Organic-inorganic hybrid perovskite microcrystal, preparation method and application thereof

Abstract

The application provides an organic-inorganic hybrid perovskite microcrystal and a preparation method and application thereof, and relates to the technical field of crystal synthesis. The preparation method comprises the following steps: according to a measurement number, mixing lead bromide, methylamine hydrobromide / cesium bromide and phenethylamine hydrobromide / phenylpropylamine bromide in a set molar ratio, adding two mutually soluble benign solvents, and dissolving to obtain an organic-inorganic hybrid perovskite precursor solution; coating the organic-inorganic hybrid perovskite precursor solution on a substrate, and then exposing to an anti-solvent atmosphere, and crystallizing to obtain an organic-inorganic hybrid perovskite microcrystal. The obtained microcrystal has the structural characteristics of two-dimensional perovskite, single-phase quasi-two-dimensional perovskite and three-dimensional perovskite. The crystal can simultaneously give full play to the advantages of different dimensional perovskites, such as the high stability of two-dimensional perovskite, the tunability of the luminescence wavelength of quasi-two-dimensional perovskite, and the high-efficiency photoelectric conversion capacity of three-dimensional perovskite.

Description

Technical Field

[0001] This invention relates to the field of crystal synthesis technology, and in particular to an organic-inorganic hybrid perovskite micron crystal, its preparation method, and its application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Organic-inorganic hybrid perovskite materials integrate the properties of organic and inorganic materials at the molecular scale, resulting in excellent photoelectric properties such as simple preparation methods, high carrier mobility, and tunable emission wavelength. They are widely used in optoelectronic devices such as solar cells, photodetectors, and light-emitting diodes. In particular, the power conversion efficiency (PCE) of solar cells based on three-dimensional organic-inorganic hybrid perovskites has reached 26.7% over the past decade. However, the organic components in three-dimensional organic-inorganic perovskite materials are extremely unstable in humid air and easily decompose, severely restricting the further development and practical application of this material.

[0004] Two-dimensional and single-phase quasi-two-dimensional perovskite materials have more organic hydrophobic groups, thus exhibiting higher air stability compared to three-dimensional perovskite materials. However, due to the effects of quantum confinement and dielectric confinement, two-dimensional and single-phase quasi-two-dimensional perovskites have relatively large exciton binding energies. These large exciton binding energies are not conducive to exciton dissociation, which to some extent restricts their application in fields such as photodetectors. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide an organic-inorganic hybrid perovskite microcrystal, its preparation method, and its application. This invention develops microcrystals containing two-dimensional, single-phase quasi-two-dimensional, and three-dimensional perovskite characteristics. These microcrystals not only retain the good air stability of two-dimensional perovskites but also retain the advantages of tunable emission peaks of quasi-two-dimensional perovskites and good photodetection performance of three-dimensional perovskites.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] In a first aspect, a method for preparing organic-inorganic hybrid perovskite microcrystals includes the following steps:

[0008] S1. According to the stoichiometric coefficients in the general formula of organic-inorganic hybrid perovskite, a mixture of three components in a set molar ratio, namely lead bromide (PbBr2), methylamine hydrobromic acid (MABr) and cesium bromide (CsBr), and phenethylamine hydrobromic acid (PEABr) and phenylpropylamine bromide (PhPABr), is added to dissolve and obtain an organic-inorganic hybrid perovskite precursor solution.

[0009] S2. The organic-inorganic hybrid perovskite precursor solution is coated onto the substrate and then exposed to an antisolvent atmosphere to crystallize and obtain organic-inorganic hybrid perovskite micron crystals.

[0010] The general formula of the organic-inorganic hybrid perovskite is A2B. n-1 Pb n Br 3n+1 , ∞>n>1, where A + Cs is a cesium cation. + or methylamine cation MA + B + Phenethylamine cationic PEA + or amphetamine cationic PhPA + .

[0011] Secondly, the organic-inorganic hybrid perovskite microcrystals prepared by the above-mentioned method simultaneously possess the structural characteristics of two-dimensional perovskite, single-phase quasi-two-dimensional perovskite, and three-dimensional perovskite.

[0012] Thirdly, the aforementioned organic-inorganic hybrid perovskite microcrystals have applications in the optoelectronic field.

[0013] The beneficial effects of this invention are as follows:

[0014] 1. This invention prepares a precursor solution based on the molar ratio required for quasi-two-dimensional perovskite crystals. The precursor solution is placed in an antisolvent atmosphere, allowing the antisolvent to diffuse into the precursor solution and initiate perovskite crystallization. Utilizing the differences in solubility and volatility of the two solvents, the formation of perovskites of different dimensions, such as two-dimensional and quasi-two-dimensional, is ensured. This results in organic-inorganic hybrid perovskite micron-sized crystals possessing two-dimensional, single-phase quasi-two-dimensional, and three-dimensional characteristics during the crystallization process. These crystals can simultaneously leverage the high stability of two-dimensional perovskites, the tunable emission wavelength of quasi-two-dimensional perovskites, and the high photoelectric conversion efficiency of three-dimensional perovskites, overcoming the shortcomings of organic-inorganic hybrid perovskites that only possess single-dimensional characteristics.

[0015] 2. This invention allows for the control of the composition ratio of perovskite of different dimensions in the resulting perovskite crystal by adjusting the molar ratio of the precursor material in the precursor solution. This flexibility enables researchers to prepare materials with specific photoelectric properties to meet the specific needs of different application fields such as solar cells and photodetectors. The preparation process does not require complex synthesis steps or expensive equipment, thus this method is highly economical and practical, providing strong technical support for the widespread application of perovskite-based photoelectric materials. Attached Figure Description

[0016] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0017] Figure 1 These are microscopic images of the organic-inorganic hybrid perovskite microcrystals prepared in Example 1, where (a) is an optical microscopic image and (b) is a fluorescence microscopic image.

[0018] Figure 2 The photoluminescence (PL) spectrum of the organic-inorganic hybrid perovskite microcrystal prepared in Example 1 is shown. Detailed Implementation

[0019] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0020] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0021] In the following specific embodiments, the reagents used include:

[0022] Methylamine hydrobromide (MABr), also known as methylamine hydrobromide or methylammonium bromide, CAS No.: 6876-37-5.

[0023] Phenethylamine hydrobromide (PEABr), also known as phenylethylamine bromide, CAS No.: 53916-94-2.

[0024] Phenylambromine (PhPABr), also known as phenylpropylamine bromide, CAS No.: 120375-53-3.

[0025] γ-Butyrolactone, also known as 1,4-butyrolactone, CAS No.: 96-48-0.

[0026] Dimethyl sulfoxide (DMSO), also known as dimethyl sulfoxide, CAS number: 67-68-5.

[0027] N,N-Dimethylformamide, CAS No.: 68-12-2.

[0028] A method for preparing organic-inorganic hybrid perovskite microcrystals, comprising the following steps:

[0029] S1, according to the general formula A2B of organic-inorganic hybrid perovskites. n-1 Pb n Br 3n+1 The stoichiometric ratio of lead bromide (PbBr2), methylamine hydrobromic acid (MABr) (or cesium bromide (CsBr)) and phenethylamine hydrobromic acid (PEABr) (or phenethylamine bromide (PhPABr)) is set, and then two miscible good solvents are added to dissolve and obtain an organic-inorganic hybrid perovskite precursor solution.

[0030] S2. The organic-inorganic hybrid perovskite precursor solution is coated onto the substrate and then exposed to an antisolvent atmosphere to crystallize and obtain organic-inorganic hybrid perovskite micron-sized crystals.

[0031] In the above process, an anti-solvent method is used to prepare organic-inorganic hybrid perovskite microcrystals. The mutual volatilization between solvents causes the perovskite crystals to precipitate. By adjusting the molar ratio of the precursor material in the precursor solution, the dimensional distribution and composition ratio of the obtained perovskite crystals can be controlled, thereby obtaining organic-inorganic hybrid perovskite microcrystals with two-dimensional, single-phase quasi-two-dimensional and three-dimensional characteristics.

[0032] Optionally, in S1, two benign solvents can be selected, one of which is dimethyl sulfoxide, and the other is selected from any one of γ-butyrolactone, acetonitrile, and N,N-dimethylformamide (DMF). By utilizing the differences in volatility and solubility of the two solvents, the precipitation of perovskites of different dimensions can be ensured, thereby obtaining perovskite micron crystals including two-dimensional, single-phase quasi-two-dimensional, and three-dimensional perovskite.

[0033] Optionally, in S1, the volume ratio of the two benign solvents is 1:(0.5 to 1.5). By adjusting the volume ratio of the two benign solvents, organic-inorganic hybrid perovskite micron crystals with different composition ratios can be obtained.

[0034] Optionally, in S1, the dissolution method includes: stirring at a speed of 1500-2000 r / min for 1-2 h using a magnetic stirrer to fully dissolve the crystal powders of the three raw materials: lead bromide (PbBr2), methylamine hydrobromic acid (MABr), cesium bromide (CsBr), phenethylamine hydrobromic acid (PEABr), and phenylpropylamine bromide (PhPABr), and to obtain a precursor solution.

[0035] Optionally, in S1, the dissolution process is carried out at a temperature of 60–70°C to ensure the homogeneity and stability of the solution.

[0036] Optionally, in S1, the concentration of the organic-inorganic hybrid perovskite precursor solution is 0.1–1 mol / L, so as to obtain micron-sized crystals by drop coating.

[0037] Optionally, in S2, the substrate can be a glass substrate or an ITO substrate, which are commonly used substrates for preparing perovskite crystals.

[0038] Optionally, in S2, 10–20 μL of perovskite precursor solution is precisely measured and dropped onto the substrate. The larger the volume of the dropped perovskite precursor solution, the larger the required substrate. When 10 μL of perovskite precursor solution is dropped, the required substrate area is not less than 1.5 × 1.5 cm.

[0039] Optionally, in S2, the antisolvent is selected from diethyl ether and ethyl acetate. In a semi-sealed environment, the volatile antisolvent diffuses into the drop-coated perovskite precursor solution, gradually reducing the solubility of the solution, thereby initiating the crystallization of the perovskite crystal.

[0040] Optionally, in S2, the crystallization process is carried out at a temperature of 18–22°C. The temperature control range does not require expensive equipment investment, which is highly economical and practical.

[0041] Optionally, in S2, the crystallization time is 22–26 hours.

[0042] The organic-inorganic hybrid perovskite microcrystals prepared by the above method contain perovskites of different dimensions and simultaneously possess the structural characteristics of two-dimensional perovskites, single-phase quasi-two-dimensional perovskites, and three-dimensional perovskites.

[0043] Optionally, the organic-inorganic hybrid perovskite microcrystal has a width of 10–90 μm and a length of 20–300 μm.

[0044] This crystal pack simultaneously incorporates features of two-dimensional, single-phase quasi-two-dimensional, and three-dimensional perovskites, retaining the advantages of each dimension while compensating for their respective shortcomings. This ingenious structural design not only enhances the overall stability of the crystal but also enables the resulting micron-sized crystal to exhibit superior performance in optoelectronic applications. The stability of the two-dimensional perovskite ensures the long-term reliability of the device, while the tunable emission wavelength of the quasi-two-dimensional perovskite makes it possible to realize multi-color displays and photodetectors. The high-efficiency photoelectric conversion capability of the three-dimensional perovskite significantly improves the performance of optoelectronic devices such as solar cells.

[0045] The aforementioned organic-inorganic hybrid perovskite micron-crystals have applications in the optoelectronic field, including solar cells, light-emitting diodes (LEDs), lasers, photodetectors and optical sensors, photocatalysis, image sensors, memory storage, and optical communication.

[0046] Example 1

[0047] A method for preparing organic-inorganic hybrid perovskite microcrystals includes the following steps:

[0048] S0. Dry the cleaned glass substrate with nitrogen gas and set aside for later use.

[0049] S1. Take n = 5, according to the general formula of organic-inorganic hybrid perovskite (PEA)2(MA)4Pb5Br 16 The mass of lead bromide (PbBr2), methylamine hydrobromide (MABr), and phenylethylamine hydrobromide (PEABr) was determined according to a molar ratio of 5:4:2, and the powdered raw materials were weighed. After mixing the weighed raw materials, γ-butyrolactone and dimethyl sulfoxide were added at a volume ratio of 1:1. The mixture was stirred at 1500 r / min for 3 h at 70 °C to dissolve the mixture and prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.2 mol / L.

[0050] S2. At 20°C, 10 μL of an organic-inorganic hybrid perovskite precursor solution was dropped onto a glass substrate. The substrate was then placed in a reaction flask containing 1 / 3 of its volume of diethyl ether, with the glass substrate and the ether surface at a predetermined distance to form a semi-sealed state. This exposed the organic-inorganic hybrid perovskite precursor solution to an antisolvent atmosphere, promoting the diffusion of the volatilized diethyl ether into the precursor solution. After standing for 24 hours, crystallization was performed to obtain organic-inorganic hybrid perovskite micron-sized crystals.

[0051] Example 2

[0052] A method for preparing organic-inorganic hybrid perovskite micron-crystals differs from Example 1 in that:

[0053] In S1, n=2. Based on the stoichiometric coefficients in the general formula (PEA)2MAPb2Br7 of organic-inorganic hybrid perovskite, the masses of lead bromide PbBr2, methylamine hydrobromide MABr, and phenylethylamine hydrobromide PEABr are determined and weighed according to a molar ratio of 2:1:2. The weighed raw materials are mixed, and γ-butyrolactone and dimethyl sulfoxide are added at a volume ratio of 1:0.5 to prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.5 mol / L.

[0054] All other reagents / materials and preparation methods used were the same as in Example 1.

[0055] Example 3

[0056] A method for preparing organic-inorganic hybrid perovskite micron-crystals differs from Example 1 in that:

[0057] In S1, n = 3 is taken, and according to the general formula of organic-inorganic hybrid perovskite (PEA)2MA2Pb3Br 10 The mass of lead bromide (PbBr2), methylamine hydrobromide (MABr), and phenylethylamine hydrobromide (PEABr) was determined and weighed according to a molar ratio of 3:2:2 to prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.3 mol / L.

[0058] All other reagents / materials and preparation methods used were the same as in Example 1.

[0059] Example 4

[0060] A method for preparing organic-inorganic hybrid perovskite micron-crystals differs from Example 1 in that:

[0061] In S1, n = 5 is taken, and according to the general formula (PEA)2Cs4Pb5Br of organic-inorganic hybrid perovskites. 16 The mass of lead bromide (PbBr2), cesium bromide (CsBr), and phenylethylamine hydrobromic acid (PEABr) was determined and weighed according to a molar ratio of 5:4:2 to prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.2 mol / L.

[0062] All other reagents / materials and preparation methods used were the same as in Example 1.

[0063] Example 5

[0064] A method for preparing organic-inorganic hybrid perovskite micron-crystals differs from Example 1 in that:

[0065] In S1, n = 5 is taken, and according to the general formula of organic-inorganic hybrid perovskite (PhPA)2MA4Pb5Br 16The mass of lead bromide (PbBr2), methylamine hydrobromic acid (MABr), and phenylamine bromide (PhPABr) was determined and weighed according to a molar ratio of 5:4:2 to prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.2 mol / L.

[0066] All other reagents / materials and preparation methods used were the same as in Example 1.

[0067] Example 6

[0068] A method for preparing organic-inorganic hybrid perovskite micron-crystals differs from Example 1 in that:

[0069] In S1, n = 5 is taken, and according to the general formula (PhPA)2Cs4Pb5Br of organic-inorganic hybrid perovskites... 16 The mass of lead bromide (PbBr2), cesium bromide (CsBr), and phenylpropylamine bromide (PhPABr) was determined and weighed according to a molar ratio of 5:4:2 to prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.2 mol / L.

[0070] All other reagents / materials and preparation methods used were the same as in Example 1.

[0071] Performance testing

[0072] The organic-inorganic hybrid perovskite microcrystals obtained in Example 1 were examined, and the optical microscopic images are as follows: Figure 1 As shown in (a), it can be seen that the micron-sized crystals are basically elongated strips of 40 × 100 μm; the fluorescence micrograph is as follows. Figure 1 As shown in (b), it can be seen that the central position of the crystal mainly emits green fluorescence, the upper surface of the material also emits a small amount of blue light, and other positions mainly emit pale blue fluorescence. That is, the same perovskite crystal material emits light of different colors, proving that the crystal contains the characteristics of perovskite in multiple dimensions.

[0073] The photoluminescence (PL) spectrum of the micron-sized crystal obtained in Example 1 was detected, and the results are as follows: Figure 2 As shown, it can be seen that it emits multiple peaks, further proving that the crystal prepared in this embodiment is a multifunctional organic-inorganic hybrid perovskite microcrystal that simultaneously contains two-dimensional, single-phase quasi-two-dimensional, and three-dimensional perovskites. The position of the emission peaks can be adjusted by adjusting the composition of the organic-inorganic hybrid perovskite precursor. At the same time, adjusting the molar ratio of the precursor material can also adjust the proportion of perovskite components in different dimensions, thereby changing the emission wavelength of the organic-inorganic hybrid perovskite microcrystal.

[0074] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing organic-inorganic hybrid perovskite micron-crystals, characterized in that the steps include... include: S0. Dry the cleaned glass substrate with nitrogen gas and set aside for later use. S1, according to the general formula of organic-inorganic hybrid perovskite (PEA)2(MA)4Pb5Br 16 The mass of lead bromide (PbBr2), methylamine hydrobromide (MABr), and phenylethylamine hydrobromide (PEABr) was determined according to a molar ratio of 5:4:2, and the powdered raw materials were weighed. After mixing the weighed raw materials, γ-butyrolactone and dimethyl sulfoxide were added at a volume ratio of 1:

1. The mixture was stirred at 1500 r / min for 3 h at 70 °C to dissolve the mixture and prepare an organic-inorganic hybrid perovskite precursor solution with a concentration of 0.2 mol / L. S2. At 20°C, 10 μL of an organic-inorganic hybrid perovskite precursor solution was dropped onto a glass substrate. The substrate was then placed in a reaction flask containing 1 / 3 of its volume of diethyl ether, with the glass substrate and the ether surface at a predetermined distance to form a semi-sealed state. This exposed the organic-inorganic hybrid perovskite precursor solution to an antisolvent atmosphere, promoting the diffusion of the volatilized diethyl ether into the precursor solution. After standing for 24 hours, crystallization was performed to obtain organic-inorganic hybrid perovskite micron-sized crystals.

2. An organic-inorganic hybrid perovskite microcrystal prepared by the method described in claim 1, characterized in that, It simultaneously possesses structural characteristics of two-dimensional perovskite, single-phase quasi-two-dimensional perovskite, and three-dimensional perovskite.

3. An application of the organic-inorganic hybrid perovskite microcrystal as described in claim 2 in the field of optoelectronics.

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