A crown ether iodine-modified trans-perovskite solar cell

Abstract

This invention discloses a crown ether iodine-modified inverted perovskite solar cell, belonging to the field of solar cell technology. The inverted perovskite solar cell comprises a conductive substrate, a hole transport layer, a perovskite layer, a crown ether iodine-modified layer, an electron transport layer, a hole blocking layer, and an electrode layer, sequentially stacked. This invention uses crown ether iodine complexes to modify the perovskite interface, improving perovskite interface contact, reducing charge recombination at the perovskite interface, and thus extending the lifetime of charge carriers. Simultaneously, the crown ether iodine can release iodine ions to compensate for iodine vacancy defects in the perovskite, further improving the cell's fill factor, efficiency, and long-term stability.

Description

Technical Field

[0001] This invention belongs to the field of solar cell technology, specifically relating to a crown ether iodine-modified inverse perovskite solar cell. Background Technology

[0002] As a representative of third-generation solar cell technology, perovskite solar cells have achieved significant technological breakthroughs over the past decade, with their photoelectric conversion efficiency continuously breaking records, and single-cell efficiency exceeding 26.1%. Among the various perovskite solar cell configurations, inverted devices are gradually attracting wider attention due to their mild fabrication process and suitability for multilayer stacked cell structures. A typical inverted perovskite solar cell structure includes a conductive glass substrate (such as ITO or FTO), a hole transport layer (HTL), a perovskite active layer, an electron transport layer (ETL), and a metal electrode. However, during the solution-based fabrication of the perovskite active layer, a large number of charge defect states easily form at the interface. These defect states lead to nonradiative recombination of charges, shortening the lifetime of charge carriers, thereby causing energy loss and reducing the photoelectric conversion efficiency of the cell. Therefore, developing a strategy to effectively passivate and modify perovskite interface defects to compensate for ion vacancies is of great significance for improving the efficiency and stability of inverted perovskite solar cells. Summary of the Invention

[0003] To address the above problems, this invention provides a crown ether iodine-modified inverse perovskite solar cell, which uses crown ether iodine to modify the interface of the perovskite solar cell, significantly improving the interfacial contact between the perovskite and the electron transport layer.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A crown ether iodine-modified inverse perovskite solar cell comprises a conductive substrate, a nickel oxide / Me-4PACz dual hole transport layer, a perovskite layer, a crown ether iodine-modified layer, a PCBM electron transport layer, a BCP hole blocking layer, and a silver electrode layer, which are sequentially stacked. Its fabrication method includes the following steps:

[0006] (1) After spin-coating a nickel oxide nanoparticle dispersion onto one side of a conductive substrate and annealing, spin-coating an ethanol solution of 4-(3,6-dimethyl-9h-carbazole-9-yl)butylphosphonic acid (Me-4PACz) and annealing is performed to obtain a nickel oxide / Me-4PACz double hole transport layer.

[0007] (2) A perovskite film was deposited on the nickel oxide / Me-4PACz double hole transport layer obtained in step (1) using a two-step method, namely, first spin-coating a lead iodide precursor solution and then annealing, and then dynamically spin-coating an organic salt solution containing formamidin hydroiodide (FAI) and then annealing, thereby obtaining a perovskite layer.

[0008] (3) Spin-coat a chlorobenzene solution of crown ether iodine onto the perovskite layer obtained in step (2) and anneal it to obtain a crown ether iodine modified layer;

[0009] (4) Spin-coating a chlorobenzene solution of methyl [6,6]-phenyl-C61-butyrate (PCBM) onto the crown ether iodine modified layer obtained in step (3) and annealing to obtain the PCBM electron transport layer;

[0010] (5) Spin-coat an isopropanol solution of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP) onto the PCBM electron transport layer obtained in step (4) to obtain a BCP hole blocking layer.

[0011] (6) Deposit metallic silver onto the BCP hole blocking layer obtained in step (5) to obtain a silver electrode layer.

[0012] Further, in step (1), the conductive substrate is ITO or FTO, which needs to be cleaned and treated with ozone before use; the nickel oxide nanoparticle dispersion is prepared by dispersing nickel oxide nanoparticles in deionized water, wherein the concentration of nickel oxide nanoparticles is 10 mg / ml~15 mg / ml, and its spin-coating amount is 20~25 μL / cm. 2 The spin-coating speed was 2000 rpm to 3000 rpm, the spin-coating time was 30 to 60 s, the annealing temperature was 120℃ to 150℃, and the annealing time was 15 min to 30 min; the concentration of Me-4PACz in the ethanol solution was 0.4 mg / mL to 0.5 mg / mL, and the spin-coating volume was 20 to 25 μL / cm. 2 The spin coating speed is 4000 rpm to 5000 rpm, the spin coating time is 30 to 60 s, the annealing temperature is 90℃ to 110℃, and the annealing time is 5 min to 15 min.

[0013] Further, in step (2), the lead iodide precursor solution is prepared by dissolving PbI2 and CsI in a DMF / DMSO mixed solvent with a volume ratio of 9:1, wherein the concentration of PbI2 is 1.5M, the concentration of CsI is 0.075M, and the spin-coating amount is 15~25μL / cm. 2 The spin-coating speed was 1000 rpm to 2000 rpm, the spin-coating time was 30 to 60 s, the annealing temperature was 60℃ to 80℃, and the annealing time was 30 to 90 s. The organic salt solution was prepared by dissolving formamidinium hydroiodate (FAI) and methylammonium chloride (MACl) in isopropanol at a mass ratio of 10:1, wherein the total concentration of FAI and MACl was 5 mg / ml to 15 mg / ml, and the spin-coating amount was 20 to 30 μL / cm.2 The dynamic spin coating speed was 1500 rpm to 3000 rpm, the spin coating time was 30 to 60 s, the annealing temperature was 100℃ to 150℃, the annealing time was 15 min to 30 min, and the annealing humidity was 30% to 40%; the thickness of the resulting perovskite layer was 600 nm to 900 nm.

[0014] Further, in step (3), the crown ether iodine is formed by complexing crown ether and iodine in a molar ratio of (1~2):1, wherein the crown ether is one or more of dibenzo-24-crown 8-ether (DB24C8), benzo-18-crown 6-ether (B18C6), and 15-crown ether-5 (15C5); the concentration of crown ether iodine in the chlorobenzene solution is 3.6 mg / ml~10.5 mg / ml, and its spin-coating volume is 20~25 μL / cm. 2 The spin coating speed is 3000 rpm to 6000 rpm, the spin coating time is 30 to 60 s, the annealing temperature is 80℃ to 120℃, and the annealing time is 5 min to 15 min.

[0015] Further, in step (4), the concentration of PCBM in the chlorobenzene solution of PCBM is 10 mg / ml to 30 mg / ml, and its spin-coating volume is 20 to 25 μL / cm. 2 The spin coating speed is 1500 rpm to 3000 rpm, the spin coating time is 30 to 60 s, the annealing temperature is 70℃ to 100℃, and the annealing time is 5 min to 15 min.

[0016] Further, in step (5), the concentration of BCP in the isopropanol solution is 0.3 mg / ml to 0.6 mg / ml, and the spin-coating volume is 20 to 25 μL / cm. 2 The spin coating speed is 4000 rpm to 6000 rpm, and the spin coating time is 30 to 60 s.

[0017] Furthermore, the thickness of the silver electrode layer obtained in step (6) is 80 nm to 120 nm.

[0018] The improvements of this invention not only reduce charge recombination at the interface but also effectively extend the lifetime of charge carriers, thereby improving the overall performance of the battery. The unique advantage of using crown ether iodine lies in its ability to release iodide ions. The presence of iodine ensures effective electron-hole pair separation, and the iodide ions can also fill iodine vacancy defects within the perovskite material, further enhancing the photoelectric conversion efficiency and stability of the battery. Furthermore, the use of crown ether iodine not only increases the fill factor of the battery but also helps maintain its performance during long-term operation, ensuring its reliability and durability under various environmental conditions. Through this strategy, the commercial application prospects of perovskite solar cells are further enhanced, opening up new possibilities for efficient and stable solar cell technology.

[0019] The beneficial effects of this invention are as follows:

[0020] (1) This invention proposes a method for preparing high-efficiency and stable inverted perovskite solar cells using crown ether iodide complexes as modifiers. By introducing a modifier layer between the perovskite layer and the electron transport layer, surface defects of the perovskite are passivated and the bandgap arrangement at the interface between the perovskite layer and the electron transport layer is improved, reducing charge recombination at the interface and thus suppressing nonradiative recombination at the interface. The energy conversion efficiency of photovoltaic devices prepared using this method can be significantly improved.

[0021] (2) This invention provides a new approach for the fabrication of high-efficiency and stable perovskite solar cells, which facilitates a deeper understanding of interfacial charge carrier behavior and suppresses non-radiative charge loss at the interface. This strategy is of great significance for promoting the commercial development of perovskite solar cells and comprehensively improving their performance. Detailed Implementation

[0022] A crown ether iodine-modified inverse perovskite solar cell, the preparation method of which includes the following steps:

[0023] (1) Spin-coat a dispersion of nickel oxide nanoparticles at a concentration of 10 mg / ml to 15 mg / ml onto one side of a cleaned and ozone-treated ITO or FTO conductive substrate, with a spin-coating amount of 20 to 25 μL / cm. 2 The spin-coating speed was 2000 rpm to 3000 rpm, and the spin-coating time was 30 to 60 s. Then, the mixture was annealed at 120℃ to 150℃ for 15 to 30 min, followed by spin-coating of a 0.4 mg / mL to 0.5 mg / mL Me-4PACz ethanol solution at a spin-coating volume of 20 to 25 μL / cm. 2 The spin coating speed was 4000 rpm to 5000 rpm, the spin coating time was 30 to 60 s, and then annealed at 90℃ to 110℃ for 5 min to 15 min to obtain nickel oxide / Me-4PACz dual hole transport layer.

[0024] (2) First, spin-coat the lead iodide precursor solution onto the nickel oxide / Me-4PACz dual hole transport layer obtained in step (1), with a spin-coating amount of 15~25 μL / cm. 2 The spin-coating speed was 1000 rpm to 2000 rpm, the spin-coating time was 30 to 60 s, followed by annealing at 60℃ to 80℃ for 30 to 90 s, and then dynamic spin-coating with an organic salt solution with a total concentration of 5 mg / ml to 15 mg / ml, with a spin-coating volume of 20 to 30 μL / cm. 2 The dynamic spin coating speed is 1500 rpm~3000 rpm, the spin coating time is 30~60 s, and then annealing is carried out at 100℃~150℃ and 30%~40% humidity for 15 min~30 min to obtain a perovskite layer with a thickness of 600 nm~900 nm.

[0025] (3) Spin-coating a crown ether iodine chlorobenzene solution with a concentration of 3.6 mg / ml to 10.5 mg / ml onto the perovskite layer obtained in step (2), with a spin-coating amount of 20 to 25 μL / cm. 2 The spin coating speed is 3000 rpm to 6000 rpm, the spin coating time is 30 to 60 s, and then annealing is carried out at 80℃ to 120℃ for 5 min to 15 min to obtain the crown ether iodine modified layer;

[0026] (4) Spin-coat a 10 mg / ml to 30 mg / ml PCBM chlorobenzene solution onto the crown ether iodine modified layer obtained in step (3), with a spin-coating volume of 20 to 25 μL / cm. 2 The spin coating speed is 1500 rpm to 3000 rpm, the spin coating time is 30 to 60 s, and then annealed at 70℃ to 100℃ for 5 min to 15 min to obtain the PCBM electronic transport layer.

[0027] (5) Spin-coat a 0.3 mg / ml to 0.6 mg / ml BCP isopropanol solution onto the PCBM electron transport layer obtained in step (4), with a spin-coating volume of 20 to 25 μL / cm. 2 The spin coating speed is 4000 rpm to 6000 rpm and the spin coating time is 30 to 60 s to obtain the BCP hole blocking layer;

[0028] (6) Deposit metallic silver on the BCP hole blocking layer obtained in step (5) to obtain a silver electrode layer with a thickness of 80 nm to 120 nm.

[0029] In step (2), the lead iodide precursor solution is prepared by dissolving PbI2 and CsI in a DMF / DMSO mixed solvent with a volume ratio of 9:1, wherein the concentration of PbI2 is 1.5M and the concentration of CsI is 0.075M. The organic salt solution is prepared by dissolving FAI and MACl in isopropanol at a mass ratio of 10:1.

[0030] In step (3), the crown ether iodine is formed by complexing crown ether with iodine in a molar ratio of (1~2):1, wherein the crown ether is one or more of dibenzo-24-crown 8-ether (DB24C8), benzo-18-crown 6-ether (B18C6), and 15-crown ether-5 (15C5).

[0031] To further illustrate the present invention, some specific embodiments are provided below. However, these embodiments are merely illustrative and do not represent a limitation on the scope of application of the present invention. Those skilled in the art should recognize that, while maintaining the core concept and purpose of the present invention, it is entirely feasible to make detailed adjustments or formal changes to the technical solutions of the present invention. Such adjustments and changes, as long as they do not deviate from the basic principles and spirit of the present invention, should be considered as part of the scope of protection of the present invention.

[0032] The nickel oxide nanoparticles used in the examples were purchased from Liaoning Youxuan New Energy Technology Co., Ltd., with a particle size of 5-10 nanometers and a purity of 99.9%.

[0033] Example 1:

[0034] This embodiment provides a crown ether iodine-modified inverse perovskite solar cell, the preparation method of which includes the following steps:

[0035] (1) A 2.0 cm × 2.0 cm ITO transparent conductive substrate was standardized and cleaned, and then treated with ultraviolet ozone for 20 minutes; then nickel oxide nanoparticles were added to deionized water and ultrasonically treated for 10 minutes to prepare a nickel oxide nanoparticle dispersion with a concentration of 12 mg / ml; 80 µL (i.e., spin coating amount of 20 μL / cm) was taken. 2 Nickel oxide nanoparticle dispersion was uniformly spread on ITO and spin-coated at 2000 rpm for 30 s. Then, it was heat-treated at 150℃ for 30 min. Afterward, the nickel oxide-containing ITO substrate was transferred to a glove box. Me-4PACz was dissolved in anhydrous ethanol and stirred until homogeneous to prepare a Me-4PACz spin-coating solution with a concentration of 0.45 mg / mL. 80 µL (i.e., a spin-coating volume of 20 μL / cm) was taken. 2Me-4PACz spin coating solution was evenly spread on an ITO substrate containing nickel oxide and spin coated at 4500 rpm for 30 s. Then, it was heat-treated on a hot stage at 100℃ for 10 min to obtain a hole transport layer.

[0036] (2) PbI2 and CsI were dissolved in a mixed solvent of DMF / DMSO (9:1, v / v) and stirred for 1 h. The solution was then filtered through a 0.22 μm polytetrafluoroethylene (PTFE) filter to obtain a precursor solution containing 1.5 M PbI2 and 0.075 M CsI. 80 μL (spin-coating amount of 20 μL / cm) was then added to the solution. 2 The precursor solution was spin-coated onto the hole transport layer at 1500 rpm for 30 s, and then annealed at 70 °C for 1 min. Subsequently, 9 mg FAI and 0.9 mg MACl were added to 1 mL of isopropanol and stirred until homogeneous, yielding an organic salt solution with a total concentration of 9.9 mg / mL. 100 μL (spin-coating volume 25 μL / cm) was then taken. 2 Organic salt solution was dynamically spin-coated at 1800 rpm for 30 s, and then the film was transferred from the glove box to a hot plate in air (humidity of about 35%) as soon as possible (within 35 s) and heat-treated at 150°C for 15 min to form a perovskite layer with a thickness of about 800 nm.

[0037] (3) Dissolve 4.5 mg of crown ether DB24C8 and 2.5 mg of iodine (the molar ratio of crown ether to iodine is 1:1) in 1 ml of chlorobenzene solvent to obtain a crown ether iodine spin-coating solution with a concentration of 7.0 mg / ml; then take 100 μL (spin-coating volume is 25 μL / cm) 2 The crown ether iodine spin-coating solution was dynamically spin-coated onto the perovskite layer at a spin speed of 4000 rpm for 30 s; finally, it was annealed on a 100℃ hot plate for 5 min to obtain the crown ether iodine modified layer.

[0038] (4) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2 A 15 mg / ml PCBM chlorobenzene solution was dropped onto the modified layer, spin-coated at 2000 rpm for 35 s, and then annealed at 100℃ for 10 min to obtain the electron transport layer.

[0039] (5) Take 80 µL (i.e., spin coating amount of 20 μL / cm) 2 A 0.6 mg / ml BCP isopropanol solution was dropped onto the electron transport layer and spin-coated at 5000 rpm for 30 s to obtain a hole blocking layer.

[0040] (6) A 100 nm thick silver electrode layer was obtained by vapor deposition on the hole blocking layer.

[0041] Example 2:

[0042] This embodiment provides a crown ether iodine-modified inverse perovskite solar cell, the preparation method of which includes the following steps:

[0043] (1) A 2.0 cm × 2.0 cm ITO transparent conductive substrate was standardized and cleaned, and then treated with ultraviolet ozone for 20 minutes; then nickel oxide nanoparticles were added to deionized water and ultrasonically treated for 10 minutes to prepare a nickel oxide nanoparticle dispersion with a concentration of 12 mg / ml; 80 µL (i.e., spin coating amount of 20 μL / cm) was taken. 2 Nickel oxide nanoparticle dispersion was uniformly spread on ITO and spin-coated at 2000 rpm for 30 s. Then, it was heat-treated at 150℃ for 30 min. Afterward, the nickel oxide-containing ITO substrate was transferred to a glove box. Me-4PACz was dissolved in anhydrous ethanol and stirred until homogeneous to prepare a Me-4PACz spin-coating solution with a concentration of 0.45 mg / mL. 80 µL (i.e., a spin-coating volume of 20 μL / cm) was taken. 2 Me-4PACz spin coating solution was evenly spread on an ITO substrate containing nickel oxide and spin coated at 4500 rpm for 30 s. Then, it was heat-treated on a hot stage at 100℃ for 10 min to obtain a hole transport layer.

[0044] (2) PbI2 and CsI were dissolved in a mixed solvent of DMF / DMSO (9:1, v / v) and stirred for 1 h. The solution was then filtered through a 0.22 μm polytetrafluoroethylene (PTFE) filter to obtain a precursor solution containing 1.5 M PbI2 and 0.075 M CsI. 80 μL (spin-coating amount of 20 μL / cm) was then added to the solution. 2 The precursor solution was spin-coated onto the hole transport layer at 1500 rpm for 30 s, and then annealed at 70 °C for 1 min. Subsequently, 9 mg FAI and 0.9 mg MACl were added to 1 mL of isopropanol and stirred until homogeneous, yielding an organic salt solution with a total concentration of 9.9 mg / mL. 100 μL (spin-coating volume 25 μL / cm) was then taken. 2 Organic salt solution was dynamically spin-coated at 1800 rpm for 30 s, and then the film was transferred from the glove box to a hot plate in air (humidity of about 35%) as soon as possible (within 35 s) and heat-treated at 150°C for 15 min to form a perovskite layer with a thickness of about 800 nm.

[0045] (3) Dissolve 3.1 mg of crown ether B18C6 and 2.5 mg of iodine (the molar ratio of crown ether to iodine is 1:1) in 1 ml of chlorobenzene solvent to obtain a crown ether iodine spin-coating solution with a concentration of 5.6 mg / ml; then take 100 μL (spin-coating volume is 25 μL / cm) 2 The crown ether iodine spin-coating solution was dynamically spin-coated onto the perovskite layer at a spin speed of 4000 rpm for 30 s; finally, it was annealed on a 100℃ hot plate for 5 min to obtain the crown ether iodine modified layer.

[0046] (4) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2 A 15 mg / ml PCBM chlorobenzene solution was dropped onto the modified layer, spin-coated at 2000 rpm for 35 s, and then annealed at 100℃ for 10 min to obtain the electron transport layer.

[0047] (5) Take 80 µL (i.e., spin coating amount of 20 μL / cm) 2 A 0.6 mg / ml BCP isopropanol solution was dropped onto the electron transport layer and spin-coated at 5000 rpm for 30 s to obtain a hole blocking layer.

[0048] (6) A 100 nm thick silver electrode layer was obtained by vapor deposition on the hole blocking layer.

[0049] Example 3:

[0050] This embodiment provides a crown ether iodine-modified inverse perovskite solar cell, the preparation method of which includes the following steps:

[0051] (1) A 2.0 cm × 2.0 cm ITO transparent conductive substrate was standardized and cleaned, and then treated with ultraviolet ozone for 20 minutes; then nickel oxide nanoparticles were added to deionized water and ultrasonically treated for 10 minutes to prepare a nickel oxide nanoparticle dispersion with a concentration of 12 mg / ml; 80 µL (i.e., spin coating amount of 20 μL / cm) was taken. 2 Nickel oxide nanoparticle dispersion was uniformly spread on ITO and spin-coated at 2000 rpm for 30 s. Then, it was heat-treated at 150℃ for 30 min. Afterward, the nickel oxide-containing ITO substrate was transferred to a glove box. Me-4PACz was dissolved in anhydrous ethanol and stirred until homogeneous to prepare a Me-4PACz spin-coating solution with a concentration of 0.45 mg / mL. 80 µL (i.e., a spin-coating volume of 20 μL / cm) was taken. 2Me-4PACz spin coating solution was evenly spread on an ITO substrate containing nickel oxide and spin coated at 4500 rpm for 30 s. Then, it was heat-treated on a hot stage at 100℃ for 10 min to obtain a hole transport layer.

[0052] (2) PbI2 and CsI were dissolved in a mixed solvent of DMF / DMSO (9:1, v / v) and stirred for 1 h. The solution was then filtered through a 0.22 μm polytetrafluoroethylene (PTFE) filter to obtain a precursor solution containing 1.5 M PbI2 and 0.075 M CsI. 80 μL (spin-coating amount of 20 μL / cm) was then added to the solution. 2 The precursor solution was spin-coated onto the hole transport layer at 1500 rpm for 30 s, and then annealed at 70 °C for 1 min. Subsequently, 9 mg FAI and 0.9 mg MACl were added to 1 mL of isopropanol and stirred until homogeneous, yielding an organic salt solution with a total concentration of 9.9 mg / mL. 100 μL (spin-coating volume 25 μL / cm) was then taken. 2 Organic salt solution was dynamically spin-coated at 1800 rpm for 30 s, and then the film was transferred from the glove box to a hot plate in air (humidity of about 35%) as soon as possible (within 35 s) and heat-treated at 150°C for 15 min to form a perovskite layer with a thickness of about 800 nm.

[0053] (3) Dissolve 2.2 mg of crown ether 15C5 and 2.5 mg of iodine (the molar ratio of crown ether to iodine is 1:1) in 1 ml of chlorobenzene solvent to obtain a crown ether iodine spin-coating solution with a concentration of 4.7 mg / ml; then take 100 μL (spin-coating volume is 25 μL / cm) 2 The crown ether iodine spin-coating solution was dynamically spin-coated onto the perovskite layer at a spin speed of 4000 rpm for 30 s; finally, it was annealed on a 100℃ hot plate for 5 min to obtain the crown ether iodine modified layer.

[0054] (4) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2 A 15 mg / ml PCBM chlorobenzene solution was dropped onto the modified layer, spin-coated at 2000 rpm for 35 s, and then annealed at 100℃ for 10 min to obtain the electron transport layer.

[0055] (5) Take 80 µL (i.e., spin coating amount of 20 μL / cm) 2 A 0.6 mg / ml BCP isopropanol solution was dropped onto the electron transport layer and spin-coated at 5000 rpm for 30 s to obtain a hole blocking layer.

[0056] (6) A 100 nm thick silver electrode layer was obtained by vapor deposition on the hole blocking layer.

[0057] Comparative Example 1:

[0058] This comparative example provides a conventional inverted perovskite solar cell, the fabrication method of which includes the following steps:

[0059] (1) A 2.0 cm × 2.0 cm ITO transparent conductive substrate was standardized and cleaned, and then treated with ultraviolet ozone for 20 minutes; then nickel oxide nanoparticles were added to deionized water and ultrasonically treated for 10 minutes to prepare a nickel oxide nanoparticle dispersion with a concentration of 12 mg / ml; 80 µL (i.e., spin coating amount of 20 μL / cm) was taken. 2 Nickel oxide nanoparticle dispersion was uniformly spread on ITO and spin-coated at 2000 rpm for 30 s. Then, it was heat-treated at 150℃ for 30 min. Afterward, the nickel oxide-containing ITO substrate was transferred to a glove box. Me-4PACz was dissolved in anhydrous ethanol and stirred until homogeneous to prepare a Me-4PACz spin-coating solution with a concentration of 0.45 mg / mL. 80 µL (i.e., a spin-coating volume of 20 μL / cm) was taken. 2 Me-4PACz spin coating solution was evenly spread on an ITO substrate containing nickel oxide and spin coated at 4500 rpm for 30 s. Then, it was heat-treated on a hot stage at 100℃ for 10 min to obtain a hole transport layer.

[0060] (2) PbI2 and CsI were dissolved in a mixed solvent of DMF / DMSO (9:1, v / v) and stirred for 1 h. The solution was then filtered through a 0.22 μm polytetrafluoroethylene (PTFE) filter to obtain a precursor solution containing 1.5 M PbI2 and 0.075 M CsI. 80 μL (spin-coating amount of 20 μL / cm) was then added to the solution. 2 The precursor solution was spin-coated onto the hole transport layer at 1500 rpm for 30 s, and then annealed at 70 °C for 1 min. Subsequently, 90 mg FAI and 9 mg MACl were added to 1 mL of isopropanol and stirred until homogeneous, yielding an organic salt solution with a total concentration of 9.9 mg / mL. 100 μL (spin-coating volume 25 μL / cm) was then taken... 2 Organic salt solution was dynamically spin-coated at 1800 rpm for 30 s, and then the film was transferred from the glove box to a hot plate in air (humidity of about 35%) as soon as possible (within 35 s) and heat-treated at 150°C for 15 min to form a perovskite layer with a thickness of about 800 nm.

[0061] (3) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2 A 15 mg / ml PCBM chlorobenzene solution was dropped onto the perovskite layer and spin-coated at 2000 rpm for 35 s. Then, it was annealed at 100°C for 10 min to obtain the electron transport layer.

[0062] (4) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2 A 0.6 mg / ml BCP isopropanol solution was dropped onto the electron transport layer and spin-coated at 5000 rpm for 30 s to obtain a hole blocking layer.

[0063] (5) A 100 nm thick silver electrode layer was obtained by vapor deposition on the hole blocking layer.

[0064] Comparative Example 2:

[0065] This comparative example provides a pure crown ether modified inverse perovskite solar cell, the preparation method of which includes the following steps:

[0066] (1) A 2.0 cm × 2.0 cm ITO transparent conductive substrate was standardized and cleaned, and then treated with ultraviolet ozone for 20 minutes; then nickel oxide nanoparticles were added to deionized water and ultrasonically treated for 10 minutes to prepare a nickel oxide nanoparticle dispersion with a concentration of 12 mg / ml; 80 µL (i.e., spin coating amount of 20 μL / cm) was taken. 2 Nickel oxide nanoparticle dispersion was uniformly spread on ITO and spin-coated at 2000 rpm for 30 s. Then, it was heat-treated at 150℃ for 30 min. Afterward, the nickel oxide-containing ITO substrate was transferred to a glove box. Me-4PACz was dissolved in anhydrous ethanol and stirred until homogeneous to prepare a Me-4PACz spin-coating solution with a concentration of 0.45 mg / mL. 80 µL (i.e., a spin-coating volume of 20 μL / cm) was taken. 2 Me-4PACz spin coating solution was evenly spread on an ITO substrate containing nickel oxide and spin coated at 4500 rpm for 30 s. Then, it was heat-treated on a hot stage at 100℃ for 10 min to obtain a hole transport layer.

[0067] (2) PbI2 and CsI were dissolved in a mixed solvent of DMF / DMSO (9:1, v / v) and stirred for 1 h. The solution was then filtered through a 0.22 μm polytetrafluoroethylene (PTFE) filter to obtain a precursor solution containing 1.5 M PbI2 and 0.075 M CsI. 80 μL (spin-coating amount of 20 μL / cm) was then added to the solution. 2The precursor solution was spin-coated onto the hole transport layer at 1500 rpm for 30 s, and then annealed at 70 °C for 1 min. Subsequently, 9 mg FAI and 0.9 mg MACl were added to 1 mL of isopropanol and stirred until homogeneous, yielding an organic salt solution with a total concentration of 9.9 mg / mL. 100 μL (spin-coating volume 25 μL / cm) was then taken. 2 Organic salt solution was dynamically spin-coated at 1800 rpm for 30 s, and then the film was transferred from the glove box to a hot plate in air (humidity of about 35%) as soon as possible (within 35 s) and heat-treated at 150°C for 15 min to form a perovskite layer with a thickness of about 800 nm.

[0068] (3) Dissolve 4.5 mg of crown ether DB24C8 in 1 ml of chlorobenzene solvent to obtain crown ether spin-coating solution; then take 100 μL (spin-coating volume of 25 μL / cm) 2 The crown ether spin-coating solution was dynamically spin-coated onto the perovskite layer at a spin speed of 4000 rpm for 30 s; finally, it was annealed on a 100℃ hot plate for 5 min to obtain the crown ether modified layer.

[0069] (4) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2 A 15 mg / ml PCBM chlorobenzene solution was dropped onto the modified layer, spin-coated at 2000 rpm for 35 s, and then annealed at 100℃ for 10 min to obtain the electron transport layer.

[0070] (5) Take 80 µL (i.e., spin coating amount of 20 μL / cm) 2 A 0.6 mg / ml BCP isopropanol solution was dropped onto the electron transport layer and spin-coated at 5000 rpm for 30 s to obtain a hole blocking layer.

[0071] (6) A 100 nm thick silver electrode layer was obtained by vapor deposition on the hole blocking layer.

[0072] Comparative Example 3:

[0073] This comparative example provides a crown ether bromide-modified inverse perovskite solar cell, the preparation method of which includes the following steps:

[0074] (1) A 2.0 cm × 2.0 cm ITO transparent conductive substrate was standardized and cleaned, and then treated with ultraviolet ozone for 20 minutes; then nickel oxide nanoparticles were added to deionized water and ultrasonically treated for 10 minutes to prepare a nickel oxide nanoparticle dispersion with a concentration of 12 mg / ml; 80 µL (i.e., spin coating amount of 20 μL / cm) was taken. 2Nickel oxide nanoparticle dispersion was uniformly spread on ITO and spin-coated at 2000 rpm for 30 s. Then, it was heat-treated at 150℃ for 30 min. Afterward, the nickel oxide-containing ITO substrate was transferred to a glove box. Me-4PACz was dissolved in anhydrous ethanol and stirred until homogeneous to prepare a Me-4PACz spin-coating solution with a concentration of 0.45 mg / mL. 80 µL (i.e., a spin-coating volume of 20 μL / cm) was taken. 2 Me-4PACz spin coating solution was evenly spread on an ITO substrate containing nickel oxide and spin coated at 4500 rpm for 30 s. Then, it was heat-treated on a hot stage at 100℃ for 10 min to obtain a hole transport layer.

[0075] (2) PbI2 and CsI were dissolved in a mixed solvent of DMF / DMSO (9:1, v / v) and stirred for 1 h. The solution was then filtered through a 0.22 μm polytetrafluoroethylene (PTFE) filter to obtain a precursor solution containing 1.5 M PbI2 and 0.075 M CsI. 80 μL (spin-coating amount of 20 μL / cm) was then added to the solution. 2 The precursor solution was spin-coated onto the hole transport layer at 1500 rpm for 30 s, and then annealed at 70 °C for 1 min. Subsequently, 90 mg FAI and 9 mg MACl were added to 1 mL of isopropanol and stirred until homogeneous, yielding an organic salt solution with a total concentration of 9.9 mg / mL. 100 μL (spin-coating volume 25 μL / cm) was then taken... 2 Organic salt solution was dynamically spin-coated at 1800 rpm for 30 s, and then the film was transferred from the glove box to a hot plate in air (humidity of about 35%) as soon as possible (within 35 s) and heat-treated at 150°C for 15 min to form a perovskite layer with a thickness of about 800 nm.

[0076] (3) Dissolve 4.5 mg of crown ether DB24C8 and 1.6 mg of bromine (the molar ratio of crown ether to bromine is 1:1) in 1 ml of chlorobenzene solvent to obtain a crown ether bromine spin-coating solution with a concentration of 6.1 mg / ml; then take 100 μL (spin-coating volume is 25 μL / cm) 2 The crown ether bromide spin-coating solution was dynamically spin-coated onto the perovskite layer at a spin speed of 4000 rpm for 30 s; finally, it was annealed on a 100℃ hot plate for 5 min to obtain the crown ether bromide modified layer.

[0077] (4) Take 80 µL (i.e., spin coating amount is 20 μL / cm) 2A 15 mg / ml PCBM chlorobenzene solution was dropped onto the modified layer, spin-coated at 2000 rpm for 35 s, and then annealed at 100℃ for 10 min to obtain the electron transport layer.

[0078] (5) Take 80 µL (i.e., spin coating amount of 20 μL / cm) 2 A 0.6 mg / ml BCP isopropanol solution was dropped onto the electron transport layer and spin-coated at 5000 rpm for 30 s to obtain a hole blocking layer.

[0079] (6) A 100 nm thick silver electrode layer was obtained by vapor deposition on the hole blocking layer.

[0080] The performance of the inverted perovskite solar cells prepared in the examples and comparative examples was tested under standard sunlight (AM 1.5G), and the test results are shown in Table 1.

[0081] Table 1

[0082]

[0083] As shown in Table 1, the open-circuit voltage (Voc), short-circuit current (Jsc), fill factor (FF), and power conversion efficiency (PCE) of the crown ether-modified inverted perovskite solar cells provided in Examples 1-3 are significantly higher than those of the comparative examples. This indicates that introducing a crown ether-modified layer between the perovskite layer and the electron transport layer plays an important role in improving the performance of inverted perovskite solar cells. This is because the crown ether itself has a hydrophobic external framework, which can effectively block the corrosion of perovskite materials by moisture and oxygen in the environment, and reduce the impact of these factors on the perovskite material through chemical stabilization, thereby extending the service life of the cell; the inner cavity of the crown ether can interact with metal ions (such as Pb) in the perovskite. 2+The crown ether iodine modification layer forms a complex, thereby creating a dense protective film at the interface to passivate perovskite surface defects. This film reduces non-radiative recombination centers in the perovskite, prolongs charge carrier lifetime, and reduces charge carrier loss, thus improving the photoelectric performance of the battery. Simultaneously, iodine ions in perovskite materials readily diffuse and migrate, leading to decreased battery stability. The crown ether iodine modification layer adsorbs diffused and migrated iodine ions, inhibiting their diffusion and migration, reducing perovskite material degradation, and improving long-term device stability. Furthermore, the crown ether iodine complex releases iodine ions, compensating for iodine vacancy defects in the perovskite layer, promoting self-healing of perovskite defects, and reducing charge recombination caused by defects, thereby improving battery efficiency and stability. In addition, the crown ether iodine modification layer can better match the energy levels between the perovskite layer and the electron transport layer, reducing series resistance while increasing parallel resistance, improving charge separation and transport efficiency, thus increasing the battery's fill factor and photoelectric conversion efficiency. Replacing iodine with bromine in the complex leads to the easier diffusion and migration of bromide ions into the perovskite layer due to their smaller radius. This affects the band gap of the perovskite material, thus impacting the absorption of sunlight and resulting in a significant decrease in short-circuit current density, ultimately reducing battery efficiency. Comparison of examples also shows that different crown ethers, due to their different structures, exhibit varying complexation effects with iodine, leading to different effects in the adsorption and release of iodide ions in different crown ether iodine complexes. Theoretical calculations and examples demonstrate that DB24C8 exhibits better complexation performance than B18C6 and 15C5.

[0084] The above description is merely a preferred embodiment of this application and is not intended to limit the scope of protection of this application. Under the guidance of the spirit and principles of this application, any modifications, equivalent substitutions, or improvements of any kind, as long as they are within the framework and concept of this application, should be considered as part of the scope of protection of this application.

Claims

1. A crown ether iodine-modified inverse perovskite solar cell, characterized in that, The inverted perovskite solar cell comprises a conductive substrate, a hole transport layer, a perovskite layer, a crown ether iodine modified layer, an electron transport layer, a hole blocking layer, and an electrode layer, which are sequentially stacked; its fabrication method includes the following steps: (1) A nickel oxide nanoparticle dispersion was spin-coated onto one side of a conductive substrate and then annealed. Then, an ethanol solution of Me-4PACz was spin-coated and annealed to obtain a nickel oxide / Me-4PACz double hole transport layer. (2) A perovskite film was deposited on the nickel oxide / Me-4PACz double hole transport layer obtained in step (1) using a two-step method, namely, first spin-coating a lead iodide precursor solution and then annealing, and then dynamically spin-coating an organic salt solution containing FAI and then annealing, thereby obtaining a perovskite layer. (3) Spin-coat a chlorobenzene solution of crown ether iodine onto the perovskite layer obtained in step (2) and anneal it to obtain a crown ether iodine modified layer; (4) Spin-coating a chlorobenzene solution of PCBM onto the crown ether iodine modified layer obtained in step (3) and annealing to obtain the PCBM electron transport layer; (5) Spin-coat the BCP isopropanol solution onto the PCBM electron transport layer obtained in step (4) to obtain the BCP hole blocking layer; (6) Deposit metallic silver onto the BCP hole blocking layer obtained in step (5) to obtain a silver electrode layer; In step (3), the crown ether iodine is formed by complexing crown ether with iodine in a molar ratio of (1~2):1, wherein the crown ether is one or more of dibenzo-24-crown 8-ether, benzo-18-crown 6-ether, and 15-crown ether-5; the concentration of crown ether iodine in the chlorobenzene solution is 3.6 mg / ml~10.5 mg / ml, and its spin-coating volume is 20~25 μL / cm. 2 The spin coating speed is 3000 rpm to 6000 rpm, the spin coating time is 30 to 60 s, the annealing temperature is 80℃ to 120℃, and the annealing time is 5 min to 15 min.

2. The inverted perovskite solar cell according to claim 1, characterized in that, In step (1), the conductive substrate is ITO or FTO, which needs to be cleaned and treated with ozone before use; the nickel oxide nanoparticle dispersion is prepared by dispersing nickel oxide nanoparticles in deionized water, wherein the concentration of nickel oxide nanoparticles is 10 mg / ml~15 mg / ml, and the spin-coating amount is 20~25 μL / cm. 2 The spin-coating speed was 2000 rpm to 3000 rpm, the spin-coating time was 30 to 60 s, the annealing temperature was 120℃ to 150℃, and the annealing time was 15 min to 30 min; the concentration of Me-4PACz in the ethanol solution was 0.4 mg / mL to 0.5 mg / mL, and the spin-coating volume was 20 to 25 μL / cm. 2 The spin coating speed is 4000 rpm to 5000 rpm, the spin coating time is 30 to 60 s, the annealing temperature is 90℃ to 110℃, and the annealing time is 5 min to 15 min.

3. The inverted perovskite solar cell according to claim 1, characterized in that, In step (2), the lead iodide precursor solution is prepared by dissolving PbI2 and CsI in a DMF / DMSO mixed solvent with a volume ratio of 9:1, wherein the concentration of PbI2 is 1.5M and the concentration of CsI is 0.075M, and the spin-coating amount is 15~25 μL / cm. 2 The spin-coating speed is 1000 rpm to 2000 rpm, the spin-coating time is 30 to 60 s, the annealing temperature is 60℃ to 80℃, and the annealing time is 30 to 90 s. The FAI-containing organic salt solution is prepared by dissolving FAI and MACl in isopropanol at a mass ratio of 10:1, wherein the total concentration of the two substances is 5 mg / ml to 15 mg / ml, and the spin-coating amount is 20 to 30 μL / cm. 2 The dynamic spin coating speed was 1500 rpm to 3000 rpm, the spin coating time was 30 to 60 s, the annealing temperature was 100℃ to 150℃, the annealing time was 15 min to 30 min, and the annealing humidity was 30% to 40%; the thickness of the resulting perovskite layer was 600 nm to 900 nm.

4. The inverted perovskite solar cell according to claim 1, characterized in that, In step (4), the concentration of PCBM in the chlorobenzene solution is 10 mg / ml to 30 mg / ml, and the spin-coating volume is 20 to 25 μL / cm. 2 The spin coating speed is 1500 rpm to 3000 rpm, the spin coating time is 30 to 60 s, the annealing temperature is 70℃ to 100℃, and the annealing time is 5 min to 15 min.

5. The inverted perovskite solar cell according to claim 1, characterized in that, In step (5), the concentration of BCP in the isopropanol solution is 0.3 mg / ml to 0.6 mg / ml, and the spin-coating volume is 20 to 25 μL / cm. 2 The spin coating speed is 4000 rpm to 6000 rpm, and the spin coating time is 30 to 60 s.

6. The inverted perovskite solar cell according to claim 1, characterized in that, The thickness of the silver electrode layer obtained in step (6) is 80 nm to 120 nm.

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