Modified perovskite-based photoelectric functional material containing photo-isomeric molecules, and preparation and application thereof

Abstract

The invention belongs to the technical field of metal halide perovskite photoelectric functional materials, and discloses a modified perovskite-based photoelectric functional material containing photoisomeric molecules and preparation and application thereof, and the modified perovskite-based photoelectric functional material containing the photoisomeric molecules is prepared by adding the photoisomeric molecules 1, 3, 4, 5, 6-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3 The preparation method comprises the following steps: adding 2, 3, 3-trimethylindole-beta-naphthyl dihydrofuran (SPBenz), and annealing to obtain the product. According to the invention, the characteristic that the photoisomeric molecule SPBenz forms an open loop state containing N + and C-O-under the induction of a polar solvent and solar illumination is utilized, so that a perovskite material matrix is modified from multiple aspects of regulation and control of perovskite crystals and long-acting passivation of perovskite defects; the obtained modified perovskite-based photoelectric functional material containing the photo-isomeric molecules is excellent in photoelectric property, and the photoelectric conversion efficiency and the stability are effectively improved when the modified perovskite-based photoelectric functional material containing the photo-isomeric molecules is applied to solar cells.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal halide perovskite photoelectric functional materials, and more specifically, relates to a modified perovskite-based photoelectric functional material containing photoisomerism molecules, and the preparation and application thereof. Background Art

[0002] Due to the non-renewable nature of fossil energy and the greenhouse effect it brings, energy transformation is imminent. Renewable energy sources such as wind energy, nuclear energy, geothermal energy, tidal energy, and solar energy are developing rapidly. It is worth noting that the proportion of solar energy has increased dramatically in recent years. Photovoltaic power generation through photoelectric conversion, namely solar cells, has unique advantages and has been widely studied. Therefore, it is necessary and urgent to find optoelectronic materials with excellent performance, simple preparation, and low cost.

[0003] Metal halide perovskite materials have attracted extensive attention due to their excellent optoelectronic properties. It is a direct bandgap semiconductor material with excellent performance. By adjusting the components, its bandgap can be continuously adjusted between 1.2eV and 3.0eV, thereby obtaining the corresponding bandgap. In terms of optical properties, it can have strong absorption in a wide wavelength range of 300 to 800nm. In addition, the carriers excited and generated in the perovskite material have a long lifetime and high mobility, which makes it have a considerable carrier diffusion length that is conducive to the effective separation of electron-hole pairs. At the same time, due to its good solubility in polar organic solvents, it can be prepared using a simple solution method, thereby reducing the cost in the process. Therefore, perovskite materials have been widely studied and applied as optoelectronic functional materials in the fields of electronic devices such as solar cells and photodetectors.

[0004] The photoelectric properties of perovskite materials are directly related to the performance of devices. Although significant progress has been made in the research of perovskite materials, perovskite materials prepared by solution method still have many defects that limit the performance of corresponding devices. It is crucial to explore methods to improve the quality of perovskite materials. Existing technologies mainly focus on the use of anion, cation, Lewis acid, Lewis base additives, etc. to passivate defects, and have achieved certain results. However, the above strategies can only passivate certain types of defects, and can only play a small role in the new defects generated during the subsequent operation of the device. In order to further improve the quality of perovskite materials, finding a simple and effective method for preparing modified perovskite photoelectric materials is an important means to promote the industrialization of perovskite-based photoelectric devices. Summary of the invention

[0005] In view of the above defects or improvement needs of the prior art, the object of the present invention is to provide a modified perovskite-based optoelectronic functional material containing photoisomerization molecules, and its preparation and application, wherein the perovskite material (such as ABX3 perovskite material) matrix is ​​modified by adding the photoisomerization molecule 1,3,3-trimethylindole-β-naphthyldihydrofuran (SPBenz), and the perovskite material is induced to open the ring to form zwitterions (i.e., to form N-containing) under polar solvents (such as DMF, DMAC, DMSO, GBL, NMP, NMF) and sunlight. + and CO - open ring state) and can react with Pb 2+ The coordination characteristics (taking the B-position element in ABX3 as Pb as an example) realize precursor modulation and multiple defect passivation and even inhibit the generation of new defects during device operation, thereby realizing multi-faceted modification of the perovskite material matrix. Finally, the obtained modified perovskite-based optoelectronic functional material containing photoisomerized molecules has excellent optoelectronic properties. When applied to solar cells, the photoelectric conversion efficiency and stability are effectively improved. In addition, the preparation method of the present invention is simple and low-cost, and has broad prospects for industrial application.

[0006] To achieve the above-mentioned purpose, according to one aspect of the present invention, a modified perovskite-based optoelectronic functional material containing photoisomerization molecules is provided, characterized in that it is obtained by adding photoisomerization molecules 1,3,3-trimethylindole-β-naphthyldihydrofuran (SPBenz) to a perovskite precursor solution, and then annealing to remove the solvent; wherein the perovskite precursor solution uses a polar organic solvent as a solvent.

[0007] As a further preferred embodiment of the present invention, the perovskite precursor solution can form an ABX3 perovskite material correspondingly, which is formed by dissolving an AX compound and a BX2 compound in a polar organic solvent at a molar ratio of 1:1; wherein A is a positive monovalent cation, B is a positive divalent cation, and X is a negative monovalent anion;

[0008] The photoisomerization molecules are added to the perovskite precursor solution, specifically, the molar ratio of the photoisomerization molecules to the ABX3 perovskite material is 0.01% to 0.1%.

[0009] As a further preferred embodiment of the present invention, in the ABX3 perovskite material:

[0010] The monovalent cation at position A is methylamine cation CH3NH3 + 、Formamidinium cation CH(NH2)2 + , Cesium cation Cs + 、Methylhydroxylamine cation CH3NH2OH + 、Dimethylhydroxylamine cation (CH3)2NHOH +、Guanidine cation C(NH2)3 + 、Dimethylamine cation (CH3)2NH2 + 、Methylenediamine cation NH2CH2NH3 + 、acetamidine cation CH3C(NH2)2 + One or more of;

[0011] The positive divalent cation at position B is lead ion Pb 2+ 、Sn 2+ 、Ge 2+ 、Copper ion Cu 2+ One or more of;

[0012] The negative monovalent anions at the X position are fluoride ion F-, chloride ion Cl-, bromide ion Br - 、Iodide ion I - 、cyanide ion CN - , one or more of thiocyanate ion SCN-.

[0013] According to another aspect of the present invention, the present invention provides a method for preparing the above-mentioned modified perovskite-based optoelectronic functional material containing photoisomerism molecules, characterized in that it comprises the following steps:

[0014] (1) dissolving the AX compound and the BX2 compound in an organic solvent at a molar ratio of 1:1, stirring evenly until the mixture becomes clear and transparent, to prepare a perovskite precursor solution; and the organic solvent is a polar organic solvent;

[0015] (2) dissolving the photoisomerizable molecules in an organic solvent of the same type, stirring the mixture until the mixture becomes clear and transparent, thereby obtaining an additive solution;

[0016] (3) mixing the perovskite precursor solution of step (1) with the additive solution of step (2), stirring evenly, to obtain a modified perovskite precursor solution;

[0017] (4) Using the modified perovskite precursor solution obtained in step (3) to prepare a modified perovskite material, and after annealing to remove the solvent, a modified perovskite-based optoelectronic functional material containing photoisomerizable molecules can be obtained.

[0018] As further preferred embodiment of the present invention, the organic solvent is selected from one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), gamma-martinolactone (GBL), N-methylpyrrolidone (NMP), formamide and N-methylformamide (NMF).

[0019] As a further preferred embodiment of the present invention, in step (1), the concentration of ABX3 in the perovskite precursor solution is 1.2 mol / L;

[0020] In step (2), the concentration of the additive solution is 0.12 mol / L;

[0021] In step (3), the volume ratio of the additive solution to the perovskite precursor solution is (1-10):1000.

[0022] As a further preferred embodiment of the present invention, in step (4), the annealing temperature is 80-100° C. and the annealing time is 30 min.

[0023] According to another aspect of the present invention, the present invention provides the use of the modified perovskite-based optoelectronic functional material containing photoisomerism molecules in solar cells, organic light emitting diodes or field effect transistors.

[0024] As a further preferred embodiment of the present invention, the modified perovskite-based optoelectronic functional material containing photoisomerism molecules is used as a photoactive layer, an n-type semiconductor material or a p-type semiconductor material in a solar cell;

[0025] The modified perovskite-based photoelectric functional material containing photoisomerism molecules is used as an n-type semiconductor material or a p-type semiconductor material in an organic light emitting diode or a field effect transistor.

[0026] Through the above technical scheme conceived by the present invention, compared with the prior art, the photoisomerization molecule SPBenz can be introduced to achieve multi-faceted modification of perovskite-based optoelectronic functional materials from the perspectives of precursor modulation and long-term defect passivation. The photoisomerization molecule SPBenz will form N-containing + and CO - The open ring state can passivate negatively charged defects (such as cation vacancy defects at the A site) and positively charged defects (such as iodine vacancy defects), and can also passivate uncoordinated Pb 2+ (CO - The lone pair of electrons on the O atom and the Pb 2+ The photoelectric functional material has the function of forming a coordination bond, taking the B-position element in ABX3 as Pb as an example), and the photoelectric performance of the obtained photoelectric functional material is excellent. Taking the application in solar cell devices as an example, the open circuit voltage and short circuit current of the solar cell devices can be significantly improved.

[0027] Specifically, the present invention can achieve the following beneficial effects:

[0028] (1) The present invention introduces the photoisomerization molecule SPBenz as a modified component to enhance the interaction with the positive divalent cation at the B position, thereby modulating the perovskite precursor solution and regulating the crystallization process of the perovskite material, thereby improving the crystal quality of the perovskite-based optoelectronic functional material, further reducing defects, and improving its optoelectronic performance.

[0029] (2) The photoisomerization molecule SPBenz introduced by the present invention can change the molecular configuration by simply applying light, thereby enhancing the passivation effect on defects in perovskite-based photoelectric materials. The modified perovskite-based photoisomerization molecule SPBenz obtained by the present invention has a passivation effect on the photoisomerization molecule contained therein, which does not require a separate light treatment in advance, and can be directly completed instantly when the modified perovskite-based photoelectric functional material is used as a photoelectric functional material and light is applied.

[0030] It is known in the prior art that photoisomerization molecules are a special type of organic molecule (such as SPBenz, SPOMe and SPNO2, etc.) that can undergo photoisomerization after absorbing photons. The present invention introduces a specific photoisomerization molecule SPBenz into the perovskite precursor to modulate it, thereby improving the quality of the perovskite crystal and reducing the defects therein, thereby improving the photoelectric conversion efficiency of the perovskite optoelectronic device. The microscopic mechanism may be that the photoisomerization molecule can form an intermediate phase with the perovskite precursor, thereby controlling the nucleation and growth process of the perovskite crystal. At the same time, the change in molecular configuration under light enhances the passivation effect on defects in perovskite-based optoelectronic materials, thereby further improving the quality and optoelectronic properties of the perovskite material. As described later Figure 1 As shown, the present invention introduces photoisomerization molecules into ABX3 perovskite materials, and utilizes the conversion of SP type (closed ring state) to MC type (open ring state) under illumination to passivate defects therein, reduce the occurrence of non-radiative recombination of carriers therein, and obtain optoelectronic functional materials with excellent performance. Moreover, compared with the two photoisomerization molecules SPOMe and SPNO2, taking the application in solar cells as an example, the SPBenz photoisomerization molecules used in the present invention can especially increase the PCE of the modified perovskite solar cell to 20.06%, ranking at the forefront of the PCE reported in the field of carbon-based mesoscopic printable perovskite solar cells, and the modification effect is obvious.

[0031] In addition, the modification method of the present invention can not only passivate the defects formed during the preparation of the perovskite material, but also inhibit new defects generated during the subsequent operation of the device, and has a multi-faceted modification effect. Figure 2As shown, the carrier lifetime of the unmodified perovskite material decreases after sunlight irradiation, while the carrier lifetime of the modified perovskite material obtained based on the present invention hardly changes before and after sunlight irradiation. This indicates that the modified perovskite obtained by the modification method of the present invention can also inhibit new defects generated when the device is running under sunlight.

[0032] (3) The raw materials of the photoisomerization molecules and perovskite materials used in the present invention are low in cost and can be processed by solution method, and the preparation method is simple.

[0033] (4) The perovskite-based optoelectronic functional material modified with the photoisomerized molecule SPBenz obtained by the present invention has excellent optoelectronic properties and can be applied in various optoelectronic device fields, such as solar cells, organic light-emitting diodes, field effect transistors, and electronic components. Taking the application in solar cells as an example, compared with the unmodified perovskite-based optoelectronic functional material, a significantly improved device photoelectric conversion efficiency can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a schematic diagram of SPBenz transforming from a closed-loop state SP to an open-loop state MC after ultraviolet light exposure.

[0035] Figure 2 For unmodified and SPBenz modified (CH3NH3) 0.4 (CH(NH2)2) 0.6 Time-resolved photoluminescence (TRPL) spectra of PbI3 perovskite film before and after sunlight exposure; Figure 2 (a) corresponds to the unmodified (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3 perovskite film, Figure 2 (b) corresponds to SPBenz modified (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3 perovskite film.

[0036] Figure 3 Unmodified and SPBenz, SPOMe and SPNO2 modified (CH3NH3) 0.4 (CH(NH2)2) 0.6 The solar cell device corresponding to PbI3 is 100mW / cm 2 Under the simulated sunlight, the test area is 0.1018cm 2 , measured current density-voltage (JV) curve.

[0037] Figure 4 Unmodified and SPBenz modified (CH3NH3) 0.4(CH(NH2)2) 0.6 Comparison of the photoelectric conversion efficiency (PCE) of PbI3-based encapsulated solar cell devices after continuous operation for 900 hours at 55°C and 55% relative humidity. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0039] Comparative Example 1 (unmodified)

[0040] This comparative example prepared (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3, the specific steps for preparing the material are as follows:

[0041] (1) Weigh 0.0763 g MAI, 0.1238 g FAI and 0.5532 g PbI2 and dissolve them in 1 mL DMF and DMSO mixed solvent (volume ratio = 4:1), stir until clear and transparent, and obtain a 1.2 mol / L precursor solution;

[0042] (2) Filling 4.3 μL of the perovskite precursor solution obtained in step (1) into a carbon counter electrode mesoscopic solar cell, annealing at 80° C. to obtain the unmodified (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3 perovskite-based solar cells.

[0043] The unmodified perovskite-based solar cell device obtained in the above comparative example 1 has a power of 100 mW / cm 2 Under the test conditions of simulated sunlight, the open circuit voltage (V OC ) is 930mV, short-circuit current (J SC ) is 23.99 mA / cm 2 , the fill factor (FF) is 0.77, and the photoelectric conversion efficiency (PCE) is 17.23%.

[0044] At the same time, for the precursor solution obtained in step (1) of Comparative Example 1:

[0045] 4.3 μL of the perovskite precursor solution obtained in step (1) was filled into the mesoporous mp-ZrO2+ porous C layer scaffold, annealed at 80°C for 3 h, and the porous carbon layer was mechanically peeled off with tape to obtain the unmodified sample for TRPL testing.

[0046] Comparative Example 2 (modification with SPOMe)

[0047] In this comparative example, M is spiro[1,3,3-trimethylindole-(8'-methoxychroman)] (SPOMe, CAS No.: 13433-31-3), ABX3 is (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3, the specific steps for preparing the material are as follows:

[0048] (1) Weigh 0.0763 g MAI, 0.1238 g FAI and 0.5532 g PbI2 and dissolve them in 1 mL DMF and DMSO mixed solvent (volume ratio = 4:1), stir until clear and transparent, and obtain a 1.2 mol / L precursor solution;

[0049] (2) 0.0369 g of SPOMe was dissolved in 1 mL of a mixed solvent of DMF and DMSO (volume ratio = 4:1), and the mixture was stirred until it became clear and transparent to obtain a 0.12 mol / L additive solution;

[0050] (3) adding 10 μL of the additive solution obtained in step (2) to 1 mL of the precursor solution obtained in step (1), stirring evenly, to obtain a modified perovskite precursor solution;

[0051] (4) Filling 4.3 μL of the modified perovskite precursor solution obtained in step (3) into a carbon counter electrode-based mesoscopic solar cell, annealing at 80° C., to obtain the modified perovskite-based solar cell containing photoisomerization molecules.

[0052] The modified perovskite-based solar cell device containing SPOMe photoisomerization molecules obtained in the above comparative example 2 has a high power consumption at 100 mW / cm 2 Under the test conditions of simulated sunlight source, its open circuit voltage (V OC ) and fill factor (FF) were improved, thereby increasing the photoelectric conversion efficiency (PCE) from 17.23% of the unmodified perovskite-based solar cell device to 18.81%.

[0053] Comparative Example 3 (using SPNO2 modification)

[0054] In this comparative example, M is 1,3,3-trimethylindole-6'-nitrobenzodihydropyranospirane (SPNO2, CAS No.: 1498-88-0), ABX3 is (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3, the specific steps for preparing the material are as follows:

[0055] (1) Weigh 0.0763 g MAI, 0.1238 g FAI and 0.5532 g PbI2 and dissolve them in 1 mL DMF and DMSO mixed solvent (volume ratio = 4:1), stir until clear and transparent, and obtain a 1.2 mol / L precursor solution;

[0056] (2) 0.0387 g of SPNO2 was dissolved in 1 mL of a mixed solvent of DMF and DMSO (volume ratio = 4:1), and the mixture was stirred until it became clear and transparent to obtain a 0.12 mol / L additive solution;

[0057] (3) adding 10 μL of the additive solution obtained in step (2) to 1 mL of the precursor solution obtained in step (1), stirring evenly, to obtain a modified perovskite precursor solution;

[0058] (4) Filling 4.3 μL of the modified perovskite precursor solution obtained in step (3) into a carbon counter electrode-based mesoscopic solar cell, annealing at 80° C., to obtain the modified perovskite-based solar cell containing photoisomerization molecules.

[0059] The modified perovskite-based solar cell device containing SPNO2 photoisomerization molecules has a high power density of 100 mW / cm 2 Under the test conditions of simulated sunlight source, its open circuit voltage (V OC ), short circuit current (J SC ) have been significantly improved, thereby increasing the photoelectric conversion efficiency (PCE) from 17.23% of the unmodified perovskite-based solar cell devices to 18.75%.

[0060] Example 1 (using SPBenz modification)

[0061] In this embodiment, M is 1,3,3-trimethylindole-β-naphthyldihydrofuran (SPBenz, CAS No.: 1592-43-4), ABX3 is (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3, the specific steps for preparing the material are as follows:

[0062] (1) Weigh 0.0763 g MAI, 0.1238 g FAI and 0.5532 g PbI2 and dissolve them in 1 mL DMF and DMSO mixed solvent (volume ratio = 4:1), stir until clear and transparent, and obtain a 1.2 mol / L precursor solution;

[0063] (2) 0.0393 g of SPBenz was dissolved in 1 mL of a mixed solvent of DMF and DMSO (volume ratio = 4:1), and the mixture was stirred until it became clear and transparent to obtain a 0.12 mol / L additive solution;

[0064] (3) adding 10 μL of the additive solution obtained in step (2) to 1 mL of the precursor solution obtained in step (1), stirring evenly, to obtain a modified perovskite precursor solution;

[0065] (4) Filling 4.3 μL of the modified perovskite precursor solution obtained in step (3) into a carbon counter electrode-based mesoscopic solar cell, annealing at 80° C., to obtain the modified perovskite-based solar cell containing photoisomerization molecules.

[0066] The modified perovskite-based solar cell device containing SPBenz photoisomerization molecules has a high power density at 100mW / cm 2 Under the test conditions of simulated sunlight source, its open circuit voltage (V OC ), short circuit current (J SC ) have been significantly improved, thereby increasing the photoelectric conversion efficiency (PCE) from 17.23% of the unmodified perovskite-based solar cell devices to 20.06%.

[0067] Meanwhile, for the modified perovskite precursor solution obtained in step (3) of Example 1:

[0068] 4.3 μL of the modified perovskite precursor solution obtained in step (3) was filled into the mesoporous mp-ZrO2+ porous C layer support, annealed at 80°C for 3 h, and the porous carbon layer was mechanically peeled off with tape to obtain the modified sample containing photoisomerized molecules for TRPL testing.

[0069] Performance testing:

[0070] First, the defect density of the perovskite materials prepared in Example 1 and Comparative Example 1 was characterized. 2 TRPL tests were performed on unmodified and SPBenz modified perovskite films before and after irradiation with simulated sunlight for 30 minutes. The results are shown in Figure 2As shown in the figure (where "after sunlight" specifically refers to using sunlight to irradiate the perovskite filled in the mesoporous support from the glass surface of the TRPL sample), it can be seen that the carrier lifetime of the unmodified perovskite decreases after sunlight irradiation, while the modified perovskite hardly changes. At the same time, the carrier lifetime of the modified perovskite increases significantly. This shows that the modified perovskite not only has better quality and fewer defects to avoid carrier recombination, but also because the open-ring MC-type molecules generated by light irradiation inhibit the formation of new defects.

[0071] In addition, the perovskite-based solar cells prepared in Example 1 and Comparative Examples 1 to 3 were heated to 100 mW / cm 2 The JV curve test was carried out under the conditions of simulated sunlight. The results are as follows Figure 3 As shown in FIG. 1 , the JV curve results confirm that the photoelectric performance of the modified perovskite photoelectric functional material is improved, thereby increasing the PCE of the device. In particular, the introduction of SPBenz in Example 1 makes the device performance most significantly improved. In addition, after the device is packaged (the packaging is specifically by hot-pressing the EVA film to cover the device), similarly, at 55°C and 55% relative humidity, the PCE of the unmodified packaged solar cell device is 100 mW / cm 2 After 900 hours of operation under simulated sunlight conditions, the device's thermal conductivity dropped to 80% of its initial value, while the modified device still maintained 92% of its initial value. Figure 4 The results confirm that the operational stability of the corresponding devices of modified perovskite is significantly enhanced.

[0072] The above embodiments are only examples, and the perovskite material may also be other ABX3 perovskite materials (for example, the positive monovalent cation at position A is a methylamine cation CH3NH3 + 、Formamidinium cation CH(NH2)2 + , Cesium cation Cs + 、Methylhydroxylamine cation CH3NH2OH + 、Dimethylhydroxylamine cation (CH3)2NHOH + 、Guanidine cation C(NH2)3 + 、Dimethylamine cation (CH3)2NH2 + 、Methylenediamine cation NH2CH2NH3 + 、acetamidine cation CH3C(NH2)2 + One or more of; the positive divalent cation at position B is lead ion Pb 2+ 、Sn 2+ 、Ge 2+ 、Copper ion Cu 2+ One or more of; the negative monovalent anion at position X is a fluoride ion F - 、Chloride ion Cl -、Br - 、Iodide ion I - 、cyanide ion CN - 、Thiocyanate ion SCN - In addition, the organic solvent in the present invention can be at least one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), gamma-martinol (GBL), N-methylpyrrolidone (NMP), formamide, N-methylformamide (NMF), but is not limited to the above-mentioned ones. For example, other solvents known in the prior art that can prepare perovskite thin films by solution method can be used. In addition to solar cells, the modified perovskite-based optoelectronic functional materials containing photoisomerized molecules obtained by the present invention can also be applied to optoelectronic devices such as organic light-emitting diodes, field effect transistors and electronic components to exert their optoelectronic properties.

[0073] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A modified perovskite-based optoelectronic functional material containing photoisomerizable molecules, characterized in that: The method is obtained by adding a photoisomerization molecule 1,3,3-trimethylindole-β-naphthyldihydrofuran (SPBenz) to a perovskite precursor solution and then annealing to remove the solvent; wherein the perovskite precursor solution uses a polar organic solvent as a solvent.

2. The modified perovskite-based optoelectronic functional material containing photoisomerization molecules according to claim 1, characterized in that: The perovskite precursor solution can form an ABX3 perovskite material, which is formed by dissolving an AX compound and a BX2 compound in a polar organic solvent at a molar ratio of 1:1; wherein A is a positive monovalent cation, B is a positive divalent cation, and X is a negative monovalent anion; The photoisomerization molecules are added to the perovskite precursor solution, specifically, the molar ratio of the photoisomerization molecules to the ABX3 perovskite material is 0.01% to 0.1%.

3. The modified perovskite-based optoelectronic functional material containing photoisomerization molecules according to claim 2, characterized in that: In the ABX3 perovskite material: The monovalent cation at position A is methylamine cation CH3NH3 + 、Formamidinium cation CH(NH2)2 + , Cesium cation Cs + 、Methylhydroxylamine cation CH3NH2OH + 、Dimethylhydroxylamine cation (CH3)2NHOH + 、Guanidine cation C(NH2)3 + 、Dimethylamine cation (CH3)2NH2 + 、Methylenediamine cation NH2CH2NH3 + 、acetamidine cation CH3C(NH2)2 + One or more of; The positive divalent cation at position B is lead ion Pb 2+ 、Sn 2+ 、Ge 2+ 、Copper ion Cu 2+ One or more of; The negative monovalent anion at position X is the fluoride ion F - 、Chloride ion Cl - 、Br - 、Iodide ion I - 、cyanide ion CN - , one or more of thiocyanate ion SCN-.

4. The method for preparing the modified perovskite-based optoelectronic functional material containing photoisomerizable molecules according to any one of claims 1 to 3, characterized in that: The steps include: (1) dissolving the AX compound and the BX2 compound in an organic solvent at a molar ratio of 1:1, stirring evenly until the mixture becomes clear and transparent, to prepare a perovskite precursor solution; and the organic solvent is a polar organic solvent; (2) dissolving the photoisomerizable molecules in an organic solvent of the same type, stirring the mixture until the mixture becomes clear and transparent, thereby obtaining an additive solution; (3) mixing the perovskite precursor solution of step (1) with the additive solution of step (2), stirring evenly, to obtain a modified perovskite precursor solution; (4) Using the modified perovskite precursor solution obtained in step (3) to prepare a modified perovskite material, and after annealing to remove the solvent, a modified perovskite-based optoelectronic functional material containing photoisomerizable molecules can be obtained.

5. The preparation method according to claim 4, characterized in that: The organic solvent is selected from one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), gamma-martinolactone (GBL), N-methylpyrrolidone (NMP), formamide and N-methylformamide (NMF).

6. The preparation method according to claim 4, characterized in that: In step (1), the concentration of ABX3 in the perovskite precursor solution is 1.2 mol / L; In step (2), the concentration of the additive solution is 0.12 mol / L; In step (3), the volume ratio of the additive solution to the perovskite precursor solution is (1-10):1000.

7. The preparation method according to claim 4, characterized in that: In step (4), the annealing temperature is 80-100° C. and the annealing time is 30 min.

8. Use of the modified perovskite-based optoelectronic functional material containing photoisomerizable molecules according to any one of claims 1 to 3 in solar cells, organic light emitting diodes or field effect transistors.

9. The use according to claim 8, characterized in that The modified perovskite-based photoelectric functional material containing photoisomerization molecules is used as a photoactive layer, an n-type semiconductor material or a p-type semiconductor material in a solar cell; The modified perovskite-based photoelectric functional material containing photoisomerism molecules is used as an n-type semiconductor material or a p-type semiconductor material in an organic light emitting diode or a field effect transistor.

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