite precursor solutions or MAPF6A wide band gap perovskite precursor solution.
6. The method for preparing a wide band gap perovskite solar cell with high stability as claimed in claim 4, wherein in the step d, the time for spin coating the wide band gap perovskite precursor solution is 32 s; and dripping an anti-solvent chlorobenzene solution when the spinning is carried out for 22s-27 s; and finally annealing the obtained perovskite thin film.
7. The method of claim 4, wherein the heating of the DMF solution in step c is selected from the group consisting of: the DMF solution was heated on a heating table at 100 ℃ for 5 min.
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