Perovskite photoelectric functional material containing conductive polymer

Abstract

The application belongs to the technical field of perovskite photoelectric functional materials, and discloses a perovskite photoelectric functional material containing conductive polymer, which is obtained by adding conductive polymer to a perovskite material as a base body for modification; wherein the conductive polymer contains a conjugated benzene ring structure, and the C atom on the benzene ring further forms a carbon-nitrogen single bond and / or double bond structure with the N atom. By introducing the conductive polymer with the benzene ring conjugated structure and the carbon-nitrogen single / double bond structure into the perovskite base body, the special functional groups in the conductive polymer are used to passivate the defects therein, so as to reduce the non-radiation recombination of carriers and further improve the carrier transmission. Taking a solar cell device as an example, not only the open-circuit voltage and short-circuit current of the prepared solar cell device are significantly improved, but also the overall long-term stability of the device is strengthened.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of perovskite photoelectric functional materials, more particularly, relates to a perovskite photoelectric functional material containing a conductive polymer, which is particularly suitable for metal halide perovskite materials. BACKGROUND

[0002] The overuse of fossil energy has led to a series of environmental and ecological problems, such as greenhouse effect, acid rain, haze, and garbage disposal, which are gradually showing adverse effects on the ecological environment, and energy transformation is imminent. Renewable energy includes solar energy, wind energy, water energy, and biomass energy, etc. Among them, solar energy is inexhaustible, clean and safe, is a truly green energy, and the solar power generation technology is constantly breaking through, and will dominate the future energy supply. Under this urgent background, we urgently need to find photoelectric materials with excellent performance. The preparation process of these materials should be simple and low cost to meet the requirements of energy transformation. Metal halide perovskite materials have excellent photoelectric properties and have attracted widespread attention. It is a direct band gap semiconductor material with excellent performance. Compared with other semiconductor materials, one of the biggest advantages of ABX3 perovskite material is that its band gap can be adjusted by simple and low-cost solution processing method. Through component regulation, the light absorption range of perovskite can be changed in the wavelength range of 350-1200 nm. In addition to the adjustable band gap, perovskite also has many excellent photoelectric properties. It has high extinction coefficient, low exciton binding energy, and can be dissociated into free holes or electrons at room temperature. It also has a long carrier diffusion length and high defect tolerance. At the same time, due to its good solubility in polar organic solvents, it can be prepared by simple solution method, thereby effectively reducing the preparation cost. Therefore, perovskite materials as photoelectric functional materials have been widely studied and applied in the fields of solar cells, photodetectors and other electronic devices.

[0003] The photoelectric performance of perovskite material is directly related to the performance of perovskite material in devices. Although we have made significant progress in the study of perovskite materials, there are still some limitations in the preparation of perovskite materials by solution method. Due to the difficulty in controlling the crystalline quality, solution method produces more defects, which limits the performance of related devices. Therefore, it is urgent to find a simple and efficient method to improve the quality of perovskite material, which is crucial to promote the industrialization of perovskite-based optoelectronic devices.

[0004] Among the existing strategies to improve the quality of perovskite material, the passivation agent treatment strategy is the simplest and most effective means. Chemical passivation methods include some small molecules and polymers, but the addition of passivation agents will hinder the transport of carriers in perovskite to some extent while passivating defects, limiting the improvement of photoelectric performance of perovskite material. Summary of the Invention

[0005] To address the aforementioned deficiencies or improvement needs of existing technologies, the present invention aims to provide a perovskite optoelectronic functional material containing a conductive polymer. This material incorporates a conductive polymer with special functional groups—benzene ring conjugated structures and carbon-nitrogen single / double bond structures (formed by N atoms corresponding to C atoms on the benzene ring; these can be either single or double bonds, or both)—into the perovskite matrix. These special functional groups in the conductive polymer passivate defects, thereby reducing non-radiative recombination of charge carriers and further improving carrier transport. For example, when applied to solar cell devices, this significantly improves the open-circuit voltage and short-circuit current of the fabricated solar cell devices, while also enhancing the overall long-term stability of the devices. This invention yields high-performance optoelectronic functional materials and is applicable to solution methods, with a simple and low-cost preparation process.

[0006] To achieve the above objectives, according to one aspect of the present invention, a perovskite optoelectronic functional material containing a conductive polymer is provided, characterized in that it is obtained by modifying a perovskite material matrix by adding a conductive polymer to the matrix; wherein...

[0007] The conductive polymer contains a conjugated benzene ring structure, and the C atoms on the benzene ring also form carbon-nitrogen single bonds and / or double bonds with N atoms.

[0008] As a further preferred embodiment of the present invention, (0.1 to 5) mg of conductive polymer is added for every 1.20 mmol of matrix perovskite material.

[0009] As a further preferred embodiment of the present invention, the conductive polymer is polyaniline or a derivative thereof.

[0010] As a further preferred embodiment of the present invention, the conductive polymer is selected from: polyaniline, poly(o-aminothiophenol), poly(o-phenylenediamine), and poly(o-aminophenol).

[0011] As a further preferred embodiment of the present invention, the matrix perovskite material is ABX3 perovskite material, wherein A is a positive monovalent cation, B is a positive divalent cation, and X is a negative monovalent anion;

[0012] Preferably, in the ABX3 perovskite material:

[0013] The monovalent cation at position A is methylamine cation CH3NH3 +one or more of formamidinium cation CH(NH2)2 + one or more of cesium cation Cs + one or more of methylammonium cation CH3NH3 + one or more of dimethylammonium cation (CH3)2NH2 + one or more of guanidinium cation C(NH2)3 + one or more of formamidinium cation CH(NH2)2 + one or more of formamidinium cation CH(NH2)2 + one or more of formamidinium cation CH(NH2)2 + one or more of formamidinium cation CH(NH2)2

[0014] one or more of lead ion Pb 2+ one or more of tin ion Sn 2+ one or more of copper ion Cu 2+ one or more of germanium ion Ge 2+ one or more of formamidinium cation CH(NH2)2

[0015] one or more of fluorine ion F - one or more of chlorine ion Cl - one or more of bromine ion Br - one or more of iodine ion I - one or more of cyanide ion CN - one or more of thiocyanide ion SCN - one or more of thiocyanide ion SCN

[0016] According to another aspect of the present application, the present application provides a preparation method of the above-mentioned perovskite photoelectric functional material containing conductive polymer, characterized in that, comprising the following steps:

[0017] S1. AX compound and BX2 compound are weighed according to the nominal chemical dosage ratio of perovskite material ABX3;

[0018] S2. The conductive polymer is dissolved in an organic solvent, stirred uniformly until clear and transparent, to obtain an additive solution;

[0019] S3. The sample weighed in step S1 is dissolved in the additive solution obtained in step S2, and stirred uniformly, to obtain a modified perovskite precursor solution;

[0020] S4. The modified perovskite precursor solution obtained in step S3 is used to prepare a modified perovskite material, and after annealing treatment, the perovskite photoelectric functional material containing conductive polymer is obtained.

[0021] As a further preferred embodiment of the present application, the organic solvent is selected from one or more of N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), gamma-butyrolactone (GBL), formamide and N-methylformamide (NMF).

[0022] As a further preferred embodiment of the present application, in step S3, the ratio of the amount of substance of the ABX3 perovskite material to the mass of the conductive polymer in the modified perovskite precursor solution is 1.20 mmol:(0.1-5) mg.

[0023] Preferably, in step S3, the concentration of the ABX3 perovskite material in the modified perovskite precursor solution is 1.20 mol / L; and the concentration of the additive solution is 0.1-5 mg / mL.

[0024] As a further preferred embodiment of the present application, in step S4, the annealing temperature of the annealing treatment is 80-100℃, and the annealing time is 30-40 min.

[0025] According to a further aspect of the present application, the present application provides the use of the above-mentioned perovskite optoelectronic functional material containing a conductive polymer in a solar cell, an organic light-emitting diode or a field effect transistor.

[0026] Preferably, the perovskite optoelectronic functional material containing a conductive polymer is used as a photoactive layer in a solar cell.

[0027] The perovskite optoelectronic functional material containing a conductive polymer 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.

[0028] Compared with the prior art, the above technical scheme conceived by the present application uses a perovskite material (such as an ABX3 perovskite material) as a matrix, and modifies it by adding a conductive polymer with a benzene ring conjugated structure and a carbon-nitrogen single / double bond structure (the carbon-nitrogen single / double bond is formed by a N atom corresponding to a C atom on the benzene ring, which can be a carbon-nitrogen single bond structure or a carbon-nitrogen double bond structure, or can include both a carbon-nitrogen single bond and a carbon-nitrogen double bond), which can passivate defects in the perovskite material, thereby reducing non-radiative recombination of carriers and further improving carrier transport. Moreover, the conductive polymer introduced by the present application has a conjugated structure and does not hinder the transport of carriers in the perovskite, which is significantly different from the prior art passivation agent.

[0029] The introduced conductive polymer structure is ordered, has Lewis base and conductive properties, and the N atom contains an unpaired lone pair of electrons, which is introduced into the perovskite material matrix to passivate defects and further improve the carrier transport effect, and the corresponding modified perovskite material has excellent photoelectric performance and excellent stability. Taking application in a solar cell device as an example, the solar cell prepared based on the modified perovskite photoelectric functional material of the application has been significantly improved in photoelectric conversion efficiency and stability.

[0030] Meanwhile, the modification process of the application is suitable for solution method, which is simple and easy to operate, and the cost is relatively low, so it has a wide prospect in industrial application.

[0031] Specifically, the application can achieve the following beneficial effects:

[0032] (1) The application introduces conductive polymer molecules as a modification component, and the polymer material can interact with the perovskite during crystallization, serving as a bridge to connect different grains, thereby increasing the grain size and cleverly improving the crystal quality of the ABX3 perovskite-based photoelectric functional material.

[0033] The conductive polymer molecules used in the application have a conjugated structure, which can further improve the carrier transport capacity on the basis of passivating defects.

[0034] (2) The conductive polymer molecules introduced in the application have many repeating units and multiple defect passivation sites, which enhance the passivation effect of defects in the perovskite-based photoelectric material. This improvement not only effectively reduces the defects of the material, but also significantly improves the photoelectric performance.

[0035] (3) The modified perovskite-based photoelectric functional material containing conductive polymer molecules described in the application is applied to a solar cell, which has the advantage of ordered polymer long chain structure compared with the unmodified perovskite-based photoelectric functional material. The grown crystal is fixed under the long chain polymer and will not move easily, and the crystallization quality of the perovskite material is improved, so that the device photoelectric conversion efficiency and stability can be significantly improved.

[0036] (4) The introduced conductive polymer can be polyaniline and its derivatives. In addition to the most basic polyaniline, side chain groups (such as mercapto) can be added for modification, and the corresponding polyaniline derivatives are also suitable for modifying the matrix perovskite material. Taking mercapto modification as an example, mercapto can improve the rigidity of polyaniline molecules due to their long conjugated structure, improve the solubility of the corresponding polyaniline derivatives in anti-solvent, and can be introduced by post-treatment passivation method to increase the application scenarios in perovskite solar cells.

[0037] In conclusion, the modified perovskite-based optoelectronic functional material containing conductive polymer molecules obtained by the application has excellent optoelectronic performance and can be applied in various optoelectronic device fields, such as solar cells, organic light-emitting diodes, field effect transistors and electronic components. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is unmodified (CH3NH3)I3 obtained by Comparative Example 1 and (CH3NH3)I3 modified by polyaniline (PANI) obtained by Example 1. 0.4 (CH(NH2)2) 0.6 J-V curves and statistical diagrams of the corresponding solar cell devices of PbI3.

[0039] Figure 2 is unmodified (CH3NH3)I3 obtained by Comparative Example 1 and (CH3NH3)I3 modified by polyaniline (PANI) obtained by Example 1. 0.4 (CH(NH2)2) 0.6 Storage stability test of the corresponding solar cell devices of PbI3 in an air atmosphere without packaging under the condition of 50±5% humidity at room temperature.

[0040] Figure 3 is unmodified (CH3NH3)I3 obtained by Comparative Example 1 and (CH3NH3)I3 modified by ortho-mercapto polyaniline (P2AT) obtained by Example 2. 0.4 (CH(NH2)2) 0.6 Surface morphology of the PbI3 perovskite film. Among them, Figure 3 (a) in corresponds to unmodified (CH3NH3)I3 obtained by Comparative Example 1 0.4 (CH(NH2)2) 0.6 PbI3 perovskite film, Figure 3 (b) in corresponds to P2AT modified (CH3NH3)I3 obtained by Example 2 0.4 (CH(NH2)2) 0.6 PbI3 perovskite film; the scale in the figure represents 1 μm.

[0041] Figure 4 is unmodified (CH3NH3)I3 obtained by Comparative Example 1 and (CH3NH3)I3 modified by ortho-mercapto polyaniline (P2AT) obtained by Example 2. 0.4 (CH(NH2)2) 0.6 X-ray diffraction (XRD) test diagram of the corresponding solar cell devices of PbI3 perovskite solar cells.

[0042] Figure 5 is unmodified (CH3NH3)I3 obtained by Comparative Example 1 and (CH3NH3)I3 modified by ortho-mercapto polyaniline (P2AT) obtained by Example 2. 0.4 (CH(NH2)2) 0.6The corresponding solar cell device J-V curve of PbI3. DETAILED DESCRIPTION

[0043] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not used to limit the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0044] Generally, the preparation method of the modified perovskite-based optoelectronic functional material containing conductive polymer in the present application can include the following steps:

[0045] (1) Prepare a perovskite precursor material, that is, weigh AX compounds (such as at least one of MAX, FAX, and CsX) and BX2 compounds (such as at least one of PbX2 and SnX2) according to the nominal stoichiometric ratio of the perovskite material ABX3;

[0046] For example, AX and PbI2 can be weighed according to the stoichiometric ratio;

[0047] (2) Synthesize conductive polymer molecules according to chemical polymerization. Dissolve an appropriate amount of conductive polymer molecules in an organic solvent, stir until clear, and obtain an additive solution;

[0048] (3) Dissolve the sample of step (1) in the additive solution of step (2) (of course, if the additive solution obtained in step (2) itself has a high concentration, it can also be diluted first, that is, the sample of step (1) is dissolved in a mixed solution of an organic solvent and the additive solution of step (2)), stir until uniform, and obtain a modified perovskite precursor solution;

[0049] (4) Anneal the modified perovskite precursor solution obtained in step (3) to obtain the modified perovskite-based optoelectronic functional material containing conductive polymer.

[0050] In addition, the mesoporous perovskite solar cell constructed in the following examples and Comparative Example 1 has a preparation process as follows: sequentially deposit a dense hole blocking layer, a mesoporous electron transport layer, a mesoporous spacer layer, and a porous counter electrode on a transparent conductive substrate, and finally drop fill the perovskite into the three mesoporous films.

[0051] Wherein:

[0052] The transparent conductive substrate used is fluorine-doped tin oxide (FTO);

[0053] The dense hole blocking layer is dense titanium dioxide;

[0054] The mesoporous electron transport layer is mesoporous titanium dioxide (TiO2) with a thickness of 0.6-0.8 μm;

[0055] The mesoporous spacer layer is zirconium dioxide (ZrO2) with a thickness of 2.0-2.5 μm;

[0056] The porous counter electrode is a porous carbon counter electrode (C) with a thickness of 27-29 μm.

[0057] The following are examples, the polyaniline (PANI) and poly-2-aminothiophenol (P2AT) chemical structure used in the following examples are as follows:

[0058]

[0059] Example 1

[0060] In this example, L is preferably polyaniline (PANI), and ABX3 is preferably (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3, the preparation steps are as follows:

[0061] (1) 0.0764 g of MAI, 0.1240 g of FAI and 0.5532 g of PbI2 powder were weighed;

[0062] (2) DMF and DMSO mixed solvent was prepared according to the volume ratio of DMF:DMSO = 4:1, and stirred until clear and transparent, to obtain the mixed solvent;

[0063] (3) 0.0010 g of PANI was dissolved in 1 mL of DMF and DMSO mixed solvent (volume ratio = 4:1), and stirred until clear and transparent, to obtain an additive solution of 1 mg / mL;

[0064] (4) The mixed solvent of step (2) and the additive solution of step (3) were mixed in a volume ratio of 9:1, while ensuring that the volume of the mixed solution obtained after mixing was 1 mL, and the powder of step (1) was dissolved in it, and stirred uniformly, to obtain a modified perovskite precursor solution; the additive concentration in the modified perovskite precursor solution was 0.1 mg / mL; in this step, the concentration gradient dilution method was used to mix the high-concentration conductive polymer solution with the perovskite precursor solution according to a certain volume ratio, so that the additive amount of the additive in the obtained solution system is more accurate and has a small error;

[0065] (5) 3.7 μL of the modified perovskite precursor solution obtained in step (4) was filled into a carbon counter electrode-based mesoscale solar cell, and annealed at 80°C to obtain a modified perovskite-based solar cell containing conductive polymer molecules.

[0066] (6) At the same time, 40 μL of the modified perovskite precursor solution obtained in step (4) is taken, 100 μL of the anti-solvent chlorobenzene is added dropwise to perform a two-step spin coating method, and annealing treatment is performed at 100°C to obtain a modified perovskite film containing conductive polymer molecules.

[0067] Example 2

[0068] In this embodiment, L is preferably poly-2-aminothiophenol (P2AT), and ABX3 is preferably (CH3NH3)3I 0.4 (CH(NH2)2) 0.6 PbI3, and the specific preparation steps are as follows:

[0069] (1) 0.0764 g of MAI, 0.1240 g of FAI and 0.5532 g of PbI2 powder are weighed;

[0070] (2) A mixed solvent of DMF and DMSO is prepared according to a volume ratio of DMF:DMSO = 4:1, and is stirred until it is clear and transparent to obtain the mixed solvent;

[0071] (3) 0.0100 g of P2AT is dissolved in 1 mL of the mixed solvent of DMF and DMSO (volume ratio = 4:1) to obtain an additive solution of 10 mg / mL, wherein the P2AT is obtained by polymerization according to the prior art, and the specific method is as follows: monomer (2-mercaptobenzene, 0.02 mol) is added to an acidic environment (dissolved in 100 ml of a 0.1 mol / L hydrochloric acid solution) at 0°C, and chemical oxidant ammonium persulfate 0.02 mol (dissolved in 25 ml of a 0.1 mol / L hydrochloric acid solution) is added dropwise at a rate of 3 s / d, and the reaction is stirred for 10 h, and the product is vacuum filtered, washed with acetone, and dried at 60°C for 24 h to obtain the product.

[0072] (4) The mixed solvent of step (2) and the additive solution of step (3) are mixed according to a volume ratio of 9:1, while ensuring that the volume of the mixed solution obtained after mixing is 1 mL, and the powder of step (1) is dissolved in it, and stirred uniformly to obtain a modified perovskite precursor solution; the concentration of the additive in the modified perovskite precursor solution is 1 mg / mL;

[0073] (5) 3.7 μL of the modified perovskite precursor solution obtained in step (4) is filled into a carbon-based electrode mesoscale solar cell, and annealing treatment is performed at 80°C to obtain a modified perovskite-based solar cell containing conductive polymer molecules.

[0074] (6) At the same time, 40 μL of the modified perovskite precursor solution obtained in step (4) is taken, 100 μL of the anti-solvent chlorobenzene is added dropwise to perform a two-step spin coating method, and annealing treatment is performed at 100°C to obtain a modified perovskite film containing conductive polymer molecules.

[0075] Example 3

[0076] In this example, preferably L is poly-2-aminothiophenol (P2AT), and preferably ABX3 is (CH3NH3)I 0.4 (CH(NH2)2) 0.6 PbI3; this example discusses the influence of different additive addition ratios on the performance of the battery device. The operation process is generally similar to that of Example 2, the difference is only that step (4) is mixed according to different volume ratios to obtain a plurality of parallel samples, that is:

[0077] a) Specifically, the mixed solvent of step (2) and the additive solution of step (3) are mixed at a volume ratio of 19:1, while ensuring that the volume of the mixed solution obtained after mixing is 1 mL; the additive concentration in the modified perovskite precursor solution obtained is 0.5 mg / mL; at the same time, the modified perovskite-based solar cell containing conductive polymer molecules obtained after completing step (5) is recorded as sample A;

[0078] b) Specifically, the mixed solvent of step (2) and the additive solution of step (3) are mixed at a volume ratio of 4:1, while ensuring that the volume of the mixed solution obtained after mixing is 1 mL; the additive concentration in the modified perovskite precursor solution obtained is 2 mg / mL; at the same time, the modified perovskite-based solar cell containing conductive polymer molecules obtained after completing step (5) is recorded as sample B;

[0079] c) Specifically, the mixed solvent of step (2) and the additive solution of step (3) are mixed at a volume ratio of 2.3:1, while ensuring that the volume of the mixed solution obtained after mixing is 1 mL; the additive concentration in the modified perovskite precursor solution obtained is 3 mg / mL; at the same time, the modified perovskite-based solar cell containing conductive polymer molecules obtained after completing step (5) is recorded as sample C;

[0080] d) Specifically, the mixed solvent of step (2) and the additive solution of step (3) are mixed at a volume ratio of 1:1, while ensuring that the volume of the mixed solution obtained after mixing is 1 mL; the additive concentration in the modified perovskite precursor solution obtained is 5 mg / mL; at the same time, the modified perovskite-based solar cell containing conductive polymer molecules obtained after completing step (5) is recorded as sample D.

[0081] Comparative Example 1

[0082] In this comparative example, preferably ABX3 is (CH3NH3)I 0.4 (CH(NH2)2) 0.6 PbI3, the specific preparation steps are as follows:

[0083] (1) 0.0764 g MAI, 0.1240 g FAI and 0.5532 g PbI2 were dissolved in 1 mL DMF and DMSO mixed solvent (volume ratio = 4:1) to obtain a precursor solution of 1.2 mol / L;

[0084] (2) 3.7 μL of the perovskite precursor solution (unmodified) obtained in step (1) was filled into a carbon-based counter electrode mesoscopic solar cell, and annealed at 80°C to obtain an unmodified perovskite-based solar cell.

[0085] (3) Meanwhile, 40 μL of the modified perovskite precursor solution obtained in step (1) was added dropwise with 100 μL of anti-solvent chlorobenzene to perform a two-step spin coating method, and annealed at 100°C to obtain an unmodified perovskite thin film.

[0086] Performance detection

[0087] The modified perovskite-based solar cell device containing PANI molecules obtained in Example 1 and the unmodified perovskite-based solar cell device obtained in Comparative Example 1 were tested under the test conditions of a simulated solar light source of 100 mW / cm2. 2 The photoelectric performance of the unmodified and PANI-modified (CH3NH3) 0.4 (CH(NH2)2) 0.6 PbI3 corresponding solar cell devices was detected. The J-V statistical results are shown in Figure 1 The J-V curve results further confirmed that the modified perovskite containing PANI molecules had significantly improved open-circuit voltage (V OC ), short-circuit current (J SC ), and thus the photoelectric conversion efficiency (PCE) was increased from 18.38% of the unmodified perovskite-based solar cell device to 20.24%.

[0088] The modified perovskite-based solar cell device containing PANI molecules obtained in Example 1 and the unmodified perovskite-based solar cell device obtained in Comparative Example 1 were tested under the test conditions of a simulated solar light source of 100 mW / cm2. Figure 2 The experimental results showed that the PANI-modified sample had significant advantages. The effect of PANI on the moisture resistance in the air at room temperature and relative humidity of 45-55% was evaluated by periodically measuring the unsealed perovskite-based solar cell device. As shown in Figure 2As shown, the two curves will be obviously diverged after 1030 hours, and the device modified with PANI maintained 97% efficiency after 1500 hours, while the unmodified device decreased by 10% efficiency in the same period.

[0089] The unmodified and P2AT modified (CH3NH3) 0.4 (CH(NH2)2) 0.6 The surface morphology of PbI3perovskite film was tested by SEM, and the results are shown in Figure 3 As shown, the grain size of the modified perovskite is increased, indicating that the quality of the modified perovskite crystal containing conductive polymer molecules is improved. To explore whether the quality of the perovskite in the device is improved, we tested the X-ray diffraction (XRD) of the perovskite solar cell device containing P2AT molecule modified and unmodified. The test results are shown in Figure 4 , the peak position is unchanged, and the peak intensity is increased. This shows that polyaniline does not enter the lattice, but promotes the crystallization of perovskite, which further indicates that the crystallization of perovskite in the device is improved.

[0090] The P2AT molecule modified perovskite-based solar cell device obtained in Example 2 and the unmodified perovskite-based solar cell device obtained in Comparative Example 1 were tested under the test conditions of a simulated sunlight source of 100 mW / cm 2 0.4 0.6 The photoelectric performance of the corresponding solar cell device of PbI3was detected. As shown in Table 1 and Figure 5 The J-V curve results further confirm that the modified perovskite containing P2AT molecules has significantly improved open-circuit voltage (V OC ), short-circuit current (J SC ), thereby increasing the photoelectric conversion efficiency (PCE) from 18.38% of the unmodified perovskite-based solar cell device to 19.71%.

[0091] Table 1: The unmodified and P2AT modified (CH3NH3) 0.4 (CH(NH2)2) 0.6 Comparison table of photoelectric performance of corresponding solar cell device of PbI3

[0092] V OC (mV) J SC (A / cm 2 )]]> FF (%) Efficiency (%) Unmodified 972 23.98 78.9 18.38 P2AT modified 1006 24.58 79.7 19.71

[0093] Similarly, the photoelectric performance of the battery A, B, C, D samples obtained in Example 3 was detected, and their photoelectric performance was not as good as that of Example 2, but still better than that of Comparative Example 1. ​​

[0094] The above embodiments are only examples, for example, the conductive polymer is not limited to poly-o-mercapto-polyaniline, and can also be other materials, such as polyaniline and derivatives thereof, etc., as long as they contain a benzene ring conjugated structure, and the C atom on the benzene ring also forms a carbon-nitrogen single / double bond structure with the N atom; for example, polyaniline, polyaniline doped with different acids (hydrochloric acid-doped polyaniline, sulfonic acid-doped polyaniline, phytic acid-doped polyaniline, phosphoric acid-doped polyaniline), poly-o-phenylenediamine, poly-o-aminophenol; of course, the introduced conductive polymer molecules can contain both oxidation units and reduction units, and exhibit certain redox capacity (for example, when X is iodine in ABX3, when the introduced conductive polymer molecules can contain both oxidation units and reduction units, the escape of iodine can be effectively reduced, and the working stability of the device can be further improved). For another example, the organic solvent used in the preparation process can also be one or more of N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), gamma butyrolactone (GBL), formamide and N-methyl formamide (NMF), and other organic solvents capable of dissolving ABX3 perovskite material and conductive polymer; for another example, the preparation of the conductive polymer can refer to the prior art, and the corresponding monomer is added to a chemical oxidizing agent under stirring at 0°C in an acidic environment, the product is vacuum filtered, washed with acetone, and then vacuum dried at 60°C.

[0095] Those skilled in the art will readily understand that the above description is only of the preferred embodiments of the present application and is not intended to limit the present application, and any modifications, equivalent replacements and improvements made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A perovskite optoelectronic functional material containing a conductive polymer capable of improving open-circuit voltage, characterized in that, It is obtained by modifying a perovskite material matrix by adding a conductive polymer to the matrix; wherein... The conductive polymer contains a conjugated benzene ring structure, and the C atoms on the benzene ring also form carbon-nitrogen single bonds and / or double bonds with N atoms. The conductive polymer is polyaniline, and the matrix perovskite material ABX3 is (CH3NH3). 0.4 (CH(NH2)2) 0.6 For every 1.20 mmol of PbI3 matrix perovskite material, 0.1 mg of conductive polymer is added.

2. A perovskite optoelectronic functional material containing a conductive polymer capable of improving open-circuit voltage, characterized in that, It is obtained by modifying a perovskite material matrix by adding a conductive polymer to the matrix; wherein... The conductive polymer contains a conjugated benzene ring structure, and the C atoms on the benzene ring also form carbon-nitrogen single bonds and / or double bonds with N atoms. The conductive polymer is o-thiol polyaniline, and the matrix perovskite material ABX3 is (CH3NH3). 0.4 (CH(NH2)2) 0.6 For every 1.20 mmol of PbI3 matrix perovskite material, 1 mg of conductive polymer is added.

3. The method for preparing perovskite optoelectronic functional materials containing conductive polymers capable of improving open-circuit voltage as described in claim 1 or 2, characterized in that, Includes the following steps: S1. Weigh the AX compound and BX2 compound according to the nominal chemical ratio of the perovskite material ABX3; S2. Dissolve the conductive polymer in an organic solvent and stir until it is clear and transparent to obtain an additive solution; S3. Dissolve the sample weighed in step S1 in the additive solution obtained in step S2, stir evenly, and obtain a modified perovskite precursor solution; in the modified perovskite precursor solution, the mass ratio of ABX3 perovskite material to conductive polymer is 1.20 mmol: 0.1 mg or 1.20 mmol: 1 mg; S4. Using the modified perovskite precursor solution obtained in step S3, a modified perovskite material is prepared. After annealing, a perovskite optoelectronic functional material containing a conductive polymer is obtained.

4. The preparation method according to claim 3, characterized in that, The organic solvent is selected from one or more of N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), gamma-lactone (GBL), formamide, and N-methylformamide (NMF).

5. The preparation method according to claim 3, characterized in that, In the modified perovskite precursor solution, the concentration of ABX3 perovskite material is 1.20 mol / L; the concentration of the additive solution is 0.1 mg / mL.

6. The preparation method according to claim 3, characterized in that, In step S4, the annealing temperature is 80~100℃ and the annealing time is 30~40 min.

7. The application of the perovskite optoelectronic functional material containing conductive polymer that can improve open-circuit voltage as described in claim 1 or 2 in solar cells, organic light-emitting diodes or field-effect transistors.

8. The application as described in claim 7, characterized in that, The perovskite optoelectronic functional material containing conductive polymer is used as a photoactive layer in solar cells; The perovskite optoelectronic functional material containing conductive polymer is used as an n-type semiconductor material or a p-type semiconductor material in organic light-emitting diodes or field-effect transistors.

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