Thiapyran molecule modified solar cell and preparation method thereof

Abstract

The application discloses a thietane molecule modified solar cell and a preparation method thereof. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 wide band gap perovskite film, a phenylethylammonium iodide passivation layer, an electron transport layer of [6,6]-phenyl-C61-butyric acid methyl ester, a hole blocking layer of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and an electrode layer of metal Ag; the scheme modifies the hole transport layer by thietane molecules, relieves the agglomeration of the hole transport layer, induces favorable crystal orientation, and generates a denser and more uniform self-assembled monolayer. Based on the good bottom interface obtained after the modification of the thietane molecules, the ordered growth of high-quality perovskite grains is promoted. In addition, the thietane molecule treatment effectively adjusts the energy level of the hole transport layer, and enhances the extraction and transmission of the hole transport layer to the carriers.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and in particular to a thiopyran molecule-modified solar cell and a preparation method thereof. Background Art

[0002] With growing global energy demand and increasingly prominent environmental issues, the development and utilization of renewable energy has become a hot topic in the global energy industry. New green energy sources, such as photovoltaics, offer advantages such as widespread distribution, abundant reserves, and cleanliness, making them considered one of the most promising clean energy sources. my country attaches great importance to adjusting its energy structure and strongly supports the development of the photovoltaic industry.

[0003] Perovskite solar cells, a new type of third-generation solar cell, have attracted significant attention in recent years due to their simple fabrication, low cost, and excellent photoelectric performance. Currently, single-junction perovskite solar cells have achieved a high photoelectric conversion efficiency of 26.9%. However, due to the various unavoidable thermal and optical losses inherent in single-junction perovskite solar cells, their photoelectric conversion efficiency is very close to the theoretical efficiency limit given by the Shockley-Queisser standard model. To overcome this theoretical limit, researchers have developed a novel perovskite / crystalline silicon tandem solar cell structure. In this structure, a wide-bandgap perovskite cell serves as the top cell to absorb higher-energy photons, while a narrow-bandgap silicon-based cell serves as the bottom cell to absorb lower-energy photons. This allows for segmented utilization of the solar spectrum by the sub-cells, thereby avoiding thermal losses of high-energy photons and improving solar energy utilization and cell photoelectric conversion efficiency. With continuous optimization and improvement of the cell structure, the photoelectric conversion efficiency of perovskite / crystalline silicon tandem cells has improved significantly. However, the inherent chaotic crystallization and energy level mismatch issues of wide-bandgap perovskite solar cells remain a major obstacle to achieving high photoelectric conversion efficiency and stable operation.

[0004] In order to solve the above problems, this paper proposes a thiopyran-based molecule-modified solar cell and a preparation method thereof. Summary of the Invention

[0005] The present invention aims to reduce the aggregation of the hole transport layer by thiopyran treatment, thereby inducing a favorable crystal orientation, resulting in a denser and more uniform perovskite and self-assembled monolayer. In addition, DMFP treatment effectively modulates the energy level of the hole transport layer, promoting interfacial charge extraction.

[0006] In order to achieve the above technical effects, the present invention is implemented by the following technical solutions: a thiopyran-based molecule-modified solar cell, characterized in that it includes, from bottom to top, an ITO conductive glass layer, a [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid hole transport layer modified with 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride, a Cs0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 Wide band gap perovskite film PVSK, phenylethylammonium iodide passivation layer PEAI, [6,6]-phenyl-C61-butyric acid isomethyl ester electron transport layer PCBM, 2,9-dimethyl-4,7-biphenyl-1,10-o-diazophenanthroline hole blocking layer BCP and metal Ag electrode layer.

[0007] Another object of the present invention is to provide a method for preparing a thiopyran-modified solar cell, characterized in that it comprises the following steps:

[0008] S1. Clean the glass slide by ultrasonically cleaning it with detergent, isopropyl alcohol, deionized water, and anhydrous ethanol for 12 to 18 minutes, then drying it in a drying oven and treating it with ultraviolet ozone in an ultraviolet ozone apparatus for 28 to 32 minutes.

[0009] S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid MeO-4PACZ ethanol solution and perovskite precursor Cs by stirring and then standing at 55-65°C. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 wide bandgap perovskite film PVSK, prepare a 20 mg / mL chlorobenzene solution of [6,6]-phenyl-C61-butyric acid isomethyl ester as an antisolvent, prepare a 10 mg / mL aqueous solution of 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride, and prepare a 1 mg / mL ethanol solution of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline;

[0010] S3. Take 40 μL of the prepared mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ and drop it on the ITO. Perform static spin coating at a speed of 5000 rpm, a spin coating time of 25 s, and an acceleration of 3000 rpm / s. After spin coating, place it on a heating table at 90-110°C for annealing for 8-12 minutes to obtain a hole transport layer.

[0011] S4. Pipette 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer. Perform static spin coating at a low speed of 1100 rpm, a spin coating time of 5 s, and an acceleration of 2000 rpm / s and a high speed of 6000 rpm, a spin coating time of 35 s, and an acceleration of 3000 rpm / s. Add 150 μL of anti-solvent chlorobenzene solution at a high speed of 23 to 27 s. After the spin coating is completed, immediately place the spin-coated glass slide on a heating table at 90 to 110° C. and anneal for 28 to 32 minutes, waiting for the perovskite film to crystallize on the glass slide. After annealing, let it stand to room temperature to obtain a wide-bandgap perovskite film PVSK.

[0012] S5. Take 40 μL of phenylethylammonium iodide passivation agent solution and perform dynamic suspension coating on the perovskite film at a rotation speed of 4000 rpm, a spin coating time of 30 s, and an acceleration of 3000 rpm / s. After suspension coating, place it on a heating table at 90-110°C for annealing for 9-11 minutes, and then let it stand to room temperature to obtain a passivation layer PEAI;

[0013] S6. Take 40 μL of [6,6]-phenyl-C61-butyric acid isomethyl ester chlorobenzene solution and drop it on the perovskite film with passivation layer at a speed of 1500 rpm, an acceleration of 1000 rpm / s, and a spin coating time of 50 s. After the spin coating is completed, let it stand for 13 to 17 minutes to obtain the electron transport layer PCBM;

[0014] S7, taking 7 μL of 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline ethanol solution and performing dynamic suspension coating on the PCBM layer at a rotation speed of 6000 rpm, an acceleration of 3000 rpm / s, and a spin coating time of 25 s, and the spin coating work is completed; a hole blocking layer BCP is obtained;

[0015] S8. Use tweezers to scrape off part of the active layer to expose the electrode, and then place it in the vacuum coating machine for evaporation. of silver electrodes.

[0016] Furthermore, in S2, the wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) The preparation process of 3 is as follows:

[0017] S1.1, the molar mass ratio is 0.075~0.15:0.35~0.7:1.155~2.31:0.345~0.69:1.15~2.3=CsI:PbBr2:FAI:MABr:PbI2. Weigh CsI, PbBr2, FAI, MABr and PbI2 and dissolve them in a mixed solvent of 800~1600μL N,N-dimethylformamide and 200~400μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5~3M. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 solution;

[0018] S1.2, the configured wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 Place on a magnetic stirring table at 50-70°C, heat and stir at 950-1050 rpm until all the perovskite components are dissolved, and then filter; the perovskite precursor Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3Wide bandgap perovskite film.

[0019] Furthermore, in S3, the volume ratio of the mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ is 1-2:40-80.

[0020] The beneficial effects of the present invention are:

[0021] (1) In the present invention, a hole transport layer modification strategy is adopted to reduce the aggregation of MeO-4PACZ and form a denser and more uniform self-assembled monolayer and perovskite layer by inducing a favorable crystal orientation;

[0022] (2) In the present invention, the modification strategy of thiopyran molecules provides a good bottom interface for the crystallization of perovskite, which slows down the crystal growth of perovskite, promotes the increase of perovskite grain size and reduces defect density;

[0023] (3) In the present invention, the thiopyran molecular treatment effectively regulates the energy level of the perovskite and promotes the extraction of interfacial charges. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the description of the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained without creative labor based on these drawings.

[0025] Figure 1 Statistical charts of photoelectric conversion efficiency (PCE), current density (J SC ), open circuit voltage (V OC ) and fill factor (FF) of the present application embodiments 1-2;

[0026] Figure 2 Optimal J-V curve charts of the present application embodiments 1-2;

[0027] Figure 3 Forward and reverse scanning J-V curve charts of the present application embodiments 1-2

[0028] Figure 4 XRD charts of the present application embodiments 1-2;

[0029] Figure 5 XPS charts of the present application embodiments 1-2;

[0030] Figure 6 PL and TRPL charts of the present application embodiments 1-2;

[0031] Figure 7 SEM surface charts of the hole transport layer of the present application embodiments 1-2;

[0032] Figure 8 SEM cross-section charts of the present application embodiments 1-2;

[0033] Figure 9 Defect state density SCLC charts of the present application embodiments 1-2;

[0034] Figure 10 Humidity stability curve charts of the present application embodiments 1-2. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0036] Embodiment 1

[0037] Preparation of a thiopyran-based molecule-modified solar cell comprises the following steps:

[0038] When the battery structure from bottom to top is: ITO / MeO-2PACz / PVSK / PCBM / BCP / Ag, it is prepared as follows:

[0039] S1. Clean the glass slide by ultrasonically cleaning it with detergent, isopropyl alcohol, deionized water, and anhydrous ethanol for 12 to 18 minutes, then drying it in a drying oven and treating it with ultraviolet ozone in an ultraviolet ozone apparatus for 28 to 32 minutes.

[0040] S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid MeO-4PACZ ethanol solution and perovskite precursor Cs by stirring and then standing at 55-65°C. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 wide bandgap perovskite film PVSK, prepare a 20 mg / mL chlorobenzene solution of [6,6]-phenyl-C61-butyric acid isomethyl ester as an antisolvent, prepare a 10 mg / mL aqueous solution of 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride, and prepare a 1 mg / mL ethanol solution of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline;

[0041] S3. Take 40 μL of the prepared MeO-4PACZ hole transport layer solution and drop it onto the ITO. Perform static spin coating at a speed of 5000 rpm, a spin coating time of 25 s, and an acceleration of 3000 rpm / s. After spin coating, place the solution on a heating plate at 90-110°C and anneal for 8-12 minutes to obtain a hole transport layer.

[0042] S4. Pipette 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer. Perform static spin coating at a low speed of 1100 rpm, a spin coating time of 5 s, and an acceleration of 2000 rpm / s and a high speed of 6000 rpm, a spin coating time of 35 s, and an acceleration of 3000 rpm / s. Add 150 μL of anti-solvent chlorobenzene solution at a high speed of 23 to 27 s. After the spin coating is completed, immediately place the spin-coated glass slide on a heating table at 90 to 110° C. and anneal for 28 to 32 minutes, waiting for the perovskite film to crystallize on the glass slide. After annealing, let it stand to room temperature to obtain a wide-bandgap perovskite film.

[0043] S5. Take 40 μL of phenylethylammonium iodide passivation agent solution and perform dynamic suspension coating on the perovskite film at a rotation speed of 4000 rpm, a spin coating time of 30 s, and an acceleration of 3000 rpm / s. After suspension coating, place it on a heating table at 90-110°C for annealing for 9-11 minutes, and then let it stand to room temperature to obtain a passivation layer;

[0044] S6. Take 40 μL of PCBM solution and drop it on the perovskite film with the passivation layer. Static spin coating is performed at a speed of 1500 rpm, an acceleration of 1000 rpm / s, and a spin coating time of 50 s. After the spin coating is completed, let it stand for 13 to 17 minutes to obtain the electron transport layer PCBM.

[0045] S7, take 7 μL of BCP solution and perform dynamic suspension coating on the PCBM layer at a rotation speed of 6000 rpm, an acceleration of 3000 rpm / s, and a spin coating time of 25 s to obtain a hole blocking layer BCP, and the spin coating work is completed;

[0046] S8. Use tweezers to scrape off part of the active layer to expose the electrode, and then place it in the vacuum coating machine for evaporation. of silver electrodes.

[0047] In the above S2, the wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) The preparation process of 3 is as follows:

[0048] S1.1, the molar mass ratio is 0.075~0.15:0.35~0.7:1.155~2.31:0.345~0.69:1.15~2.3=CsI:PbBr2:FAI:MABr:PbI2. Weigh CsI, PbBr2, FAI, MABr and PbI2 and dissolve them in a mixed solvent of 800~1600μL N,N-dimethylformamide and 200~400μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5~3M. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 solution;

[0049] S1.2, the configured wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23)3 Place on a magnetic stirring table at 50-70°C, heat and stir at a speed of 950-1050 rpm until all the perovskite components are dissolved, and then filter; the perovskite precursor Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3Wide bandgap perovskite film.

[0050] Example 2

[0051] Preparation of a thiopyran-based molecule-modified solar cell comprises the following steps:

[0052] When the battery structure from bottom to top is: ITO / MeO-2PACz / PVSK / PEAI / PCBM / BCP

[0053] / Ag, its preparation is as follows:

[0054] S1. Cleaning the glass sheet: ultrasonically cleaning the glass sheet with detergent, isopropyl alcohol, deionized water, and anhydrous ethanol for 12 to 18 minutes, drying the glass sheet in a drying oven, and treating the glass sheet with ultraviolet ozone in an ultraviolet ozone apparatus for 28 to 32 minutes to obtain an ITO conductive glass layer;

[0055] S2. Prepare 1 mg / mL ethanol solution of [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACZ) at 55-65°C by stirring evenly and then letting it stand, and prepare the perovskite precursor Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 wide bandgap perovskite film (PVSK), prepare a 20 mg / mL chlorobenzene solution of [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM) as an antisolvent, prepare a 10 mg / mL aqueous solution of 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride, and prepare a 1 mg / mL ethanol solution of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP);

[0056] S3. Take 40 μL of the prepared mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ and drop it on the ITO. Perform static spin coating at a speed of 5000 rpm, a spin coating time of 25 s, and an acceleration of 3000 rpm / s. After spin coating, place it on a heating table at 90-110°C for annealing for 8-12 minutes to obtain a hole transport layer.

[0057] S4. 50 μL of perovskite precursor PVSK solution was applied to the upper layer of the hole transport layer, and static spin coating was performed at a low speed of 1100 rpm, a spin coating time of 5 s, and an acceleration of 2000 rpm / s, and a high speed of 6000 rpm, a spin coating time of 35 s, and an acceleration of 3000 rpm / s; 150 μL of anti-solvent chlorobenzene solution was added dropwise at a high speed of 23 to 27 s; after the spin coating was completed, the spin-coated glass slide was immediately placed on a heating table at 90 to 110° C. for annealing for 28 to 32 minutes, waiting for the perovskite film to crystallize on the glass slide. After annealing, the slide was allowed to stand at room temperature to obtain a wide-bandgap perovskite film PVSK.

[0058] S5. Take 40 μL of phenylethylammonium iodide (PEAI) passivation agent solution and perform dynamic suspension coating on the perovskite film at a rotation speed of 4000 rpm, a spin coating time of 30 s, and an acceleration of 3000 rpm / s. After suspension coating, place it on a heating table at 90-110°C for annealing for 9-11 minutes, and then let it stand to room temperature to obtain a passivation layer PEAI;

[0059] S6. Take 40 μL of PCBM solution and drop it on the perovskite film with the passivation layer. Static spin coating is performed at a speed of 1500 rpm, an acceleration of 1000 rpm / s, and a spin coating time of 50 s. After the spin coating is completed, let it stand for 13 to 17 minutes to obtain the electron transport layer PCBM.

[0060] S7, take 7 μL of BCP solution and perform dynamic suspension coating on the PCBM layer at a rotation speed of 6000 rpm, an acceleration of 3000 rpm / s, and a spin coating time of 25 s to obtain a hole blocking layer BCP. The spin coating work is completed;

[0061] S8. Use tweezers to scrape off part of the active layer to expose the electrode, and then place it in the vacuum coating machine for evaporation. of silver electrodes.

[0062] In the above S2, the wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) The preparation process of 3 is as follows:

[0063] S1.1, CsI, PbBr2, FAI, MABr and PbI2 are weighed in a molar mass ratio of 0.075-0.15:0.35-0.7:1.155-2.31:0.345-0.69:1.15-2.3 = CsI:PbBr2:FAI:MABr:PbI2, and dissolved in 800-1600 μL of a mixed solvent of N, N-dimethylformamide and 200-400 μL of dimethyl sulfoxide to form a 1.5-3 M wide-bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 solution;

[0064] S1.2, the prepared wide-bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 is placed on a magnetic stirring table at 50-70°C, and heated and stirred at a speed of 950-1050 rpm until the perovskite components are completely dissolved and filtered; a perovskite precursor Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 wide-bandgap perovskite film.

[0065] In the above S3, the volume ratio of the mixed hole transport layer solution of the thioxane molecule and MeO-4PACZ is 1:40.

[0066] Example 3

[0067] The different structure solar cells prepared in combination with Examples 1-2 are each tested for performance, as follows:

[0068] It can be seen from Figure 2 and Figure 3 that the photoelectric conversion efficiency of the perovskite device by introducing the thioxane molecule has been greatly improved, from 20.59% to 21.97%, which is significant. In addition, in the case of forward and reverse scanning, the hysteresis factor decreases from 6.6% to 5.7%, and the smaller the hysteresis factor, the less affected by the hysteresis phenomenon, indicating that the number of defects is effectively reduced.

[0069] It can be seen from Figure 4It can be seen that the (110) peak intensity of the film deposited after the hole transport layer was modified with thiopyran molecules is higher than that of the control group. The increase in peak intensity helps to increase the crystallinity of the perovskite film and is conducive to the formation of smoother and more ordered perovskite grains.

[0070] pass Figure 5 Compared to the control MeO-4PACZ hole transport layer, the hole transport layer film modified with thiopyran molecules exhibits an s 2p peak near 168.5 eV, demonstrating the successful incorporation of thiopyran molecules into MeO-4PACZ. Furthermore, the p 2p peak shifts after thiopyran modification, demonstrating a strong interaction between the thiopyran molecules and the phosphate groups of MeO-4PACZ. This interaction exerts a balancing force on MeO-4PACZ, thereby reducing its aggregation.

[0071] pass Figure 6 The luminescence intensity of the perovskite film modified with thiopyran molecules is significantly lower than that of the control perovskite film within the same emission wavelength range, indicating that the thiopyran-modified hole transport layer promotes effective photoinduced charge transfer between the perovskite and the hole transport interface layer. Combined with TRPL, the perovskite film modified with thiopyran molecules also exhibits high carrier extraction efficiency.

[0072] pass Figure 7 and Figure 8 The addition of thiopyran molecules resulted in a more uniform morphology for the MeO-4PACZ film, demonstrating that thiopyran molecules promote the formation of a denser and more uniform self-assembled monolayer (SAM) at the bottom. Furthermore, thiopyran-modified hole transport layers provide a favorable buried growth environment for perovskite crystallization. SEM cross-sections of perovskite films with thiopyran-modified hole transport layers demonstrate vertical crystal penetration, fewer disordered grains at the buried interface, and smaller grain boundaries, contributing to a reduction in trap density.

[0073] pass Figure 9 It can be seen that after the hole transport layer is modified with thiopyran molecules, the perovskite film exhibits less hole defect state density. Less defect state density is conducive to carrier migration, thereby showing a significantly improved short-circuit current density and better device performance.

[0074] pass Figure 10 It can be seen that after modification with thiopyran molecules, the humidity stability is better than that of the control device. The device modified with thiopyran molecules can still maintain more than 95% of the initial efficiency after being placed in a nitrogen glove box for 1500 hours. Previous characterization has proved that the film has less defect state density and stronger carrier extraction and transmission capabilities, which greatly improves the stability of the device.

Claims

1. A thiopyran-based molecule-modified solar cell, characterized in that: From bottom to top, it includes an ITO conductive glass layer, a [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid hole transport layer modified with 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride, and a Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 Wide band gap perovskite film PVSK, phenylethylammonium iodide passivation layer PEAI, [6,6]-phenyl-C61-butyric acid isomethyl ester electron transport layer PCBM, 2,9-dimethyl-4,7-biphenyl-1,10-o-diazophenanthroline hole blocking layer BCP and metal Ag electrode layer.

2. A method for preparing a thiopyran-based molecule-modified solar cell, characterized in that: The steps include: S1. Clean the glass slide by ultrasonically cleaning it with detergent, isopropyl alcohol, deionized water, and anhydrous ethanol for 12 to 18 minutes, then drying it in a drying oven and treating it with ultraviolet ozone in an ultraviolet ozone apparatus for 28 to 32 minutes. S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid MeO-4PACZ ethanol solution and perovskite precursor Cs by stirring and then standing at 55-65°C. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 wide bandgap perovskite film PVSK, prepare a 20 mg / mL chlorobenzene solution of [6,6]-phenyl-C61-butyric acid isomethyl ester as an antisolvent, prepare a 10 mg / mL aqueous solution of 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride, and prepare a 1 mg / mL ethanol solution of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline; S3. Take 40 μL of the prepared mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ and drop it on the ITO. Perform static spin coating at a speed of 5000 rpm, a spin coating time of 25 s, and an acceleration of 3000 rpm / s. After spin coating, place it on a heating table at 90-110°C for annealing for 8-12 minutes to obtain a hole transport layer. S4. Pipette 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer. Perform static spin coating at a low speed of 1100 rpm, a spin coating time of 5 s, and an acceleration of 2000 rpm / s and a high speed of 6000 rpm, a spin coating time of 35 s, and an acceleration of 3000 rpm / s. Add 150 μL of anti-solvent chlorobenzene solution at a high speed of 23 to 27 s. After the spin coating is completed, immediately place the spin-coated glass slide on a heating table at 90 to 110° C. and anneal for 28 to 32 minutes, waiting for the perovskite film to crystallize on the glass slide. After annealing, let it stand to room temperature to obtain a wide-bandgap perovskite film PVSK. S5. Take 40 μL of phenylethylammonium iodide passivation agent solution and perform dynamic suspension coating on the perovskite film at a rotation speed of 4000 rpm, a spin coating time of 30 s, and an acceleration of 3000 rpm / s. After suspension coating, place it on a heating table at 90-110°C for annealing for 9-11 minutes, and then let it stand to room temperature to obtain a passivation layer PEAI; S6. Take 40 μL of [6,6]-phenyl-C61-butyric acid isomethyl ester chlorobenzene solution and drop it on the perovskite film with passivation layer at a speed of 1500 rpm, an acceleration of 1000 rpm / s, and a spin coating time of 50 s. After the spin coating is completed, let it stand for 13 to 17 minutes to obtain the electron transport layer PCBM; S7, taking 7 μL of 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline ethanol solution and performing dynamic suspension coating on the PCBM layer at a rotation speed of 6000 rpm, an acceleration of 3000 rpm / s, and a spin coating time of 25 s to obtain a hole blocking layer BCP, and the spin coating work is completed; S8. Use tweezers to scrape off part of the active layer to expose the electrode, and then place it in the vacuum coating machine for evaporation. of silver electrodes.

3. The method for preparing a thiopyran-based molecule-modified solar cell according to claim 2, characterized in that: In S2, the wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) The preparation process of 3 is as follows: S1.1, the molar mass ratio is 0.075~0.15:0.35~0.7:1.155~2.31:0.345~0.69:1.15~2.3=CsI:PbBr2:FAI:MABr:PbI2. Weigh CsI, PbBr2, FAI, MABr and PbI2 and dissolve them in a mixed solvent of 800~1600μL N,N-dimethylformamide and 200~400μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5~3M. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 solution; S1.2, the configured wide bandgap perovskite film Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 Place on a magnetic stirring table at 50-70°C, heat and stir at a speed of 950-1050 rpm until all the perovskite components are dissolved, and then filter; the perovskite precursor Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3Wide bandgap perovskite film.

4. The method for preparing a thiopyran-modified solar cell according to claim 2, characterized in that In S3, the volume ratio of the mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ is 1-2:40-80.

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