Perovskite photoelectric functional material, preparation method and application thereof

Abstract

The application belongs to the technical field of photoelectric functional materials, and particularly relates to a perovskite photoelectric functional material, a preparation method and application thereof. The first aspect of the application provides a perovskite photoelectric functional material, which comprises a perovskite base and a perovskite analogue for modifying the perovskite base; wherein the perovskite analogue is M(B1X13)y; wherein M is an organic small molecule group, X1 is a monovalent anion, B1 is a divalent metal cation; and 0 < y < 3. The perovskite photoelectric functional material has excellent electrochemical performance, very high carrier mobility, high hole rate, high molar extinction coefficient, good two-pole charge transport property, long life of electrons and holes in the perovskite base photoelectric functional material, and excellent carrier diffusion length, so that charge separation is easier.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photoelectric functional materials, and more particularly relates to a perovskite photoelectric functional material, a preparation method and application thereof. BACKGROUND

[0002] In recent years, solar power generation technology has developed rapidly, and the first generation of silicon solar cells has been successfully commercialized on a large scale, making a great contribution to replacing traditional fossil fuels. However, the preparation process of silicon cells is complex, and the preparation conditions are harsh. Therefore, finding a simple and inexpensive photoelectric material is an urgent problem to be solved.

[0003] In addition to the preparation process and device structure of perovskite, the electrical properties of perovskite material itself also greatly affect the performance of the device, and finding a method to improve the electrical properties of perovskite is an important way to further improve the performance of the device. Therefore, finding a simple and inexpensive method to improve the photoelectric properties of perovskite material is an important method and means to improve the photoelectric conversion efficiency of perovskite solar cells and solve the industrialization of perovskite solar cells.

[0004] Patent document CN103762344A discloses a method for improving the performance of the corresponding device by improving the electrical properties of perovskite material itself. In this scheme, an organic amphoteric molecule is used to modify M z A y BX z+y+2 The perovskite-based photoelectric functional material is modified by using an organic amphoteric molecule M as a modification component to modify ABX3 perovskite material, so as to obtain a perovskite-based photoelectric functional material with a molecular formula of M x A y BX x+y+2 The modification of the material greatly improves the crystallization performance, and the photoelectric conversion efficiency and stability show obvious advantages. When applied to mesoscopic solar cells based on carbon counter electrodes, the photoelectric conversion efficiency and stability are significantly higher than that of the unmodified material ABX3 applied to such batteries.

[0005] Patent document CN105405974A discloses a P-type doped perovskite photoelectric functional material and its application. In this scheme, it is proposed that the perovskite-based photoelectric functional material ABX3 is used as a base, and an organic or inorganic dopant is used as a P-type dopant for doping to obtain a perovskite-based photoelectric functional material with a chemical formula of (A1) x (A2) 1- x B(X1) y (X2) 3-y, wherein 0≤x≤1, 0≤y≤3, A1 is a monovalent organic or inorganic cation, A2 is a monovalent organic or inorganic cation, B is a divalent metal cation, X1 or X2 is a monovalent anion. The P-type doped perovskite-based photoelectric functional material can significantly improve the carrier concentration, hole mobility and conductivity, and a perovskite photoelectric functional material with excellent electrical performance can be obtained.

[0006] The above scheme also has some problems or deficiencies. The open-circuit voltage and fill factor of the perovite-based battery modified based on the above scheme are relatively low, which further leads to a relatively low photoelectric conversion efficiency. The low open-circuit voltage and fill factor may be caused by the serious recombination of electrons and holes due to the low conductivity and hole mobility of the amphoteric molecule modified perovskite, which further causes serious efficiency loss. SUMMARY

[0007] The purpose of the present application is to provide a perovskite photoelectric functional material, a preparation method and an application thereof, aiming to solve the problem of low photoelectric conversion efficiency of perovskite solar cells in the prior art.

[0008] To achieve the above application purposes, the technical scheme adopted by the present application is as follows:

[0009] The first aspect of the present application provides a perovskite photoelectric functional material, comprising a perovskite base and a perovskite analog for modifying the perovskite base; wherein the perovskite analog is M(B1X13)y; wherein M is an organic small molecule group, X1 is a monovalent anion, and B1 is a divalent metal cation; 0<y≤3.

[0010] The perovskite photoelectric functional material provided by the present application comprises a perovskite base and a perovskite analog. The perovskite analog can improve the high crystallinity of the perovskite photoelectric functional material after modifying the perovskite base. The perovskite analog comprises an organic small molecule group or an inorganic cation, a divalent metal ion and a monovalent anion. Under the condition of the coefficient constraint (0<y≤3) in the present application, the perovskite analog with high crystallinity and excellent photoelectric properties can be formed. The perovskite analog can modify the perovskite base, so that the perovskite photoelectric functional material has excellent electrochemical performance, very high carrier mobility, high hole rate, high molar extinction coefficient, good two-pole charge transport property, long lifetime of electrons and holes in the perovskite base photoelectric functional material, and excellent carrier diffusion length, making charge separation easier.

[0011] The second aspect of the present application provides a preparation method of the above-mentioned perovskite photoelectric functional material, comprising the following steps:

[0012] The perovskite analog, the perovskite base and the organic solvent are mixed to obtain a modified perovskite precursor solution;

[0013] Annealing of the modified perovskite precursor solution yields perovskite optoelectronic functional materials.

[0014] The method for preparing perovskite optoelectronic functional materials in this application introduces perovskite analogs onto the perovskite precursor. Firstly, the perovskite analogs can act as additives, mixing with the perovskite matrix to improve the crystallinity of the mixture. Secondly, the perovskite analogs, distributed within the perovskite matrix, modify the matrix, thereby increasing the crystallinity of the mixture. Therefore, the perovskite analogs enhance the crystallinity of the perovskite matrix, reducing defects in the perovskite precursor and minimizing non-radiative recombination. This significantly improves the electrical performance of the perovskite-based optoelectronic functional materials, increasing the open-circuit voltage and improving the photoelectric conversion efficiency of perovskite optoelectronic devices. This solves the technical problem of poor photoelectric performance in existing perovskite materials. Thirdly, the raw material costs of the perovskite precursor and the perovskite analog modification components are low, they can be processed entirely from solution, the preparation method is simple, and the equipment is easy to operate.

[0015] The third aspect of this application provides the application of the perovskite optoelectronic functional materials described above in solar cells or semiconductors.

[0016] Because the perovskite optoelectronic functional material provided in this application has good optoelectronic properties, it can be used as a light scavenger or as a semiconductor material in organic light-emitting diodes, field-effect transistors, and electronic components. Attached Figure Description

[0017] Figure 1 The (TFPbI3) modified with CH3NH3PbI3 and iodine-lead-thiophene-formamidinium (TFPbI3) one-dimensional perovskite analogs provided in the embodiments of this application is (TFPbI3). 0.2 XRD pattern of CH3NH3PbI3;

[0018] Figure 2 It is CH3NH3PbI3 provided in the embodiments of this application;

[0019] Figure 3 This application provides an example of a one-dimensional perovskite analogue modified with iodine-lead-thiophene-formamidinium (TFPbI3) as described in the embodiments of this application. 0.2 SEM image of CH3NH3PbI3. Detailed Implementation

[0020] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0021] In this application, the term "and / or", describes an association relationship of associated objects, which means that there can be three kinds of relationships, for example, A and / or B can represent the following three cases: A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents that the associated objects before and after it are in an "or" relationship.

[0022] In this application, "at least one" means one or more, and "multiple" means two or more. "At least one" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0023] It should be understood that in various embodiments of the present application, the size of the sequence number of the above processes does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence. The execution order of each process should be determined according to its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0024] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0025] The weight of the related components mentioned in the embodiments of the present application can not only refer to the specific content of each component, but also represent the weight ratio relationship between each component. Therefore, as long as the content of the related components in the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the embodiments of the present application. Specifically, the mass mentioned in the embodiments of the present application can be μg, mg, g, kg and other mass units commonly known in the chemical field.

[0026] The terms "first" and "second" are only used for description purposes, to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. For example, without departing from the scope of the embodiments of the present application, the first XX can also be referred to as the second XX, and similarly, the second XX can also be referred to as the first XX. Therefore, the features limited by "first" and "second" can explicitly or implicitly include one or more of the features.

[0027] The first aspect of the embodiment of the present application provides a perovskite photoelectric functional material. The perovskite photoelectric functional material of the embodiment of the present application comprises a perovskite base and a perovskite analog for modifying the perovskite base; wherein the perovskite analog is M(B1X13)y; wherein M is an organic small molecule group, X1 is a monovalent anion, B1 is a divalent metal cation; 0

[0028] The perovskite photoelectric functional material provided by the embodiment of the present application comprises a perovskite base and a perovskite analog. After the perovskite analog modifies the perovskite base, the crystallinity of the perovskite photoelectric functional material can be improved, so that the perovskite photoelectric functional material has the following advantages:

[0029] (1) very high carrier mobility, high hole rate, high molar extinction coefficient, good two-pole charge transport, long lifetime of electrons and holes in the perovskite base photoelectric functional material, excellent carrier diffusion length, and easy charge separation.

[0030] (2) the perovskite analog comprises an organic small molecule group, a divalent metal ion and a monovalent anion, and under the constraint condition (0

[0031] In some embodiments, the perovskite base is A1 a A2 b A3 1-a-b B2 c B3 1-c X2 d X3 e X4 3-d-e The chemical general formula of the perovskite photoelectric functional material is:

[0032] (M(B1X13) y ) z A1 a A2 b A3 1-a-b B2 c B3 1-c X2 d X3 e X4 3-d-ewherein 0≤a≤1, 0≤b≤1, 0≤c≤1, 0≤d≤3, 0≤e≤3, 0<z≤1, and a+b≤1, d+e≤3, wherein the coefficients are in the amount of chemical moles, A1, A2 and A3 are each independently selected from monovalent organic or inorganic cations, B2 and B3 are each independently selected from divalent metal cations, and X2, X3 and X4 are each independently selected from monovalent anions. The perovskite photoelectric functional material of the embodiments of the present application comprises organic small molecule groups or inorganic cations, divalent metal ions and monovalent anions, and under the condition of the coefficient constraints of the embodiments of the present application, a perovskite photoelectric functional material with good optical performance can be formed. Among them, a can be 0, 0.5 and 1, etc., b can be 0, 0.5 and 1, etc., d can be 0, 1, 2 and 3, etc., e can be 0, 1, 2 and 3, etc., and z can be 0.5, 0.7 and 1, etc., and a+b≤1, d+e≤3, for example, when a=0, b=0, c=0, d=0, e=0, z=1, the perovskite photoelectric functional material is M(B1X13) y A3B3X43, when a=1, b=0, c=1, d=3, e=0, z=1, the perovskite photoelectric functional material is M(B1X13) y A1B2X23, in the embodiments of the present application, A1, A2, A3, B1, B2, B3, X1, X2, X3 and X4 are not limited to the types described above in the embodiments of the present application, they can have various modifications or substitutions, and in fact, generally only need to satisfy A1, A2, A3 are monovalent organic or inorganic cations, B1, B2, B3 are divalent metal cations, and X1, X2, X3, X4 are monovalent anions. Among them, the value range of z, a, b, c, d, e is also not limited to the specific values in the above embodiments, and in fact, as long as 0<a≤1, 0≤b≤1, 0≤c≤1, 0≤d≤3, 0≤e≤3, 0<y≤3, 0<z≤1, it can be selected according to actual needs.

[0033] Correspondingly, in the preparation of the perovskite analog modified perovskite-based photoelectric functional material described above, the values of various components are also not limited to the specific numerical values in the above embodiments, for example, the addition ratio range of each component in the preparation of the precursor solution, the content of the modified component, etc., the amount and ratio can be determined according to the determined values of z, a, b, c, d, e, y, z and the corresponding atomic ratio relationship. In some embodiments, when the molar percentage n of the iodo-lead thiophene formamidine modification component (relative to the perovskite photoelectric functional material) satisfies 10%<n≤30%, the performance of the battery is improved.

[0034] In some embodiments, the organic cation comprises at least one of a methylamine group, a formamidinium group, a guanidinium group, a phenethylamine group. A1, A2, and A3 are each independently selected from one of a methylamine group, a formamidinium group, a guanidinium group, a phenethylamine group, a cesium ion, or a rubidium ion, and the ions or groups at A1, A2, and A3 sites can be different or the same. The methylamine group, the formamidinium group, the guanidinium group, and the phenethylamine group provided in embodiments of the present application can further improve the electrical performance of the perovskite optoelectronic functional material.

[0035] In some embodiments, the inorganic cation comprises at least one of a cesium ion, a rubidium ion. The ions or groups at A1, A2, and A3 sites can be different or the same. The methylamine group, the formamidinium group, the guanidinium group, and the phenethylamine group provided in embodiments of the present application can further improve the electrical performance of the perovskite optoelectronic functional material. In some embodiments, the perovskite optoelectronic functional material comprises (TFPbI3) 0.2 CH3NH3PbI3, (TFSnI3) 0.2 CH3NH3SnI3, (TFSnI3) 0.2 CH3NH3CuI3, (TFSnI3) 0.2 CH3NH3GeI3, but embodiments of the present application are not limited thereto.

[0036] In some embodiments, the divalent metal cation comprises at least one of a lead ion, a tin ion, a copper ion, and a germanium ion. B1, B2, and B3 are each independently selected from one of a lead ion, a tin ion, a copper ion, and a germanium ion, and the ions at B1, B2, and B3 sites can be different or the same. The lead ion provided in embodiments of the present application is easy to obtain, has low manufacturing cost, and is conducive to the stability of the perovskite optoelectronic functional material. For example, the perovskite optoelectronic functional material comprises (TFPbI3) 0.2 CH3NH3PbI3, (TFSnI3) 0.2 CH3NH3SnI3, (TFSnI3) 0.2 CH3NH3CuI3, (TFSnI3) 0.2 CH3NH3GeI3, but embodiments of the present application are not limited thereto.

[0037] In some embodiments, X1, X2, and X3 are each independently selected from one of F - , I - , Br - , Cl - , BF4 - , PF6 - , and SCN - , and the ions at X1, X2, and X3 sites can be different or the same. The I -obtainable, low in manufacturing cost, and conducive to the stability of the perovskite photoelectric functional material. For example, the perovskite photoelectric functional material includes (TFPbI3) 0.2 CH3NH3PbI3, (BZPbI3) 0.05 CH3NH3PbI3, and (2-MPPbI3) 0.03 (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3, (TFPbI3) 0.2 CH3NH3PbI, (TFPbF3) 0.2 CH3NH3PbI, (TFPbF3) 0.2 CH3NH3PbF, (TFPbBr3) 0.2 CH3NH3PbBr, (TFPbSCN3) 0.2 CH3NH3PbSCN, and the like, but the embodiments of the present application are not limited thereto.

[0038] In some embodiments, the organic small molecule group includes one of a thiophene group and a benzene group. The one-dimensional perovskite analog formed by the thiophene group and the benzene group is conducive to improving the electrochemical performance of the perovskite matrix and can significantly improve the carrier fluorescence lifetime, so that a perovskite photoelectric functional material with excellent photoelectric performance can be obtained, and the preparation process is simple and low in cost. In some embodiments, the thiophene group includes a thiophene formamidine group. The purpose of the embodiments of the present application is to provide a one-dimensional perovskite analog, which is different from the perovskite (ABX3) in that the A cation site is a thiophene formamidine group. Further, the defect state density can be reduced to improve the open-circuit voltage of the device, and the photoelectric conversion efficiency and stability of the solar cell prepared thereby are greatly improved.

[0039] In some embodiments, the perovskite analog is distributed inside the perovskite matrix to modify the perovskite matrix. The preparation method of the perovskite photoelectric functional material provided in the embodiments of the present application can introduce a one-dimensional perovskite analog on the perovskite matrix, thereby improving the crystallinity of the perovskite crystal. On the one hand, the perovskite defects are reduced, the non-radiative recombination is reduced, the electrical performance of the perovskite-based photoelectric functional material is greatly improved, the open-circuit voltage is increased, the photoelectric conversion efficiency of the perovskite photoelectric device is improved, thereby solving the technical problem of poor photoelectric performance of the existing perovskite material. On the other hand, the raw material cost of the perovskite and the one-dimensional perovskite analog modification component is low, the processing can be fully solution processed, the preparation method is simple, and the equipment is easy to operate.

[0040] In some embodiments, the one-dimensional perovskite analog includes one of iodine lead thiophene formamidine, iodine lead benzimidazole, iodine lead benzimidazole, and iodine lead tetrabutylammonium bromide. The I- Easy to obtain, low in manufacturing cost, and conducive to the stability of the perovskite photoelectric functional material.

[0041] In some embodiments, the crystal shape of the one-dimensional perovskite analogues includes at least one of a rod shape or a needle shape. In some embodiments, the crystal of the one-dimensional perovskite analogues is a transparent crystal. In some embodiments, the crystal length of the one-dimensional perovskite analogues is 1 mm to 10 cm. The one-dimensional perovskite analogues in the embodiments of the present application have excellent crystallization performance. The one-dimensional perovskite analogues can be distributed inside the perovskite matrix to modify the perovskite matrix, thereby improving the crystallinity of the perovskite matrix and improving the photoelectric performance thereof.

[0042] The second aspect of the embodiments of the present application provides a preparation method of the perovskite photoelectric functional material described above in the embodiments of the present application, including the following steps:

[0043] Step S1: mixing and processing perovskite analogues, a perovskite matrix, and an organic solvent to obtain a modified perovskite precursor solution;

[0044] Step S2: annealing the modified perovskite precursor solution to obtain a perovskite photoelectric functional material.

[0045] The preparation method of the perovskite photoelectric functional material in the embodiments of the present application can introduce perovskite analogues to the perovskite precursor. On the one hand, the perovskite analogues can be mixed with the perovskite matrix as an additive to improve the crystallinity of the mixture. On the other hand, the perovskite analogues can be distributed inside the perovskite matrix to improve the crystallinity of the mixture. Therefore, the perovskite analogues can improve the crystallinity of the perovskite matrix, thereby having the following advantages:

[0046] (1) The perovskite precursor defects are reduced, the non-radiative recombination is reduced, the electrical performance of the perovskite-based photoelectric functional material is greatly improved, the open-circuit voltage is increased, and the photoelectric conversion efficiency of the perovskite photoelectric device is improved, thereby solving the technical problem of poor photoelectric performance of the existing perovskite material;

[0047] (2) The raw material cost of the perovskite precursor and the perovskite analogue modification component is low, the preparation method is simple, and the equipment is easy to operate.

[0048] In some embodiments, in the modified perovskite precursor solution, the concentration of the perovskite analogues is 0.1 to 2.0 mmol / mL, and the concentration of the perovskite precursor is 0.5 to 2.0 mmol / mL. In this concentration range, the stability of the perovskite photoelectric functional material can be improved.

[0049] In some embodiments, the step S1 specifically includes the following steps:

[0050] Step S101: mixing the one-dimensional perovskite analog and the first solvent to obtain the one-dimensional perovskite analog. In some embodiments, the one-dimensional perovskite analog is formed by benzamidine hydroiodide, 2-methylpiperidine hydroiodide, benzimidazole hydroiodide, and metal halide.

[0051] In some embodiments, the method for preparing the one-dimensional perovskite analog includes: mixing an organic small molecule and B1X1 3y In some embodiments, the one-dimensional perovskite analog is prepared in a solution by mixing, for example, the metal halide can be PbI2, the organic small molecule is benzamidine hydroiodide, the benzamidine group occupies the cation site, and I - occupies the anion site to combine with PbI2 to form the one-dimensional perovskite analog. In some embodiments, in the step S101, the first solvent includes at least one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), gamma butyrolactone (GBL), N-methyl pyrrolidone (NMP), formamide, and N-methyl formamide (NMF), which can improve the solubility of the one-dimensional perovskite analog in the organic solvent.

[0052] In some embodiments, the step S1 specifically includes:

[0053] Step S102: mixing the small molecule organic matter, the metal halide, and the second solvent to obtain a perovskite precursor solution. In some embodiments, the small molecule organic matter contains at least one of a methylamine group, a formamidine group, an ethylidine group, and a phenethylamine group. In some embodiments, the metal halide contains at least one of cesium ions and rubidium ions. In some embodiments, in the step S102, the second solvent includes at least one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), gamma butyrolactone (GBL), N-methyl pyrrolidone (NMP), formamide, and N-methyl formamide (NMF), which can improve the solubility of the small molecule organic matter and the metal halide in the organic solvent.

[0054] In some embodiments, the step S1 specifically includes:

[0055] Step S103: mixing the one-dimensional perovskite analog solution and the perovskite precursor solution to obtain a modified perovskite precursor solution.

[0056] In some embodiments, the annealing treatment in step S2 has two effects: the first is to remove the organic solvent, and the second is to improve the crystallinity of the perovskite photoelectric functional material. The temperature of the annealing treatment is 70-200°C, the heating rate is 1-10°C / min, and the annealing time is 10-40 min. The present application uses a one-dimensional perovskite analogue to modify the perovskite precursor (ABX3). It is found that the annealing process needs to be adjusted accordingly. According to the traditional annealing method of ABX3 perovskite precursor, the crystallinity is not high, resulting in an undesirable photoelectric conversion efficiency. Further, the annealing temperature is 100°C, the heating rate is 10°C / min, and the annealing time is 10 min. In combination with the improved annealing step, the control of the heating rate increases the crystallinity and further improves the photoelectric conversion efficiency of the perovskite photoelectric functional material.

[0057] The third aspect of the present application provides the use of the perovskite photoelectric functional material described above in the present application in a solar cell or a semiconductor.

[0058] The perovskite photoelectric functional material provided by the present application has good photoelectric performance, and therefore can be used as a light trapping agent or as a semiconductor material in an organic light-emitting diode, a field effect transistor, and an electronic component.

[0059] To enable the above-mentioned implementation details and operations of the present application to be clearly understood by those skilled in the art, and to enable the performance of the perovskite photoelectric functional material, the preparation method thereof, and the application thereof to be significantly embodied, the above-mentioned technical solutions are illustrated by multiple examples as follows.

[0060] Example 1

[0061] The present application provides a (TFPbI3) 0.2 The CH3NH3PbI3 perovskite-based photoelectric functional material is a one-dimensional perovskite analogue of iodine lead thiophene formamidine (TFPbI3) formed by TFI and PbI2. The CH3NH3PbI3 constitutes a perovskite base. The TFPbI3 is combined with the CH3NH3PbI3 to constitute a perovskite base and modifies the CH3NH3PbI3 to constitute a perovskite base.

[0062] (TFPbI3) 0.2 The preparation of the CH3NH3PbI3 perovskite-based photoelectric functional material includes the following steps:

[0063] (1) 0.461 g of PbI2 and 0.159 g of CH3NH3I (in a stoichiometric ratio of 1:1) are weighed and completely dissolved in 0.8 mL of DMF to obtain solution A;

[0064] (2) Weigh 0.143g of TFPbI3 (relative to (TFPbI3)) 0.2 Solution B is obtained by completely dissolving 20% ​​(molar fraction of CH3NH3PbI3) in 0.2 mL of DMSO.

[0065] (3) Add solution B to solution A and mix thoroughly to obtain chloroformamidine modified perovskite precursor solution C;

[0066] (4) Take an appropriate amount of perovskite precursor solution C and fill it into a carbon-based mesoscopic solar cell, and dry it at 100°C for 10 min.

[0067] This embodiment uses a printable mesoscopic solar cell with a structure of FTO glass substrate / dense TiO2 / mesoporous TiO2 / mesoporous ZrO2 / carbon electrode.

[0068] The open-circuit voltage (V) of the perovskite solar cell fabricated using the above-mentioned chloromethanemid-modified perovskite optoelectronic functional material oc ), short-circuit current (J) sc The fill factor (FF) and photoelectric conversion efficiency (PCE) have all been significantly improved.

[0069] At 100mW cm -2 Under simulated solar light test conditions, the unmodified CH3NH3PbI3 solar cell showed a photoelectric conversion efficiency of 12.00%, while the CH3NH3PbI3 solar cell modified with lead iodide, thiophene, and formamidinium showed a significantly improved photoelectric conversion efficiency of 17.42%.

[0070] Figure 1 It is the one-dimensional perovskite analog of lead iodide thiophene formamidinium (TFPbI3) modified in Example 1 (TFPbI3). 0.2 XRD pattern of CH3NH3PbI3; (TFPbI3) 0.2 The XRD pattern of the CH3NH3PbI3 perovskite film shows increased peak intensity compared to CH3NH3PbI3, indicating increased crystallinity. Please refer to [reference needed]. Figures 2 to 3 As shown, (TFPbI3) 0.2 Compared to CH3NH3PbI3, the CH3NH3PbI3 perovskite film has larger grains, indicating increased crystallinity. This helps reduce defects and improves film quality, resulting in a significant enhancement of the photoelectric performance of perovskite-based optoelectronic functional materials.

[0071] Example 2

[0072] This embodiment provides a (BZPbI3) solution. 0.05CH3NH3PbI3 is a perovskite-based optoelectronic material, where M is benzamide hydroiodide (BZI). BZI can form a one-dimensional perovskite analog with PbI2, which has the structure of lead iodide benzamide (BZPbI3). CH3NH3PbI3 constitutes the perovskite matrix, and BZPbI3 is bonded to the CH3NH3PbI3-based perovskite matrix, thus modifying the CH3NH3PbI3-based perovskite matrix.

[0073] (BZPbI3) 0.05 The preparation of CH3NH3PbI3 perovskite-based optoelectronic functional materials includes the following steps:

[0074] (1) Weigh 0.461g PbI2 and 0.159g HCNH2NH2I (in a stoichiometric ratio of 1:1) and completely dissolve them in 0.8ml DMF to obtain solution A;

[0075] (2) Weigh 0.035g of lead iodide benzamide (relative to (BZPbI3)). 0.05 Solution B is obtained by completely dissolving CH3NH3PbI3 (5% by mass) in 0.2 ml of DMSO.

[0076] (3) Add solution B to solution A and mix thoroughly to obtain iodine-lead-benzamide-modified perovskite precursor solution C;

[0077] (4) Take an appropriate amount of perovskite precursor solution C and spin-coat it onto a transparent ITO conductive glass substrate deposited with PTAA, and anneal it at 105°C for 5 minutes. Then vacuum evaporate C in sequence. 60 BCP and Ag electrodes.

[0078] This embodiment uses an inverted perovskite solar cell with the following structure: glass substrate / anode (ITO) / hole transport layer (PTAA) / perovskite light-absorbing layer / electron transport layer (C). 60 ) / Interface modification layer (BCP) / Cathode (Ag).

[0079] The open-circuit voltage (V) of the perovskite solar cell fabricated using the above-mentioned iodine-lead-benzamidinium modified perovskite optoelectronic functional material oc ), short-circuit current (J) sc The fill factor (FF) and photoelectric conversion efficiency (PCE) have all been significantly improved.

[0080] At 100mW cm -2 Under simulated solar light test conditions, the unmodified CH3NH2PbI3 solar cell showed a photoelectric conversion efficiency of 16.2%, while the (BZPbI3) modified with a one-dimensional perovskite analogue of lead iodide benzamide showed a higher efficiency. 0.05CH3NH3PbI3solar cell shows a significantly improved photoelectric conversion efficiency of 18.35%.

[0081] Example 3

[0082] This example provides a (2-MPPbI3) 0.03 (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3perovskite-based optoelectronic functional material. 2-MP can form a one-dimensional perovskite analogue with PbI2in the structure of iodine lead 2-methyl piperidine (2-MPPbI3). (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3constitutes a perovskite base, and the 2-MPPbI3is combined on (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3and to (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3perovskite base is modified.

[0083] (2-MPPbI3) 0.03 (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 The preparation of the CH3NH3PbI3perovskite-based optoelectronic functional material includes the following steps:

[0084] (1) 0.461 g of PbI2, 0.024 g of CH3NH3I, and 0.138 g of HCNH2NH2I and 0.0130 g of CsI are weighed and completely dissolved in 0.9 ml of DMF to obtain solution A;

[0085] (2) 0.0168 g of 2-MPPbI3(relative to (2-MPPbI3) 0.03 (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3is 3%) is completely dissolved in 0.1 ml of NMF to obtain solution B;

[0086] (3) Solution B is added to solution A and mixed thoroughly to obtain a lead iodine 2-methyl piperidine modified perovskite precursor solution C;

[0087] (4) Take appropriate amount of perovskite precursor solution C spin coating on the transparent ITO conductive glass substrate deposited with PTAA, 105°C annealing for 5 minutes. Then vacuum evaporate C 60 , BCP and Ag electrode in turn.

[0088] This embodiment adopts trans perovskite solar cell, the structure is: glass substrate / anode (ITO) / hole transport layer (PTAA) / perovskite light absorption layer / electron transport layer (C 60 ) / interface modification layer (BCP) / cathode (Ag).

[0089] The open circuit voltage (V oc ), short circuit current (J sc ), fill factor (FF) and photoelectric conversion efficiency (PCE) of the perovskite solar cell prepared by using the above iodine lead 2-methyl piperidine modified perovskite photoelectric functional material are greatly improved.

[0090] Under the test conditions of 100 mW cm -2 of simulated sunlight source, the unmodified (CH3NH3) 0.15 (HC(NH2)2) 0.85 Cs 0.05 PbI3 solar cell shows a photoelectric conversion efficiency of 18.32%, while the iodine lead 2-methyl piperidine modified (2-MPPbI3) 0.03 (CH3NH2) 0.15 (HCNH2NH) 0.8 Cs 0.05 PbI3 solar cell shows a significantly improved photoelectric conversion efficiency of 21.24%.

[0091] Example 4

[0092] In this embodiment, a (BnPbI3) 0.15 HCNH2NH2PbI3 perovskite-based photoelectric functional material is provided. BnI can form a one-dimensional perovskite analogue with PbI2, which has a structure of iodine lead benzimidazole (BnPbI3). HCNH2NH2PbI3 constitutes a perovskite base. The BnPbI3 is combined on and modifies the HCNH2NH2PbI3 perovskite base.

[0093] The (BnPbI3) 0.15 HCNH2NH2PbI3 perovskite-based photoelectric functional material is prepared by the following steps:

[0094] (1) Take 0.461g PbI2, 0.172g HCNH2NH2I completely dissolved in 0.5ml DMF to obtain solution A;

[0095] (2) Weigh 0.0869g of lead iodide benzimidazole (BnPbI3) (relative to (BnPbI3) 0.15 Solution B is obtained by completely dissolving HCNH2NH2PbI3 (15% molar fraction) in 0.5 ml of DMF.

[0096] (3) Add solution B to solution A and mix thoroughly to obtain fluoroformamidine modified perovskite precursor solution C;

[0097] (4) Take an appropriate amount of perovskite precursor solution C and spin-coat it onto a transparent ITO conductive glass substrate with SnO2 deposited on it, and anneal it at 120°C for 10 minutes. Then spin-coat Sprio-OMeTAD and vapor-deposit Au electrodes.

[0098] This embodiment uses an inverted perovskite solar cell with the following structure: glass substrate / anode (ITO) / electron transport layer (SnO2) / perovskite light-absorbing layer / hole transport layer (Sprio-OMeTAD) / cathode (Au).

[0099] The open-circuit voltage (V) of the perovskite solar cell prepared using the above-mentioned iodine-lead-benzimidazole modified perovskite optoelectronic functional material oc ), short-circuit current (J) sc The fill factor (FF) and photoelectric conversion efficiency (PCE) have all been significantly improved.

[0100] At 100mW cm -2 Under simulated solar light conditions, the unmodified HCNH2NH2PbI3 solar cell exhibited a photoelectric conversion efficiency of 19.46%, while the (BnPbI3) modified with lead iodine and benzimidazole showed a lower efficiency. 0.15 The HCNH2NH2PbI3 solar cell exhibited a significantly improved photoelectric conversion efficiency of 22.32%.

[0101] Comparative Example 1

[0102] This comparative example provides a perovskite analog with the chemical formula CH3NH3PbI3. The specific steps for preparing this material are as follows:

[0103] (1) Weigh 0.461g PbI2 and 0.159g CH3NH3I and completely dissolve them in 1.0ml DMF to obtain solution A;

[0104] (4) Take an appropriate amount of perovskite precursor solution A and fill it into a carbon-based mesoscopic solar cell, and dry it at 120°C.

[0105] At 100mW cm -2Under simulated solar light test conditions, the unmodified MAPbI3 solar cell showed a photoelectric conversion efficiency of 12.00%.

[0106] Comparative Example 2

[0107] This comparative example provides a perovskite matrix with the chemical formula (CH3NH2). 0.15 (HCNH2NH) 0.8 Cs 0.05 The specific steps for preparing PbI3 are as follows:

[0108] (1) Weigh 0.461g PbI2, 0.024g CH3NH3I, 0.138g HCNH2NH2I and 0.0130g CsI and completely dissolve them in 1.0ml DMF to obtain solution A;

[0109] (2) Take an appropriate amount of perovskite precursor solution C and spin-coat it onto a transparent ITO conductive glass substrate deposited with PTAA, and anneal it at 105°C for 5 minutes. Then vacuum evaporate C in sequence. 60 BCP and Ag electrodes.

[0110] At 100mW cm -2 Under simulated solar light conditions, the unmodified MAPbI3 solar cell exhibited a photoelectric conversion efficiency of 19.85%.

[0111] Compared with Comparative Examples 1 and 2, Examples 1 to 4 showed a significant improvement in photoelectric conversion efficiency, with Example 4 exhibiting the highest efficiency at 22.32%. Furthermore, compared with Comparative Examples 1 and 2, the perovskite analog in Comparative Example 1 showed the lowest photoelectric conversion efficiency, indicating its inherently poor photoelectric conversion efficiency. Compared with Comparative Example 1 and Example 4, the (BnPbI3) in Example 4 showed the highest efficiency. 0.15 After modification with BnPbI3, the photoelectric conversion efficiency of HCNH2NH2PbI3 increased from 19.85% to 22.32%.

[0112] Those skilled in the art will readily understand that the above description is merely 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 within the scope of protection of the present invention.

Claims

1. A perovskite photoelectric functional material, characterized in that, A perovskite analog comprising a perovskite matrix and a perovskite analog modifying said perovskite matrix; wherein said perovskite analog is M(B1X13) y ; wherein said M is an organic small molecule group, said X1 is I - , said B1 is Pb 2+ , and y = 1. M(B1X13) of the perovskite analog y The perovskite analog is at least one of iodine lead thiophene formamidine (TFPbI3), iodine lead benzimidazole (BZPbI3), iodine lead benzimidazole (BnPbI3), and iodine lead 2-methylpiperidine (2-MPPbI3), and the perovskite matrix is A1 a A2 b A3 1-a-b B2 c B3 1-c X2 d X3 e X4 3-d-e The chemical general formula of the perovskite photoelectric functional material is: (M(B1X13) y ) z A1 a A2 b A3 1-a-b B2 c B3 1-c X2 d X3 e X4 3-d-e wherein 0 < a < 1, 0 < b < 1, 0 < c < 1, 0 < d < 3, 0 < e < 3, 0 < z < 1, and a + b < 1, d + e < 3, wherein the coefficients are amounts in chemical moles; The A1, A2 and A3 are each independently selected from a monovalent organic cation or a monovalent inorganic cation; The B2 and B3 are each independently selected from a divalent metal cation; The X2, X3 and X4 are each independently selected from a monovalent anion.

2. The perovskite photoelectric functional material according to claim 1, characterized in that, The organic cation comprises at least one of a methylamine group, a formamidine group, an acetamidine group, a phenylethylamine group; or / and The inorganic cation comprises at least one of a cesium ion, a rubidium ion; or / and The divalent metal cation comprises at least one of a lead ion, a tin ion, a copper ion and a germanium ion; or / and The monovalent anion includes at least one of F - , I - , Br - , Cl - , BF4 - , PF6 - , and SCN - .

3. The perovskite optoelectronic functional material according to any one of claims 1-2, wherein, The perovskite analogues are distributed inside the perovskite matrix to modify the perovskite matrix.

4. The perovskite optoelectronic functional material according to claim 3, characterized in that, The crystal shape of the perovskite analogues comprises at least one of a rod shape or a needle shape; or / and The crystal of the perovskite analogues is a transparent crystal; or / and The crystal length of the perovskite analogues is 1 mm to 10 cm.

5. A method for preparing the perovskite photoelectric functional material according to any one of claims 1-4, characterized in that, The method comprises the following steps: The perovskite analogues, the perovskite matrix and the organic solvent are mixed to obtain a modified perovskite precursor solution; The modified perovskite precursor solution is annealed to obtain a perovskite photoelectric functional material.

6. The method of claim 5, wherein a concentration of the perovskite analogues in the modified perovskite precursor solution is 0.1-2.0 mmol / mL, and a concentration of the perovskite precursor is 0.5-2.0 mmol / mL. The organic solvent comprises at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, gamma butyrolactone, N-methyl pyrrolidone, formamide and N-methyl formamide.

7. The method for preparing the perovskite optoelectronic functional material as described in claim 5, characterized in that, 9. The perovskite photoelectric functional material according to any one of claims 1-4, wherein the perovskite photoelectric functional material is used in a solar cell.

8. The method for preparing the perovskite optoelectronic functional material according to any one of claims 5-7, characterized in that, The temperature in the annealing process is , the heating rate is , and the annealing time is 10-40 min. ​

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