Perovskite indoor photovoltaic cell and preparation method thereof

Abstract

The invention relates to the technical field of photovoltaic cells, in particular to a perovskite indoor photovoltaic cell and a preparation method thereof. Comprising the following steps: providing a substrate which comprises a first electrode; preparing a hole transport layer on the surface of the first electrode; coating the surface of the hole transport layer with a halide ammonium salt solution containing a benzene ring, and carrying out first annealing treatment to obtain a first optimization layer; preparing a perovskite layer on the surface of the first optimization layer; coating the surface of the perovskite layer with a binary halide ammonium salt solution, and carrying out second annealing treatment to obtain a second optimization layer; preparing an electron transport layer on the surface of the second optimization layer; and preparing a second electrode on the surface of the electron transport layer. By adopting the preparation method provided by the invention, the energy level matching between the perovskite layer and the hole transport layer and the electron transport layer can be improved, and the defect state density of the upper and lower interfaces of the perovskite layer can be effectively reduced, so that the photoelectric conversion efficiency of the perovskite indoor photovoltaic cell can be effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photovoltaic cells, and in particular to a perovskite indoor photovoltaic cell and a preparation method thereof. Background Art

[0002] With the rapid development of 5G Internet of Things technology, the demand for indoor photovoltaic power generation and energy replenishment devices that can match it has also increased sharply. At present, the photoelectric performance of amorphous silicon photovoltaic devices, dye-sensitized battery devices, and III-V photovoltaic devices under indoor light sources has been deeply studied. Their theoretical and experimental processes have been basically mature, and their photoelectric conversion efficiency has also reached a bottleneck. At the same time, many studies have shown that photovoltaic devices with excellent photoelectric performance under AM1.5 simulated sunlight do not necessarily have excellent photoelectric performance under indoor light sources such as fluorescent energy-saving lamps and LED lamps. This is mainly because indoor light sources have a small spectral range (wavelengths concentrated in 400-700nm), low incident light energy density (under 1000lux illumination, Pin is often less than 300μW / cm 2 Therefore, designing and preparing photovoltaic cells that are compatible with the spectrum of indoor light sources is an important path to expand the application of photovoltaic devices.

[0003] In the field of indoor photovoltaics, research has shown that wide-bandgap perovskite cells are well-suited to indoor light sources. However, wide-bandgap perovskite cells suffer from disadvantages such as high voltage loss, high defect density, and poor phase stability. Studies have shown that the density of defect states at the interfaces between the upper and lower perovskite layers in cell devices is much greater than that in the bulk phase, making defect-induced carrier recombination at these interfaces more severe. Furthermore, under illumination, interfacial defects are a key factor in the formation of vacancies and the induction of phase separation between iodine and bromide ions.

[0004] Therefore, the existing technology still needs to be improved and developed. Summary of the Invention

[0005] In view of the above-mentioned deficiencies in the prior art, the present invention provides a perovskite indoor photovoltaic cell and a preparation method thereof, so as to solve the problem of high defect state density at the upper and lower interfaces of the perovskite layer in the existing perovskite indoor photovoltaic cell.

[0006] The technical solutions adopted by the present invention to solve the above technical problems are as follows:

[0007] A first aspect of the present invention provides a method for preparing a perovskite indoor photovoltaic cell, the method comprising the following steps:

[0008] providing a substrate, the substrate comprising a first electrode;

[0009] preparing a hole transport layer on the surface of the first electrode;

[0010] Coating a halide ammonium salt solution containing a benzene ring on the surface of the hole transport layer and performing a first annealing treatment to obtain a first optimized layer;

[0011] preparing a perovskite layer on the surface of the first optimized layer;

[0012] coating a binary halide ammonium salt solution on the surface of the perovskite layer and performing a second annealing treatment to obtain a second optimized layer;

[0013] preparing an electron transport layer on the surface of the second optimized layer;

[0014] A second electrode is prepared on the surface of the electron transport layer.

[0015] Preferably, the ammonium halide salt solution containing a benzene ring is composed of an ammonium halide salt containing a benzene ring and a first solvent, the ammonium halide salt containing a benzene ring is selected from one or more of p-fluorophenethylamine iodine, p-fluorophenethylamine bromide, m-fluorophenethylamine iodine, m-fluorophenethylamine bromide, m-fluorophenethylamine chloride, p-trifluoromethylphenethylamine iodine, p-trifluoromethylphenethylamine bromide, p-trifluoromethylphenethylamine chloride, p-chlorophenethylamine iodine, p-chlorophenethylamine bromide, and p-chlorophenethylamine chloride, and the first solvent is ethanol or isopropanol.

[0016] Preferably, the concentration of the ammonium halide salt solution containing a benzene ring is 1-5 mg / mL.

[0017] Preferably, in the step of coating the surface of the hole transport layer with a halide ammonium salt solution containing a benzene ring, the coating is performed by spin coating at a rotation speed of 3000-5000 rpm for 30 seconds.

[0018] Preferably, the temperature of the first annealing treatment is 80-120° C., and the time is 10 minutes.

[0019] Preferably, the dibasic halide ammonium salt solution is composed of a dibasic halide ammonium salt and a second solvent, the dibasic halide ammonium salt is selected from one of ethylenediamine dihydrobromide, ethylenediamine dihydroiodide, 1,3-diaminopropane dihydrobromide, 1,3-diaminopropane dihydroiodide, 1,4-diaminobutane dihydroiodide, 1,6-diaminohexane dihydroiodide, and 1,8-diaminooctane dihydroiodide, and the second solvent is a mixed solvent of isopropanol and toluene.

[0020] Preferably, the concentration of the dibasic halide ammonium salt solution is 0.5-1 mg / mL.

[0021] Preferably, in the step of coating the dibasic halide ammonium salt solution on the surface of the perovskite layer, the coating method is spin coating, the spin coating speed is 2000-8000 rpm, and the time is 30 seconds.

[0022] Preferably, the second annealing treatment is performed at a temperature of 80-120° C. and for 10 minutes.

[0023] A second aspect of the present invention provides a perovskite indoor photovoltaic cell, which is prepared using the above-mentioned preparation method.

[0024] Beneficial effects:

[0025] This invention discloses a perovskite indoor photovoltaic cell and its preparation method. The preparation method improves the energy level matching between the perovskite layer and the hole and electron transport layers, effectively reducing the defect state density at the upper and lower interfaces of the perovskite layer, thereby effectively improving the photoelectric conversion efficiency of the perovskite indoor photovoltaic cell. Ultimately, the perovskite indoor photovoltaic cell provided by the invention can achieve a photoelectric conversion efficiency of up to 42.1% under white LED light at 4000K and 1000 lux illumination.

[0026] The preparation method provided by the present invention is simple to operate and highly controllable. It can match the preparation process of large-area perovskite battery modules, can effectively promote the development of perovskite indoor photovoltaics, and has the hope of successfully applying perovskite batteries in the field of Internet of Things, and has huge application potential. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a flow chart of a method for preparing a perovskite indoor photovoltaic cell in a preferred embodiment of the present invention;

[0028] Figure 2 Schematic diagram of the structure of the perovskite indoor photovoltaic cell in a preferred embodiment of the present invention, from bottom to top: first electrode, hole transport layer, first optimized layer, perovskite layer, second optimized layer, electron transport layer, second electrode;

[0029] Figure 3 Schematic diagram of the microscopic lattice interface of the perovskite device before and after treatment;

[0030] Figure 4 The current density-voltage test curves of the perovskite indoor photovoltaic cells prepared in Example 3 of the present invention and Comparative Example 1;

[0031] Figure 5 This is an efficiency stability test curve of the perovskite indoor photovoltaic cells prepared in Example 3 of the present invention and Comparative Example 1 under 500 lux continuous indoor light illumination;

[0032] Figure 6 The current density-voltage test curves of the perovskite indoor photovoltaic cells prepared in Example 1 and Comparative Example 1 of the present invention;

[0033] Figure 7The current density-voltage test curves of the perovskite indoor photovoltaic cells prepared in Example 2 of the present invention and Comparative Example 1 are shown;

[0034] Figure 8 The current density-voltage test curves of the perovskite indoor photovoltaic cells prepared in Example 4 of the present invention and Comparative Example 1 are shown;

[0035] Figure 9 These are the current density-voltage test curves of the perovskite indoor photovoltaic cells prepared in Example 5 of the present invention and Comparative Example 1. DETAILED DESCRIPTION

[0036] The present invention provides a perovskite indoor photovoltaic cell and a method for preparing the same. To clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.

[0037] The embodiment of the present invention provides a method for preparing a perovskite indoor photovoltaic cell, the structure of which is shown in FIG. Figure 2 As shown, the preparation method comprises the following steps:

[0038] providing a substrate, the substrate comprising a first electrode;

[0039] preparing a hole transport layer on the surface of the first electrode;

[0040] Coating a halide ammonium salt solution containing a benzene ring on the surface of the hole transport layer and performing a first annealing treatment to obtain a first optimized layer;

[0041] preparing a perovskite layer on the surface of the first optimized layer;

[0042] coating a binary halide ammonium salt solution on the surface of the perovskite layer and performing a second annealing treatment to obtain a second optimized layer;

[0043] preparing an electron transport layer on the surface of the second optimized layer;

[0044] A second electrode is prepared on the surface of the electron transport layer.

[0045] The present invention provides a method for preparing a perovskite indoor photovoltaic cell. The method improves the performance of the perovskite indoor photovoltaic cell by simultaneously passivating the upper and lower interfaces of the perovskite layer: (1) coating a halide ammonium salt solution containing a benzene ring on the surface of the hole transport layer to treat the interface between the hole transport layer and the perovskite layer; and (2) coating a binary halide ammonium salt solution on the perovskite layer to regulate the interface between the perovskite layer and the electron transport layer. Based on the above two treatments, the defects of the upper and lower interfaces of the perovskite layer can be effectively passivated and the open circuit voltage of the perovskite indoor photovoltaic cell can be significantly improved. In addition, the iodine-bromine phase separation problem in the perovskite layer can be effectively suppressed, significantly improving the light stability of the perovskite indoor photovoltaic cell under continuous irradiation of indoor light sources.

[0046] Specifically, by pre-embedding a benzene ring-containing ammonium halide salt into the lower interface of the perovskite layer and selecting a binary ammonium halide salt to modify the upper interface of the perovskite layer, the defects of the upper and lower interfaces of the perovskite layer are passivated, and the phase separation problem of iodine and bromide ions in the perovskite layer is effectively suppressed. Among them, the fluorine ions or chloride ions connected to the benzene ring structure of the benzene ring-containing ammonium halide salt can form hydrogen bonds with the hole transport layer material, and the benzene ring structure on the benzene ring-containing ammonium halide salt can form a conjugated bond stacking effect with the hole transport layer material, firmly anchoring it to the lower interface of the perovskite layer. The ammonium halide group can passivate the halogen vacancy defects and cation vacancy defects at the lower interface of the perovskite layer. The binary ammonium halide salt can be spread on the surface of the perovskite layer, and simultaneously passivate the halogen vacancy and dislocation defects at the upper interface of the perovskite layer and the lower interface of the electron transport layer. On the one hand, the binary ammonium halide salt can reduce the number of defects at the upper interface of the perovskite, and on the other hand, it can optimize the interface energy level structure and promote carrier transport. The dual-interface processing strategy provided by the embodiment of the present invention improves the photoelectric conversion efficiency and long-term light stability of perovskite indoor photovoltaic cells. Figure 3 This is a schematic diagram of the perovskite battery before and after treatment. It can be seen from the figure that there are many defects on the upper and lower interfaces before treatment, and the defects on the upper and lower interfaces are fully passivated after treatment.

[0047] In some embodiments, the ammonium halide salt solution containing a benzene ring is composed of an ammonium halide salt containing a benzene ring and a first solvent, wherein the ammonium halide salt containing a benzene ring is selected from one or more of p-fluorophenethylamine iodine, p-fluorophenethylamine bromide, m-fluorophenethylamine iodine, m-fluorophenethylamine bromide, m-fluorophenethylamine chloride, p-trifluoromethylphenethylamine iodine, p-trifluoromethylphenethylamine bromide, p-trifluoromethylphenethylamine chloride, p-chlorophenethylamine iodine, p-chlorophenethylamine bromide, and p-chlorophenethylamine chloride, and the first solvent is ethanol or isopropanol.

[0048] In some embodiments, the hole transport layer material is a single-molecule self-assembly material such as nickel oxide, 2PACz, MeO-2PACz, Me-4PACz, or a composite of nickel oxide and single-molecule self-assembly material.

[0049] In some embodiments, the concentration of the ammonium halide solution containing a benzene ring is 1-5 mg / mL. The concentration of the ammonium halide solution containing a benzene ring can be 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, or 5 mg / mL.

[0050] The concentration of the ammonium halide solution containing a benzene ring determines the thickness of the first optimized layer that remains on the surface of the hole transport layer after spin coating. At the same spin speed, higher concentrations result in thicker first optimized layers. Too low a concentration results in a thin first optimized layer, which fails to completely passivate surface defects. Too high a concentration results in an excessively thick first optimized layer, limiting carrier transport in the first optimized layer and thus affecting the performance of perovskite indoor photovoltaic cells.

[0051] In some preferred embodiments, the concentration of the ammonium halide salt solution containing a benzene ring is 4 mg / mL.

[0052] In some embodiments, in the step of coating the surface of the hole transport layer with a halide ammonium salt solution containing a benzene ring, the coating method is spin coating, the spin coating speed is 3000-5000 rpm, and the time is 30 seconds. The spin coating speed can be 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, or 5000 rpm.

[0053] The spin coating speed determines the thickness of the first optimized layer. If the spin coating speed is too high, the first optimized layer thickness will be too low, resulting in incomplete passivation of defects at the interface. If the spin coating speed is too low, the first optimized layer thickness on the surface of the hole transport layer will be too high, affecting the carrier transport between the perovskite layer and the hole transport layer, thereby affecting the performance of the perovskite indoor photovoltaic cell.

[0054] In some preferred embodiments, in the step of coating the surface of the hole transport layer with a halide ammonium salt solution containing a benzene ring, the coating is performed by spin coating at a speed of 5000 rpm for 30 seconds.

[0055] In some embodiments, the first annealing treatment may be performed at a temperature of 80-120° C. for 5-30 minutes. The first annealing treatment may be performed at a temperature of 80° C., 85° C., 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., or 120° C. for 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes.

[0056] The purpose of heating and annealing the first optimized layer is to remove residual solvent from the surface of the optimized layer after spin coating, assist in the bonding of the first optimized layer material with the hole transport layer, and thus construct a stable bottom interface first optimized layer. If the temperature is too low, the solvent cannot be completely dried out, affecting the preparation of the next perovskite layer; if the temperature is too high, the hole transport layer material will be destroyed, affecting the extraction and diffusion of holes in the perovskite indoor photovoltaic cell, resulting in a decrease in the performance of the perovskite indoor photovoltaic cell.

[0057] In some preferred embodiments, the temperature of the first annealing treatment is 100° C. and the duration is 10 minutes.

[0058] In some embodiments, the dibasic ammonium halide salt solution is composed of a dibasic ammonium halide salt and a second solvent, wherein the dibasic ammonium halide salt is selected from one of ethylenediamine dihydrobromide, ethylenediamine dihydroiodide, 1,3-diaminopropane dihydrobromide, 1,3-diaminopropane dihydroiodide, 1,4-diaminobutane dihydroiodide, 1,6-diaminohexane dihydroiodide, and 1,8-diaminooctane dihydroiodide, and the second solvent is a mixed solvent of isopropanol and toluene.

[0059] In some embodiments, the concentration of the dibasic ammonium halide salt solution is 0.5-1 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 0.9 mg / mL, or 1 mg / mL.

[0060] The concentration of the divalent ammonium halide salt determines the thickness of the second optimized layer (OIL) that remains on the perovskite surface after spin coating. At the same spin speed, higher concentrations result in thicker OILs. Too low a concentration results in a thin OIL that fails to completely passivate surface defects. Too high a concentration results in an excessively thick OIL, limiting carrier transport in the OIL and thus compromising the performance of perovskite indoor photovoltaic cells.

[0061] In some preferred embodiments, the concentration of the dibasic halide ammonium salt solution is 0.5 mg / mL.

[0062] In some embodiments, in the step of coating the dibasic halide ammonium salt solution on the surface of the perovskite layer, the coating method is spin coating, the spin coating speed is 2000-8000 rpm, and the time is 30 seconds. The spin coating speed can be 2000 rpm, 3000 rpm, 4000 rpm, 5000 rpm, 6000 rpm, 7000 rpm, or 8000 rpm, and the time can be 30 seconds.

[0063] The spin coating speed determines the thickness of the second optimized layer. If the spin coating speed is too high, the thickness of the second optimized layer will be too low, resulting in incomplete passivation of defects on the surface of the perovskite layer. If the spin coating speed is too low, the thickness of the second optimized layer will be too high, affecting the carrier transport between the perovskite layer and the electron transport layer, thereby affecting the performance of the perovskite indoor photovoltaic cell.

[0064] In some preferred embodiments, in the step of coating the divalent halide ammonium salt solution on the surface of the perovskite layer, the coating method is spin coating, the spin coating speed is 5000 rpm, and the time is 30 seconds.

[0065] In some embodiments, the second annealing treatment may be performed at a temperature of 80-120° C. for 10 minutes, or at a temperature of 80° C., 85° C., 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., or 120° C. for 10 minutes.

[0066] The second optimized layer is subjected to a heating annealing treatment primarily to remove residual solvent from the surface of the perovskite layer after spin coating, assisting the binding of the binary halide ammonium salt passivation material to the surface defects of the perovskite, thereby effectively passivating the surface defects of the perovskite layer. Too low a temperature prevents the solvent from being completely dried out on the surface of the perovskite layer, resulting in an incomplete passivation reaction and failure to achieve the optimal effect of the passivation material. Too high a temperature decomposes the methylamine and formamidinium cations in the perovskite layer, leading to degradation and destruction of the perovskite layer.

[0067] In some preferred embodiments, the second annealing treatment is performed at a temperature of 100° C. and for a time of 10 minutes.

[0068] In some embodiments, the method for preparing the perovskite indoor photovoltaic cell comprises the following steps:

[0069] Step 1: Clean the conductive glass ITO substrate, which includes a first electrode, and then ultraviolet treat it for 15 minutes. Then, spin-coat a 10 mg / mL hole transport layer solution (nickel oxide, 2PACz, MeO-2PACz, Me-4PACz, or a nickel oxide / single-molecule self-assembly material composite) on the first electrode at a spin coating speed of 4000 rpm for 30 seconds. The substrate is then moved to a heating table for annealing at 150°C for 10 minutes to obtain a hole transport layer.

[0070] Step 2: Weigh 1-5 mg of ammonium halide salt containing a benzene ring, add 1 mL of isopropanol or ethanol to obtain a 4 mg / mL ammonium halide salt solution containing a benzene ring, and spin-coat the obtained ammonium halide salt solution containing a benzene ring on the surface of the hole transport layer at a spin coating speed of 5000 rpm for 30 seconds. Move the layer to a heating table for annealing at a temperature of 100°C for 10 minutes to complete the preparation of the first optimized layer.

[0071] Step 3: 0.026 g of methylammonium bromide (MABr), 0.204 g of formamidinium iodine (FAI), 0.020 g of cesium iodide (CsI), 0.332 g of lead iodide (PbI2), and 0.286 g of lead bromide (PbBr2) were dissolved in 1 ml of a mixed solvent (N, N-dimethylformamide: dimethyl sulfoxide, a volume ratio of 3:1), and heated and stirred to obtain a 1.5 mol / L perovskite precursor solution, which was filtered using a 0.22 μm PTFE filter head. The perovskite precursor solution was spin-coated on the surface of the first optimized layer at a spin coating speed of 4000 rpm for 40 seconds, and 300 μL of chlorobenzene was added as an anti-solvent at the 10th second. The mixture was then moved to a heating stage for annealing at a temperature of 100°C for 10 minutes to obtain a perovskite layer.

[0072] Step 4: Weigh 0.5-1 mg of dibasic ammonium halide salt, add 1 mL of mixed solvent (isopropanol and toluene, volume ratio of 4:3) to obtain 0.5 mg / mL dibasic ammonium halide salt solution, spin-coat the obtained dibasic ammonium halide salt solution on the surface of the perovskite layer at a spin coating speed of 5000 rpm for 30 seconds, and move to a heating table to complete annealing treatment at an annealing temperature of 100°C for 10 minutes to obtain a second optimized layer;

[0073] Step 5: Using vacuum thermal evaporation process, C 60 and BCP (spin coating process can also be used to spin coat PCBM and BCP on the surface of the perovskite layer in sequence, the concentrations of PCBM and BCP solutions are 20 mg / mL and 0.5 mg / mL respectively; the spin coating conditions are 3000 rpm, 30 seconds and 5000 rpm, 30 seconds respectively. The annealing conditions are both 100 ° C, 10 minutes.) to obtain an electron transport layer, wherein C 60 , and the thickness of BCP are 20 nm and 5 nm, respectively;

[0074] Step 6: Using vacuum thermal evaporation technology, evaporate Au, Ag or Cu second electrode on the surface of the electron transport layer. The thickness of the second electrode is 120nm.

[0075] An embodiment of the present invention provides a perovskite indoor photovoltaic cell, which is prepared using the above-mentioned preparation method.

[0076] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them, and are intended only to illustrate the present invention and in no way limit the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are also within the scope of protection of the present invention.

[0077] Example 1

[0078] A preparation method of a perovskite indoor photovoltaic cell comprises the following steps:

[0079] Perovskite MA 0.16 FA 0.79 Cs 0.05 Pb(Br 0.4 I 0.6 )3 Preparation of precursor solution: MAI (methylamine iodide), FAI (formamidine iodide), CsI (cesium iodide), PbI2 (lead iodide) and PbBr2 (lead bromide) were dissolved in a mixed solvent of DMF (N,N-dimethylformamide) and DMSO (dimethyl sulfoxide) (volume ratio of 0.8:0.2) at a molar ratio of 0.16:0.79:0.05:0.48:0.52 to prepare a perovskite precursor solution with a molar concentration of 1.5 mol / L. The above perovskite precursor solution was placed in a glove box and stirred for 6 hours and filtered using a 0.22 μm PTFE filter head.

[0080] An ITO glass substrate was ultrasonically cleaned in deionized water, acetone, and isopropyl alcohol for 15 minutes each, then dried in a 70°C oven for 6 hours. The cleaned ITO glass substrate was then treated with UV-ozone for 15 minutes to remove any remaining organic matter and improve the wettability of the ITO glass substrate. A 10 mg / mL aqueous nickel oxide dispersion was applied to the ITO surface at a spin coating speed of 4000 rpm for 30 seconds. The resulting film was placed on a 150°C hotplate and annealed for 30 minutes to form a hole transport layer.

[0081] Dissolve p-fluorophenethylamine iodine in IPA (isopropyl alcohol) to obtain a 4 mg / mL solution of a benzene ring-containing ammonium halide salt. This solution was spin-coated onto the hole transport layer at 5000 rpm for 30 seconds. The layer was then annealed on a heating plate at 100°C for 10 minutes to obtain the first optimized layer.

[0082] The perovskite precursor solution was spin-coated on the surface of the first optimized layer (spin-coating parameters were: 4000 rpm, 40 seconds, and the anti-solvent chlorobenzene was added at the 10th second). After that, the film was placed on a heating table at 100°C and annealed for 10 minutes to form a perovskite layer.

[0083] 1,3-Diaminopropane dihydroiodide was dissolved in a 4:3 mixture of IPA (isopropyl alcohol) and CB (chlorobenzene) to produce diamine halide solutions with concentrations ranging from 0.5 to 1 mg / mL. These solutions were spin-coated onto the perovskite layer at 5000 rpm and annealed on a hotplate at 100°C for 10 minutes to form a second optimized layer.

[0084] The prepared second optimized layer is placed in a vacuum plating chamber with an air pressure of less than 9×10 -5 Pa was then thermally evaporated to deposit 20 nm C 60 , 5nm BCP and 120nm Cu.

[0085] Example 2

[0086] A preparation method of a perovskite indoor photovoltaic cell is basically the same as that of Example 1, except that:

[0087] Using 2PACz as the hole transport layer material, a 0.5 mg / mL 2PACz isopropanol solution was applied to an ITO glass substrate at a spin coating speed of 4000 rpm. The film was then placed on a heating plate at 100°C and annealed for 30 minutes to form a hole transport layer.

[0088] The first optimized layer material was m-fluorophenethylamine iodine, dissolved in IPA (isopropyl alcohol) at a concentration of 4 mg / mL. The ammonium halide solution containing a benzene ring was spin-coated onto the hole transport layer at 5000 rpm and annealed on a 100°C heating plate for 10 minutes.

[0089] The second optimized layer material was ethylenediamine dihydroiodide, dissolved in a mixture of IPA (isopropyl alcohol) and CB (chlorobenzene) (4:3 by volume) at a concentration of 1 mg / mL. Solutions of dibasic ammonium halide salts of varying carbon chain lengths were spin-coated onto the perovskite layer at 5000 rpm and annealed on a 100°C hotplate for 10 minutes.

[0090] Example 3

[0091] A preparation method of a perovskite indoor photovoltaic cell is basically the same as that of Example 1, except that:

[0092] Using MeO-2PACz as the hole transport layer material, a 0.6 mg / mL MeO-2PACz isopropanol solution was applied to an ITO glass substrate at a spin coating speed of 4000 rpm. The film was then placed on a heating plate at 100°C and annealed for 30 minutes to form the hole transport layer.

[0093] For the first optimized layer, p-fluorophenethylamine bromide and p-chlorophenethylamine bromide were dissolved in IPA (isopropyl alcohol) at a mass ratio of 1:2 to a concentration of 4 mg / mL. The ammonium halide solution containing a benzene ring was spin-coated onto the hole transport layer at 5000 rpm and annealed on a heating plate at 100°C for 10 minutes.

[0094] The second optimized layer consisted of 1,3-diaminopropane dihydrobromide and 1,4-diaminobutane dihydroiodide, dissolved in a 1:1 mass ratio in a 4:3 volume ratio of IPA (isopropyl alcohol) and CB (chlorobenzene) to a concentration of 1 mg / mL. Solutions of dibasic ammonium halide salts of varying carbon chain lengths were spin-coated onto the perovskite surface at 5000 rpm and annealed on a 100°C heating plate for 10 minutes.

[0095] Example 4

[0096] A preparation method of a perovskite indoor photovoltaic cell is basically the same as that of Example 1, except that:

[0097] Using MeO-2PACz as the hole transport layer material, a 0.6 mg / mL MeO-2PACz isopropanol solution was applied to an ITO glass substrate at a spin coating speed of 4000 rpm. The film was then placed on a heating plate at 100°C and annealed for 30 minutes to form the hole transport layer.

[0098] The first optimized layer material was p-trifluoromethylphenylethylamine iodide, dissolved in IPA (isopropyl alcohol) at a concentration of 4 mg / mL. The ammonium halide solution containing a benzene ring was spin-coated onto the hole transport layer at 5000 rpm and annealed on a 100°C heating plate for 10 minutes.

[0099] The second optimized layer material was 1,8-diaminooctane dihydroiodide, dissolved in a mixture of IPA (isopropyl alcohol) and CB (chlorobenzene) (4:3 by volume) at a concentration of 1 mg / mL. Solutions of dibasic ammonium halide salts of varying carbon chain lengths were spin-coated onto the perovskite surface at 5000 rpm and annealed on a 100°C heating plate for 10 minutes.

[0100] Example 5

[0101] A preparation method of a perovskite indoor photovoltaic cell is basically the same as that of Example 1, except that:

[0102] Using MeO-2PACz as the hole transport layer material, a 0.6 mg / mL MeO-2PACz isopropanol solution was applied to an ITO glass substrate at a spin coating speed of 4000 rpm. The film was then placed on a heating plate at 100°C and annealed for 30 minutes to form the hole transport layer.

[0103] The first optimized layer material was p-trifluoromethylphenylethylamine bromide, dissolved in IPA (isopropyl alcohol) at a concentration of 4 mg / mL. The ammonium halide solution containing a benzene ring was spin-coated onto the hole transport layer at 5000 rpm and annealed on a heating plate at 100°C for 10 minutes.

[0104] The second optimized layer material was 1,8-diaminooctane dihydroiodide, dissolved in a mixture of IPA (isopropyl alcohol) and CB (chlorobenzene) (4:3 by volume) at a concentration of 1 mg / mL. Solutions of dibasic ammonium halide salts of varying carbon chain lengths were spin-coated onto the perovskite surface at 5000 rpm and annealed on a 100°C heating plate for 10 minutes.

[0105] Comparative Example 1

[0106] A preparation method of a perovskite indoor photovoltaic cell is basically the same as that of Example 1, except that:

[0107] MeO-2PACz was used as the hole transport layer (HTL) material. A 0.6 mg / mL MeO-2PACz isopropanol solution was applied to an ITO glass substrate at a spin coating speed of 4000 rpm. The film was then annealed on a heating plate at 100°C for 30 minutes to form the HTL.

[0108] Performance testing experiment

[0109] The current density-voltage test was performed on the perovskite indoor photovoltaic cells prepared in Example 3 and Comparative Example 1. The light source used in the test was a 4000K white light LED lamp with an illumination of 1000 lux. The results are as follows: Figure 4 shown.

[0110] The efficiency stability curve of the perovskite indoor photovoltaic cells prepared in Example 3 and Comparative Example 1 was tested under 500 lux continuous indoor light. The results are as follows: Figure 5 shown.

[0111] The current density-voltage test was performed on the perovskite indoor photovoltaic cells prepared in Example 1 and Comparative Example 1. The results are as follows: Figure 6 As shown;

[0112] The current density-voltage test was performed on the perovskite indoor photovoltaic cells prepared in Example 2 and Comparative Example 1. The results are as follows: Figure 7 As shown;

[0113] The current density-voltage test was performed on the perovskite indoor photovoltaic cells prepared in Example 4 and Comparative Example 1. The results are as follows: Figure 8 As shown;

[0114] The current density-voltage test was performed on the perovskite indoor photovoltaic cells prepared in Example 5 and Comparative Example 1. The results are as follows: Figure 9 As shown;

[0115] Under a 4000K white light LED lamp with an illumination of 1000 lux, the perovskite indoor photovoltaic cells prepared in Examples 1-5 and Comparative Example 1 were tested, and the performance parameters of the cells are shown in Table 1.

[0116] Table 1

[0117]

[0118] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for preparing a perovskite indoor photovoltaic cell, characterized in that: The preparation method comprises the following steps: providing a substrate, the substrate comprising a first electrode; preparing a hole transport layer on the surface of the first electrode; Coating a halide ammonium salt solution containing a benzene ring on the surface of the hole transport layer and performing a first annealing treatment to obtain a first optimized layer; preparing a perovskite layer on the surface of the first optimized layer; coating a binary halide ammonium salt solution on the surface of the perovskite layer and performing a second annealing treatment to obtain a second optimized layer; preparing an electron transport layer on the surface of the second optimized layer; A second electrode is prepared on the surface of the electron transport layer.

2. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: The ammonium halide salt solution containing a benzene ring comprises an ammonium halide salt containing a benzene ring, and the ammonium halide salt containing a benzene ring is selected from one or more of p-fluorophenethylamine iodine, p-fluorophenethylamine bromide, m-fluorophenethylamine iodine, m-fluorophenethylamine bromide, m-fluorophenethylamine chloride, p-trifluoromethylphenethylamine iodine, p-trifluoromethylphenethylamine bromide, p-trifluoromethylphenethylamine chloride, p-chlorophenethylamine iodine, p-chlorophenethylamine bromide, and p-chlorophenethylamine chloride.

3. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: The concentration of the ammonium halide salt solution containing a benzene ring is 1-5 mg / mL.

4. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: In the step of coating the surface of the hole transport layer with a halide ammonium salt solution containing a benzene ring, the coating method is spin coating, the spin coating speed is 3000-5000 rpm, and the time is 30 seconds.

5. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: The temperature of the first annealing treatment is 80-120° C., and the time is 5-30 minutes.

6. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: The dibasic halide ammonium salt solution includes a dibasic halide ammonium salt, and the dibasic halide ammonium salt is selected from one of ethylenediamine dihydrobromide, ethylenediamine dihydroiodide, 1,3-diaminopropane dihydrobromide, 1,3-diaminopropane dihydroiodide, 1,4-diaminobutane dihydroiodide, 1,6-diaminohexane dihydroiodide, and 1,8-diaminooctane dihydroiodide.

7. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: The concentration of the dibasic halide ammonium salt solution is 0.5-1 mg / mL.

8. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: In the step of coating the divalent halide ammonium salt solution on the surface of the perovskite layer, the coating method is spin coating, the spin coating speed is 2000-8000 rpm, and the time is 30 seconds.

9. The method for preparing a perovskite indoor photovoltaic cell according to claim 1, wherein: The temperature of the second annealing treatment is 80-120° C., and the time is 5-30 minutes.

10. A perovskite indoor photovoltaic cell, characterized in that: The perovskite indoor photovoltaic cell is prepared by the preparation method according to any one of claims 1 to 9.

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