A p-i-n type perovskite solar cell based on stress release photo-cycle stability of light-dark reversible isomerization molecules and a preparation method thereof

Abstract

The application discloses a p-i-n type perovskite solar cell based on stress release light cycle stability of light-dark reversible isomerization molecules and a preparation method thereof, and belongs to the solar cell field. In the preparation method, a series of light-dark reversible isomerization molecules are used as a grain boundary buffer layer of the perovskite solar cell. The anti-expansion characteristics of the light-dark reversible isomerization molecules can effectively buffer the expansion and shrinkage of a perovskite thin film under light-dark cycle conditions, and inhibit the film degradation caused by the expansion and shrinkage of the perovskite thin film. The passivation group at one end of the light-dark reversible isomerization molecules can form coordination with Pb 2+ , guarantee the ordered growth of the thin film, reduce the defect density, improve the charge transport rate, and further realize the preparation of the high-efficiency and stable p-i-n type perovskite solar cell. The method provides a preparation method for improving the p-i-n type perovskite solar cell in an actual light-dark cycle operation environment, and plays a great promoting role in the commercialization of the p-i-n type perovskite solar cell.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of solar cells, and particularly relates to a p-i-n type perovskite solar cell based on light-dark reversible isomer stress release light cycle stability and a preparation method thereof. BACKGROUND

[0002] Perovskite solar cells have become a breakthrough technology in the field of photovoltaics, with high efficiency and low production cost. However, its stability is a major challenge for commercialization, especially under actual operating conditions. Although recent progress has improved the resistance of perovskite solar cells to light, heat, bias voltage and humidity, their stability in outdoor environments has not been well improved due to large changes in daily and seasonal weather conditions.

[0003] When simulating outdoor conditions, high-energy ultraviolet light can cause irreversible damage, significantly reducing device performance. In addition, cyclic illumination can produce more adverse effects and accumulate harmful effects, ultimately shortening the lifetime and reliability of perovskite solar cells. Here, standard accelerated aging tests, such as continuous light soaking, are insufficient to simulate the outdoor cycling process. Therefore, we use light-dark cycle testing to simulate real-world day-night alternating conditions to reveal indoor rapid light cycle to accelerate device aging and better estimate the long-term stability of perovskite solar cells in the real world. Light cycle-induced accumulation of stress inside the absorber leads to crystal breakage at the grain boundaries, resulting in lattice strain in the perovskite thin film and leading to rapid degradation of perovskite solar cells. To address these issues, we have developed a grain boundary elasticity strategy using photo-switchable isomers triggered by ultraviolet light for dynamic stress release to improve the durability of the device during light cycling. SUMMARY

[0004] The purpose of the present application is to provide a p-i-n type perovskite solar cell based on light-dark reversible isomer stress release light cycle stability and a preparation method thereof, which introduces a series of materials with dynamic stress release characteristics as additives to the perovskite precursor solution, adjusts the perovskite lattice stress during light cycling, and repairs the perovskite damage caused by light cycling through molecular π-π interactions, Lewis acid-base reactions and other effects. The photovoltaic device prepared by this strategy has significantly improved energy conversion efficiency and excellent light cycle stability.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] A preparation method of a p-i-n type perovskite solar cell based on light-dark reversible isomer stress release light cycle stability, the preparation method comprising the following steps:

[0007] (1) spin-coating an ethanol solution of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) and [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) mixture on a washed, dried and ozone-treated substrate to obtain a hole selection layer;

[0008] (2) doping a light-dark reversible isomerization molecule into a raw perovskite precursor solution to obtain an optimized perovskite precursor solution;

[0009] (3) depositing the optimized perovskite precursor solution and annealing to obtain a perovskite layer;

[0010] (4) preparing [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM) on the perovskite layer by spin-coating, doctor-blading, screen printing or the like or preparing fullerene (C 60 ) by evaporation or inkjet printing to obtain a uniform electron transport layer;

[0011] (5) preparing a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) modification layer or a tin oxide (SnO2) modification layer on the electron transport layer by evaporation or inkjet printing;

[0012] (6) preparing a cathode metal electrode on the BCP or SnO2 modification layer by evaporation or inkjet printing.

[0013] Further, the substrate in step (1) is an ITO or FTO conductive substrate, the total concentration of 2PACz and Me-4PACz in the ethanol solution is 0.1-0.5 mg / mL (the mass ratio of 2PACz and Me-4PACz is 1:1-3), the spin-coating amount is 10-20 μL / cm 2 , the spin-coating speed is 3000-5000 r / min, the annealing temperature is 100-120 ℃, and the annealing time is 5-10 min. The thickness of the hole selection layer is 2-10 nm.

[0014] Further, the light-dark reversible isomerization molecule material in step (2) is at least one of azobenzene (Abz), azobenzene-4-benzoic acid (Ca-Abz), azobenzene-4,4-dicarboxylic acid (Dca-Abz) and 4-(phenylazo)benzenesulfonic acid (SA-Abz) for triggering dynamic stress release under ultraviolet light. The molecular formula of azobenzene (Abz), azobenzene-4-benzoic acid (Ca-Abz), azobenzene-4,4-dicarboxylic acid (Dca-Abz) and 4-(phenylazo)benzenesulfonic acid (SA-Abz) is shown in Figure 1 .

[0015] Preferably, the concentration of the light-dark reversible isomer molecules doped in the perovskite precursor is 1-2 mg / mL.

[0016] Further, the original perovskite precursor solution in step (2) is specifically Cs 0.05 MA 0.1 FA 0.85 PbI3, and the perovskite concentration is 1.5-2 mol / L. Cs 0.05 MA 0.1 FA 0.85 PbI3. The preparation process of the perovskite precursor solution is as follows: lead iodide (PbI2), formamidinium iodide (FAI), methylammonium iodide (MAI), methylammonium chloride (MACl), and cesium iodide (CsI) are dissolved in a 1 mL mixed solvent composed of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a proportion, and stirred uniformly to obtain a perovskite precursor solution. The volume ratio of DMSO and DMF in the mixed solvent is 1:4.

[0017] Further, the perovskite annealing temperature in step (3) is 100-120 ℃, and the annealing time is 20-45 min.

[0018] Preferably, the spin coating amount of the perovskite precursor solution is 10-20 μL / cm 2 , and the spin coating speed is 3000-5000 r / min. The anti-solvent is chlorobenzene, and the spin coating amount of the anti-solvent is 15-35 μL / cm 2 .

[0019] Preferably, the thickness of the perovskite layer in step (3) is 500-700 nm.

[0020] Further, the thickness of the C 60 or PC 61 BM electron transport layer in step (4) is 30-40 nm.

[0021] Further, the thickness of the BCP or SnO2 modification layer in step (5) is 10-25 nm.

[0022] Further, the cathode electrode in step (6) is Au, Ag, or Cu, and the electrode thickness is 70-110 nm.

[0023] The p-i-n type perovskite solar cell based on the light-dark reversible isomer stress release light cycle stable prepared by the preparation method.

[0024] The present application provides a light-dark reversible isomerization stress release light cycle stable perovskite solar cell, by introducing a series of materials with light-dark reversible isomerization characteristics as additives in the perovskite precursor solution, the materials regulate the perovskite stress in the light cycle through reversible isomerization characteristics, thereby repairing the perovskite grain boundary damage dominated by defects caused by thermal expansion and contraction under light cycle. The finally prepared perovskite photovoltaic device has excellent light cycle stability while realizing high energy conversion efficiency. The present application is conducive to in-depth understanding of the correlation mechanism of perovskite lattice strain and defects and perovskite operation stability under outdoor conditions, and provides a new idea for preparing high-efficiency and light cycle stable perovskite photovoltaic devices. The strategy has important significance for promoting the commercial development of perovskite solar cells and comprehensively improving the performance of perovskite solar cells. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 Molecular formula of azobenzene (Abz), azobenzene-4-benzoic acid (Ca-Abz), azobenzene-4,4-dicarboxylic acid (Dca-Abz) and 4-(phenylazo) benzenesulfonic acid (SA-Abz);

[0026] Figure 2 Structure diagram of the p-i-n type perovskite solar cell prepared by the preparation method of the present application;

[0027] Figure 3 Perovskite solar cell device of Example 1 with azobenzene (Abz) as an additive J-V curve;

[0028] Figure 4 Perovskite solar cell device of Example 2 with azobenzene-4-benzoic acid (Ca-Abz) as an additive J-V curve;

[0029] Figure 5 Perovskite solar cell device of Example 3 with azobenzene-4,4-dicarboxylic acid (Dca-Abz) as an additive J-V curve;

[0030] Figure 6 Perovskite solar cell device of Example 4 with 4-(phenylazo) benzenesulfonic acid (SA-Abz) as an additive J-V curve;

[0031] Figure 7 Perovskite solar cell device of Comparative Example 1 J-V curve;

[0032] Figure 8 Light cycle stability curve of the perovskite solar cell devices of Examples 1-4 and Comparative Example 1. DETAILED DESCRIPTION

[0033] The present application will be further described in conjunction with specific examples, but the examples are only exemplary and do not constitute any limitation on the scope of the present application. Those skilled in the art should understand that the details and forms of the technical solutions of the present application can be modified or replaced without departing from the spirit and scope of the present application, and such modifications and replacements all fall within the protection scope of the present application.

[0034] Example 1

[0035] A preparation method of a p-i-n type perovskite solar cell based on stress release light cycle stability of light-dark reversible isomerization molecules, comprising the following steps:

[0036] (1) A 2.5 cm*2.5 cm FTO transparent conductive substrate was first rubbed with glass detergent on both sides, then ultrasonic cleaned with ultrapure water, acetone and anhydrous ethanol for 15 min each, and then dried in an oven at 60 ℃;

[0037] (2) Lead iodide (PbI2), formamidinium iodide (FAI), methylammonium iodide (MAI), methylammonium chloride (MACl) and cesium iodide (CsI) were dissolved in 1 mL of a mixed solvent composed of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (volume ratio 1:4), 1 mg of Abz molecular material was added at the same time, and stirred for 8 hours until uniform, obtaining a perovskite precursor solution of Cs 0.05 MA 0.1 FA 0.85 PbI3with Abz as an additive;

[0038] (3) 0.17 mg of 2PACz and 0.33 mg of Me-4PACz were dissolved in 3 mL of ethanol and stirred uniformly to obtain a hole selection layer solution;

[0039] (4) The FTO cleaned in step (1) was treated with ozone for 30 min, 100 μL of the hole selection layer solution was added, rotated at a speed of 3000 r / min for 30 s, and then annealed at a temperature of 100 ℃ for 10 min to obtain a solidified hole selection layer with a thickness of 3~5 nm;

[0040] (5) 100 μL of the perovskite precursor solution was added to the substrate obtained in step (4), rotated at a speed of 4000 r / min for 40 s, and 200 μL of anti-solvent (chlorobenzene) was added at 20 s, then annealed at a temperature of 100 ℃ for 45 min to obtain a perovskite layer with a thickness of about 600 nm;

[0041] (6) Fullerene C was prepared by vapor deposition. 60 An electron transport layer, 40 nm thick;

[0042] (7) A modified layer of 2,9-dimethyl-4,7-diphenyl-1,10-o-diazaphenanthroline (BCP) with a thickness of 15 nm was prepared by vapor deposition.

[0043] (8) A cathode electrode Ag with a thickness of 100 nm was prepared by vapor deposition, and its structure is as follows: Figure 2 As shown, from bottom to top, the layers are: FTO substrate, hole-selective layer, perovskite layer, and C. 60 Perovskite solar cell device with BCP layer and Ag electrode layer under AM1.5G simulated sunlight. J-V Curves Figure 3 As shown, its PCE is 26.38%. V OC It is 1.19 V. J SC 26.3 mA / cm 2 FF was 84.3%.

[0044] Example 2

[0045] A method for fabricating a pin-type perovskite solar cell based on light-dark reversible isomeric molecular stress release and photocycle stability includes the following steps:

[0046] (1) First, wash the front and back sides of the 2.5 cm*2.5 cm FTO transparent conductive substrate with glass detergent, then use ultrapure water, acetone and anhydrous ethanol to ultrasonically clean for 15 min each, and then dry it in an oven at 60°C.

[0047] (2) Lead iodide (PbI2), formamidine iodide (FAI), methylamine iodide (MAI), methylamine chloride (MACl), and cesium iodide (CsI) were dissolved in 1 mL of a mixed solvent consisting of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (volume ratio 1:4). At the same time, 1 mg of Ca-Abz molecular material was added, and the mixture was stirred for 8 hours until homogeneous to obtain CsI with a concentration of 1.5 mmol / mL. 0.05 MA 0.1 FA 0.85 PbI3 perovskite precursor solution with Ca-Abz as additive;

[0048] (3) Dissolve 0.17 mg 2PACz and 0.33 mg Me-4PACz in 3 mL of ethanol and stir until homogeneous to obtain a hole-selective layer solution;

[0049] (4) The FTO treated in step (1) was treated with ozone for 30 min, 100 μL of hole selection layer solution was added dropwise, and rotation was performed at a speed of 3000 r / min for 30 s, followed by annealing at a temperature of 100℃ for 10 min to obtain a solidified hole selection layer with a thickness of 3-5 nm;

[0050] (5) 100 μL of perovskite precursor solution was added dropwise on the substrate obtained in step (4), and rotation was performed at a speed of 4000 r / min for 40 s, 200 μL of anti-solvent (chlorobenzene) was added dropwise at 20 s, and then annealing was performed at a temperature of 100℃ for 45 min to obtain a perovskite layer with a thickness of about 600 nm;

[0051] (6) Fullerene C 60 an electron transport layer with a thickness of 40 nm;

[0052] (7) A modification layer 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was prepared by evaporation with a thickness of 15 nm;

[0053] (8) A cathode electrode Ag was prepared by evaporation with a thickness of 100 nm, and the perovskite solar cell device J-V The curve is as shown in Figure 4 , and the PCE is 27.10%, V OC 1.20 V, J SC 26.5 mA / cm 2 , and the FF is 85.2%.

[0054] Example 3

[0055] A preparation method of a p-i-n type perovskite solar cell based on stress release light cycle stability of light-dark reversible isomerization molecules, comprising the following steps:

[0056] (1) A 2.5 cm*2.5 cm FTO transparent conductive substrate was first scrubbed on both sides with glass detergent, then ultrasonically cleaned with ultrapure water, acetone and anhydrous ethanol for 15 min each, and then dried in an oven at 60℃;

[0057] (2) Lead iodide (PbI2), formamidine iodide (FAI), methylamine iodide (MAI), methylamine chloride (MACl), and cesium iodide (CsI) were dissolved in 1 mL of a mixed solvent consisting of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (volume ratio 1:4). At the same time, 1 mg of Dca-Abz molecular material was added, and the mixture was stirred for 8 hours until homogeneous to obtain CsI with a concentration of 1.5 mmol / mL. 0.05 MA 0.1 FA 0.85 PbI3 perovskite precursor solution with Dca-Abz as additive.

[0058] (3) Dissolve 0.17 mg 2PACz and 0.33 mg Me-4PACz in 3 mL of ethanol and stir until homogeneous to obtain a hole-selective layer solution;

[0059] (4) Treat the FTO that has been cleaned in step (1) with ozone for 30 min, add 100 μL of hole selective layer solution, rotate at 3000 r / min for 30 s, and then anneal at 100℃ for 10 min to obtain a solidified hole selective layer with a thickness of 3~5 nm.

[0060] (5) 100 μL of perovskite precursor solution was dropped onto the substrate obtained in step (4), and the mixture was rotated at 4000 r / min for 40 s. At 20 s, 200 μL of antisolvent (chlorobenzene) was dropped on for treatment. Then, the mixture was annealed at 100℃ for 45 min to obtain a perovskite layer with a thickness of about 600 nm.

[0061] (6) Fullerene C was prepared by vapor deposition. 60 An electron transport layer, 40 nm thick;

[0062] (7) A modified layer of 2,9-dimethyl-4,7-diphenyl-1,10-o-diazaphenanthroline (BCP) with a thickness of 15 nm was prepared by vapor deposition.

[0063] (8) A cathode electrode of Ag with a thickness of 100 nm was prepared by vapor deposition. Under AM1.5G simulated sunlight, the perovskite solar cell device... J-V Curves Figure 5 As shown, its PCE is 26.80%. V OC It is 1.20 V. J SC 26.4 mA / cm 2 FF is 84.6%.

[0064] Example 4

[0065] A preparation method of a p-i-n type perovskite solar cell based on stress release light cycle stability of light-dark reversible isomeric molecules, comprising the following steps:

[0066] (1) A 2.5 cm*2.5 cm FTO transparent conductive substrate is first rubbed on both sides with glass detergent, then ultrasonic cleaning is performed with ultrapure water, acetone and anhydrous ethanol for 15 min each, and then drying is performed in an oven at 60°C;

[0067] (2) Lead iodide (PbI2), formamidinium iodide (FAI), methylammonium iodide (MAI), methylammonium chloride (MACl) and cesium iodide (CsI) are dissolved in 1 mL of a mixed solvent composed of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (volume ratio 1:4), 1 mg of SA-Abz molecular material is added at the same time, stirring is performed for 8 hours until uniform, and a perovskite precursor solution with a concentration of 1.5 mmol / mL is obtained, wherein SA-Abz is used as an additive; 0.05 MA 0.1 FA 0.85 PbI3 and SA-Abz is used as an additive;

[0068] (3) 0.17 mg of 2PACz and 0.33 mg of Me-4PACz are dissolved in 3 mL of ethanol to obtain a hole selection layer solution;

[0069] (4) The FTO treated in step (1) is subjected to ozone treatment for 30 min, 100 μL of the hole selection layer solution is added dropwise, rotation is performed at a speed of 3000 r / min for 30 s, and then annealing is performed at a temperature of 100°C for 10 min to obtain a solidified hole selection layer with a thickness of 3-5 nm;

[0070] (5) 100 μL of the perovskite precursor solution is added dropwise on the substrate obtained in step (4), rotation is performed at a speed of 4000 r / min for 40 s, 200 μL of anti-solvent (chlorobenzene) is added dropwise at 20 s, and then annealing is performed at a temperature of 100°C for 45 min to obtain a perovskite layer with a thickness of about 600 nm;

[0071] (6) Fullerene C 60 An electron transport layer with a thickness of 40 nm is prepared by evaporation;

[0072] (7) A modification layer of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) is prepared by evaporation, and the thickness is 15 nm;

[0073] (8) The cathode electrode Ag is prepared by evaporation method, and the thickness is 100 nm. Under AM1.5G simulated sunlight, the perovskite solar cell device J-V The curve is as shown in Figure 6 The PCE is 27.13%, V OC 1.20 V, J SC 26.50 mA / cm 2 , and the FF is 85.3%.

[0074] Comparative Example 1

[0075] The preparation method of the traditional anti-perovskite solar cell comprises the following steps:

[0076] (1) The 2.5 cm*2.5 cm FTO transparent conductive substrate is first rubbed on both sides with glass detergent, and then ultrasonically cleaned with ultrapure water, acetone and anhydrous ethanol for 15 min, and then dried in an oven at 60°C;

[0077] (2) Lead iodide (PbI2), formamidinium iodide (FAI), methylammonium iodide (MAI), methylammonium chloride (MACl) and cesium iodide (CsI) are dissolved in 1 mL of mixed solvent (volume ratio 1:4) composed of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF), stirred for 8 hours to be uniform, and a Cs 0.05 MA 0.1 FA 0.85 PbI3perovskite precursor solution with Abz as an additive is obtained;

[0078] (3) 0.17 mg 2PACz and 0.33 mg Me-4PACz are dissolved in 3 mL of ethanol to obtain a hole selection layer solution;

[0079] (4) The FTO treated in step (1) is ozone treated for 30 min, 100 μL of the hole selection layer solution is added, rotated at a speed of 3000 r / min for 30 s, and then annealed at a temperature of 100°C for 10 min to obtain a solidified hole selection layer with a thickness of 3~5 nm;

[0080] (5) 100 μL of the perovskite precursor solution is added to the substrate obtained in step (4), rotated at a speed of 4000 r / min for 40 s, and 200 μL of anti-solvent (chlorobenzene) is added at 20 s, and then annealed at a temperature of 100°C for 45 min to obtain a perovskite layer with a thickness of about 600 nm;

[0081] (6) Fullerene C60 was prepared by evaporation method 60 an electron transport layer with a thickness of 40 nm;

[0082] (7) A modification layer 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was prepared by evaporation method, with a thickness of 15 nm;

[0083] (8) A cathode electrode Ag was prepared by evaporation method, with a thickness of 100 nm. Under AM1.5G simulated sunlight, the perovskite solar cell device J-V The curve is shown in Figure 7 , with a PCE of 24.95%, V OC 1.16 V, J SC 26.2 mA / cm 2 , and an FF of 82.1%.

[0084] Table 1

[0085]

[0086] As can be seen from Comparative Examples 1-4 and Comparative Example 1, the energy conversion efficiency of the perovskite solar cell device using the light-dark reversible isomerization material as an additive is significantly improved compared with the traditional original device, with a maximum of 27.13%. At the same time, the perovskite device improved by the light-dark reversible isomerization material also shows excellent light cycle stability, as shown in Table 1, Figures 3 to 8 , the best device based on SA-Cbz exhibits the best device efficiency and light cycle stability (12 hours of light and 12 hours of darkness), with a stability of 98% of the initial value, while Comparative Example 1 (the marker) only maintains 56% of the initial value, and the devices based on Abz, Ca-Abz and Dca-Abz maintain 83%, 92% and 96% of the initial value, respectively.

Claims

1. A method for preparing a p-i-n type perovskite solar cell based on stress release photo-cycle stable photodark reversible isomeric molecules, characterized in that, The method comprises the following steps: (1) spin-coating a mixed ethanol solution of 2PACz and Me-4PACz on a washed, dried and ozone-treated substrate to obtain a hole selection layer; (2) doping a photo-dark reversible isomer into a raw perovskite precursor solution to obtain an optimized perovskite precursor solution; the photo-dark reversible isomer is at least one of azobenzene-4-benzoic acid (Ca-Abz) and 4-(phenylazo) benzenesulfonic acid (SA-Abz); the concentration of the photo-dark reversible isomer in the perovskite precursor solution is 1-2 mg / mL; (3) depositing the optimized perovskite precursor solution and annealing to obtain a perovskite layer; (4) preparing PC on the perovskite layer 61 BM or C 60 layer, obtaining a uniform electron transport layer; (5) preparing a BCP or SnO2 modification layer on the electron transport layer; (6) preparing a cathode metal electrode on the BCP or SnO2 modification layer.

2. The production method according to claim 1, characterized by, The substrate in the step (1) is an ITO or FTO conductive substrate; the total concentration of 2PACz and Me-4PACz in the mixed ethanol solution of 2PACz and Me-2PACz is 0.1-0.5 mg / mL, the mass ratio of 2PACz to Me-4PACz is 1: (1-3), the annealing temperature of the hole selection layer is 100-120℃, and the annealing time is 5-10 min.

3. The preparation method according to claim 1, characterized in that, The original perovskite precursor solution is specifically Cs 0.05 MA 0.1 FA 0.85 The PbI3 perovskite precursor solution has a concentration of 1.5-2 mol / L, and the solvent is a mixed solvent of DMSO and DMF in a volume ratio of 1:

4.

4. The method of claim 1, wherein, In the step (3), the annealing temperature is 100-120℃, and the annealing time is 20-45 min.

5. The preparation method according to claim 1, characterized in that, The thickness of the perovskite film in the step (3) is 500-700 nm.

6. The preparation method according to claim 1, characterized in that, The PC in the step (4) 61 BM or C 60 The thickness of the electron transport layer is 30-40 nm.

7. The preparation method according to claim 1, characterized in that, The thickness of the BCP or SnO2 modification layer in the step (5) is 10-25 nm.

8. The method of claim 1, wherein, The cathode electrode in the step (6) is Au, Ag or Cu, and the electrode thickness is 70-110 nm.

9. The p-i-n type perovskite solar cell with stress release and light cycle stability of photo-dark reversible isomer prepared by the method of any one of claims 1-8.

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