Thiapyran molecule modified solar cell and preparation method thereof

Abstract

The invention discloses a thiapyran molecule modified solar cell and a preparation method thereof. The cell sequentially comprises an ITO (Indium Tin Oxide) conductive glass layer, a 4-aminotetrahydro-2H-thiapyran-1, 1-dioxide hydrochloride modified [4-(3, 6-dimethoxy-9H-carbazole-9-yl) butyl] phosphonic acid hole transport layer, a Cs0.05 (FA < 0.77 > MA < 0.23 >) < 0.95 > Pb < (I < 0.77 > Br < 0.23 >) 3 wide-band gap perovskite thin film, a phenethyl ammonium iodide passivation layer, an electron transport layer of [6, 6]-phenyl-C61-butyric acid isomethyl ester, a 2, 9-dimethyl-4, 6, 7-tetrahydro-2H-thiapyran-1, 1-dioxide hydrochloride modified [4-(3, 6-dimethoxy-9H-carbazole-9-yl) butyl] the hole barrier layer is made of 1, 7-biphenyl-1, 10-phenanthroline; the electrode layer is made of metal Ag; according to the scheme, the hole transport layer is modified through thiapyran molecules, agglomeration of the hole transport layer is relieved, and a more compact and more uniform self-assembled single layer is generated by inducing favorable crystal orientation. A good bottom interface is obtained based on thiapyran molecule modification, and ordered growth of high-quality perovskite crystal grains is promoted. In addition, the energy level of the hole transport layer is effectively adjusted through thiapyran molecule treatment, and the extraction and transmission of carriers by the hole transport layer are enhanced.

Description

Technical Field

[0001] The 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 the growth of global energy demand and increasingly prominent environmental problems, the development and utilization of renewable energy has become a hot spot in the development of the global energy industry. New green energy represented by photovoltaics has the advantages of wide distribution, rich reserves and cleanliness, and is considered to be one of the most promising clean energy sources. my country attaches great importance to the adjustment of energy structure and strongly supports the development of the photovoltaic industry.

[0003] As a new type of third-generation solar cell, perovskite solar cells have attracted much attention in recent years due to their simple preparation, low cost and excellent photoelectric performance. At present, single-junction perovskite solar cells have achieved a high photoelectric conversion efficiency of 26.9%. However, due to the existence of a variety of unavoidable thermal and optical losses 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. In order to break through the theoretical limit, researchers have developed a new type of perovskite / crystalline silicon tandem solar cell structure, in which a wide-bandgap perovskite cell is used as a top cell to absorb higher-energy photons, and a narrow-bandgap silicon-based cell is used as a bottom cell to absorb lower-energy photons to achieve segmented utilization of the solar spectrum by the sub-cells, thereby avoiding the thermal loss of high-energy photons and improving the utilization rate of solar energy and the photoelectric conversion efficiency of the cell. With the continuous optimization and improvement of the cell structure, the photoelectric conversion efficiency of perovskite / crystalline silicon tandem cells has made certain progress, but the inherent chaotic crystallization and energy level mismatch problems of wide-bandgap perovskite solar cells are still one of the main obstacles to achieving high-efficiency photoelectric conversion efficiency and stable operation of perovskite / crystalline silicon tandem cells.

[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, produce denser and more uniform perovskite and self-assembled monolayer by inducing favorable crystal orientation. In addition, DMFP treatment effectively adjusts the energy level of the hole transport layer and promotes the extraction of interfacial charge.

[0006] In order to achieve the above technical effects, the present invention is implemented by the following technical scheme: a thiopyran 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 by 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 bandgap perovskite film PVSK, phenethylammonium iodide passivation layer PEAI, [6,6]-phenyl-C61-butyric acid isomethyl ester electron transport layer PCBM, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline 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-based molecule-modified solar cell, which comprises the following steps:

[0008] S1. Clean the glass sheet 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 instrument for 28 to 32 minutes;

[0009] S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid MeO-4PACZ ethanol solution at 55-65°C by stirring evenly and then standing, 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 20 mg / mL [6,6]-phenyl-C61-butyric acid isomethyl ester chlorobenzene solution as anti-solvent, prepare 10 mg / mL 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride aqueous solution and prepare 1 mg / mL 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline ethanol solution;

[0010] S3, take 40 μL of the prepared mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ and drop it on ITO, and 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, draw 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer, and 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 sheet on a heating table at 90 to 110°C for annealing for 28 to 32 minutes, wait for the perovskite film to crystallize on the glass sheet, and after the annealing is completed, let it stand to room temperature; obtain a wide-bandgap perovskite film PVSK;

[0012] S5, take 40 μL of phenylethyl ammonium 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 the suspension coating is completed, 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 the passivation layer at a rotation 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, take 7 μL of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline ethanol 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, 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 electrode.

[0016] Further, 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 800-1600 μL N,N-dimethylformamide and 200-400 μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5-3 M. 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 perovskite components are dissolved, 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 films.

[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, increases the grain size of perovskite, and reduces the 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 invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0025] Figure 1 The photoelectric conversion efficiency (PCE) and current density (J SC ), open circuit voltage (V OC ) and fill factor (FF) statistics;

[0026] Figure 2 The best JV curve diagram of Example 1-2 of the present invention;

[0027] Figure 3 The forward scanning and reverse scanning JV curves of the embodiment 1-2 of the present invention are shown in FIG.

[0028] Figure 4 is the XRD diagram of Example 1-2 of the present invention;

[0029] Figure 5 It is the XPS graph of Example 1-2 of the present invention;

[0030] Figure 6 PL and TRPL diagrams of Examples 1-2 of the present invention;

[0031] Figure 7 This is a SEM surface image of the hole transport layer of Example 1-2 of the present invention;

[0032] Figure 8 is a SEM cross-sectional view of Example 1-2 of the present invention;

[0033] Fig. 9 SCLC diagram of defect state density of Example 1-2 of the present invention;

[0034] Fig.10 It is a humidity stability curve diagram of Examples 1-2 of the present invention. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Example 1

[0037] A thiopyran-based molecule-modified solar cell is prepared, comprising 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 sheet 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 instrument for 28 to 32 minutes;

[0040] S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid MeO-4PACZ ethanol solution at 55-65°C by stirring evenly and then standing, 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 20 mg / mL [6,6]-phenyl-C61-butyric acid isomethyl ester chlorobenzene solution as anti-solvent, prepare 10 mg / mL 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride aqueous solution and prepare 1 mg / mL 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline ethanol solution;

[0041] S3, take 40 μL of the prepared MeO-4PACZ hole transport layer solution and drop it on the ITO, and perform static spin coating at a rotation speed of 5000 rpm, a spin coating time of 25 s, and an acceleration of 3000 rpm / s; after the spin coating is completed, place it on a heating table at 90-110°C for annealing for 8-12 minutes to obtain a hole transport layer;

[0042] S4, draw 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer, and 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 sheet on a heating table at 90 to 110°C for annealing for 28 to 32 minutes, wait for the perovskite film to crystallize on the glass sheet, and let it stand to room temperature after annealing; obtain a wide bandgap perovskite film;

[0043] S5, take 40 μL of phenylethyl ammonium 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 the suspension coating is completed, place it on a 90-110° C. heating table 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, and statically spin-coat it at a rotation 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 800-1600 μL N,N-dimethylformamide and 200-400 μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5-3 M. 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 950-1050 rpm until all perovskite components are dissolved, 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 films.

[0050] Example 2

[0051] A thiopyran-based molecule-modified solar cell is prepared, comprising 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 in sequence for 12 to 18 minutes, then drying it in a drying oven and treating it with ultraviolet ozone in an ultraviolet ozone instrument for 28 to 32 minutes to obtain an ITO conductive glass layer;

[0055] S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACZ) ethanol solution at 55-65°C by stirring evenly and then standing to 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 20 mg / mL [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM) chlorobenzene solution as antisolvent, prepare 10 mg / mL 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride aqueous solution and prepare 1 mg / mL 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP) ethanol solution;

[0056] S3, take 40 μL of the prepared mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ and drop it on ITO, and 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, draw 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer, and 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 sheet on a heating table at 90 to 110°C for annealing for 28 to 32 minutes, wait for the perovskite film to crystallize on the glass sheet, and after the annealing is completed, let it stand to 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 the suspension coating is completed, place it on a 90-110° C. heating table 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, and statically spin-coat it at a rotation 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, and 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 electrode.

[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, 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 800-1600 μL N,N-dimethylformamide and 200-400 μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5-3 M. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 solution;

[0064] 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 perovskite components are dissolved, 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 films.

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

[0066] Example 3

[0067] The performance of the solar cells with different structures prepared in combination with Examples 1-2 is tested as follows:

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

[0069] pass Figure 4It can be seen that the (110) peak intensity of the film deposited after the hole transport layer is modified by 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 It can be seen that compared with the control MeO-4PACZ hole transport layer, the hole transport layer film modified with thiopyran molecules showed an s 2p peak near 168.5eV, proving that the thiopyran molecules were successfully incorporated into MeO-4PACZ. In addition, after the modification of thiopyran molecules, the p 2p peak also shifted, proving that there is a strong interaction between the thiopyran molecules and the phosphate groups of MeO-4PACZ, which can exert a balancing force on MeO-4PACZ, thereby reducing the aggregation of MeO-4PACZ itself.

[0071] pass Figure 6 It can be seen that within the same emission wavelength range, the luminescence intensity of the perovskite film modified with thiopyran molecules is significantly lower than that of the control perovskite film, 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 with the thiopyran-modified hole transport layer also exhibits a high carrier extraction efficiency.

[0072] pass Figure 7 and Figure 8 It can be seen that after adding thiopyran molecules, the morphology of MeO-4PACZ film is more uniform, proving that thiopyran molecules can promote the formation of a denser and more uniform self-assembled monolayer (SAM) at the bottom. In addition, thiopyran molecules modify the hole transport layer to provide a good buried growth environment for the crystallization of perovskite. The SEM cross-section of the perovskite film with thiopyran molecules modifying the hole transport layer shows vertical penetration of the crystal, fewer disordered grains at the buried interface, and smaller grain boundaries. This is conducive to reducing the trap density.

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

[0074] pass Fig.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-carbazole-9-yl)butyl]phosphonic acid hole transport layer modified by 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 bandgap perovskite film PVSK, phenethylammonium iodide passivation layer PEAI, [6,6]-phenyl-C61-butyric acid isomethyl ester electron transport layer PCBM, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline 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 sheet 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 instrument for 28 to 32 minutes; S2. Prepare 1 mg / mL [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid MeO-4PACZ ethanol solution at 55-65°C by stirring evenly and then standing, 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 20 mg / mL [6,6]-phenyl-C61-butyric acid isomethyl ester chlorobenzene solution as anti-solvent, prepare 10 mg / mL 4-aminotetrahydro-2H-thiopyran 1,1-dioxide hydrochloride aqueous solution and prepare 1 mg / mL 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline ethanol solution; S3, take 40 μL of the prepared mixed hole transport layer solution of thiopyran molecules and MeO-4PACZ and drop it on ITO, and 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, draw 50 μL of perovskite precursor PVSK solution and spread it on the upper layer of the hole transport layer, and 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 sheet on a heating table at 90 to 110°C for annealing for 28 to 32 minutes, wait for the perovskite film to crystallize on the glass sheet, and after the annealing is completed, let it stand to room temperature; obtain a wide-bandgap perovskite film PVSK; S5, take 40 μL of phenylethyl ammonium 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 the suspension coating is completed, 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 the passivation layer at a rotation 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, take 7 μL of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline ethanol 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; 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 800-1600 μL N,N-dimethylformamide and 200-400 μL dimethyl sulfoxide to form a wide bandgap perovskite film CsI with a thickness of 1.5-3 M. 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 films.

4. The method for preparing a thiopyran-based molecule-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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