Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photoelectric functional materials, and relates to a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal as well as a preparation method and application thereof. The chiral hybrid perovskite crystal is a non-centrosymmetric P212121 space group of an orthorhombic crystal system, and has the advantages of shortened inorganic interlayer spacing, eliminated interlayer Van der Waals gaps and excellent structural stability. The specific synthesis method comprises the following steps: completely dissolving the lead-based semiconductor in a haloid acid solution; adding chiral diamine organic molecules into the solution, and heating to completely dissolve the chiral diamine organic molecules; standing, and carrying out gradient cooling to room temperature to obtain millimeter-scale crystals; and after washing, putting into a vacuum drying oven for drying, so as to obtain the Dion-Jacobson type organic-inorganic hybrid chiral perovskite single crystal. The obtained single crystal has a non-centrosymmetric structure, shows strong chiral characteristics, and can be applied to the fields of circularly polarized photoelectric detectors, circularly polarized luminescence, light emitting diodes, displays, nonlinear optics and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of optoelectronic functional materials, and specifically relates to a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal, a preparation method and application thereof in the field of optoelectronic devices. Background Art

[0002] In 2D hybrid chiral perovskites, chiral organic cations divide metal halide octahedra into 2D layered structures. Currently, 2D hybrid chiral perovskites are the most widely studied and developed. In 2D hybrid chiral perovskites, inorganic octahedral layers are alternately arranged with monoamine or diamine chiral organic cations to obtain Ropper-Ruddlesden and Dion-Jacobson hybrid chiral perovskites, respectively. Different interlayer cations in Ropper-Ruddlesden and Dion-Jacobson hybrid chiral perovskites lead to different chemical bonds and different structures, which also give Ropper-Ruddlesden and Dion-Jacobson hybrid chiral perovskites different chemical and physical properties. There are two layers of hydrophobic monoamine chiral organic cations between the inorganic layers of Ropper-Ruddlesden hybrid chiral perovskites. The van der Waals gap between the inorganic layers not only hinders the transport of carriers, but also affects the stability of the device and the circularly polarized light detection performance. By introducing diamine chiral organic cations with amino groups at both ends, a more compact Dion-Jacobson chiral perovskite can be synthesized. The diamine chiral organic cation interacts with the inorganic octahedral layer through hydrogen bonds at both ends, shortening the distance between the inorganic layers while avoiding relative slip between the inorganic layers, showing high structural stability and good thermal stability. With the elimination of the van der Waals gap between the layers, the carrier transport of the Dion-Jacobson chiral perovskite along the out-of-plane is also improved, so it is expected to show great application potential in high-sensitivity and high-stability photodetectors.

[0003] However, in current research, the application of Dion-Jacobson perovskites is limited to the detection of linear polarized light, natural light and X-rays, and it is necessary to expand their application in the field of circularly polarized light (CPL) detection. Summary of the invention

[0004] The present invention designs and prepares Dion-Jacobson type two-dimensional hybrid chiral perovskite single crystals, which have the advantages of eliminated interlayer van der Waals gap, shortened interlayer spacing, enhanced structural stability, strong chiral characteristics and excellent out-of-plane carrier transmission efficiency, and show excellent ability to distinguish right-handed circularly polarized light (RCP) and left-handed circularly polarized light (LCP), and have great application prospects in the field of circularly polarized photoelectric detection.

[0005] One of the purposes of the present invention is to provide a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal; the second purpose of the present invention is to provide a method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal; the third purpose of the present invention is to provide (R / S-3AMPY)PbX 4 and (R / S-4AMPY)PbX 4 Application of (X=I, Br) chiral perovskite single crystals in optoelectronic devices.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] Before the present invention is described in detail, the abbreviations of the professional terms used in the present invention are first defined as follows: (R)-1-(3-pyridyl)ethylamine is abbreviated as "R-3AMPY", (S)-1-(3-pyridyl)ethylamine is abbreviated as "S-3AMPY", (R)-1-(4-pyridyl)ethylamine is abbreviated as "R-4AMPY", (S)-1-(4-pyridyl)ethylamine is abbreviated as "S-4AMPY". The structures of the chiral diamine organic molecules R / S-3AMPY and R / S-4AMPY are shown below:

[0008]

[0009] The present invention provides a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal, wherein the chemical formula of the chiral perovskite is (R / S-3AMPY)PbX 4 and (R / S-4AMPY)PbX 4 (X=I, Br). The single crystal material has a non-centrosymmetric structure and intrinsic chirality. It has excellent ability to distinguish circularly polarized light, and its anisotropy factor can reach 0.6.

[0010] Crystals I, II, V and VI are red crystals, crystals III and IV are light yellow crystals, all of which are orthorhombic crystals and non-centrosymmetric P2 1 2 1 2 1 Space Group:

[0011] Crystal I, (R-3AMPY)PbI 4 , its unit cell parameters are: α=90°, β=90°, γ=90°.

[0012] Crystal II, (S-3AMPY)PbI 4 , its unit cell parameters are: α=90°, β=90°, γ=90°;

[0013] Crystal III, (R-3AMPY)PbBr 4 , its unit cell parameters are: α=90°, β=90°, γ=90°;

[0014] Crystal IV, (S-3AMPY)PbBr 4 , its unit cell parameters are: α=90°, β=90°, γ=90°.

[0015] Crystalline V, (R-4AMPY)PbI 4 , its unit cell parameters are: α=90°, β=90°, γ=90°.

[0016] Crystal VI, (S-4AMPY)PbI 4 , its unit cell parameters are: α=90°, β=90°, γ=90°.

[0017] The above (R / S-3AMPY)PbX 4 and (R / S-4AMPY)PbX 4 (X=I, Br) has shortened inorganic interlayer spacing, eliminated interlayer van der Waals gap and excellent structural stability. 2+ ion and the six adjacent Br - or I - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by Br - or I - The inorganic layered structure is formed by ionic connection. The inorganic octahedral layer interacts with the diamine organic cation R / S-3AMPY or R / S-4AMPY through hydrogen bonds.

[0018] The present invention provides a method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal, which is synthesized using chiral diamine organic molecules and lead-based semiconductors as raw materials. The obtained single crystal is a non-centrosymmetric two-dimensional hybrid chiral perovskite material that exhibits strong chiral characteristics. Specifically, the method comprises the following steps:

[0019] (1) The lead-based semiconductor is completely dissolved in a hydrohalic acid solution to obtain a clear solution; specifically, the lead-based semiconductor can be completely dissolved in the hydrohalic acid solution by heating.

[0020] (2) Then, a chiral diamine organic molecule is added to the solution obtained in the above (1) to completely dissolve the chiral diamine organic molecule to obtain a clear solution; specifically, heating can be used to completely dissolve the chiral diamine organic molecule in the solution obtained in (1).

[0021] (3) After standing for a period of time, the temperature is gradually lowered to room temperature. As the solution temperature decreases, millimeter-sized crystals are precipitated;

[0022] (4) The crystal obtained in (3) is washed multiple times with a weakly polar solvent and dried in a vacuum drying oven to obtain a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal.

[0023] Among them, the lead-based semiconductor is PbI 2 、PbBr 2 and PbO. The hydrohalic acid solution is one or both of hydroiodic acid solution and hydrobromic acid solution. The concentration of the hydroiodic acid solution is 47-58 wt.%, and the concentration of the hydrobromic acid solution is 33-48 wt.%. The heating temperature is 90-200°C.

[0024] The chiral diamine organic molecule is any one of R / S-3AMPY and R / S-4AMPY, and the molar ratio of the chiral diamine organic molecule to the lead-based semiconductor is 1:0.25-4. The standing time is 2-12 hours. The cooling rate is 0.1-5°C / h. The weak polar solvent is one or more of cyclohexane, n-hexane, isopropanol, and ether. The vacuum drying temperature is 40-80°C.

[0025] The present invention provides the application of the Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal in circularly polarized photodetectors, light-emitting diodes and displays.

[0026] The present invention also provides a method for constructing a circularly polarized photodetector based on a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal, comprising the following steps:

[0027] (1) dissolving the Dion-Jacobson type organic-inorganic hybrid chiral perovskite single crystal prepared above in a benign solvent and heating it sufficiently to obtain a corresponding precursor solution;

[0028] (2) Dropping the precursor solution onto the cleaned substrate surface, and immediately placing the sample on a 120° C. heating table for annealing for 15 min after spin coating, thereby obtaining an organic-inorganic hybrid chiral perovskite film; the spin coating is specifically performed by using a spin coater at a low speed of 1000 rpm / min for 10 s, and then at a high speed of 5000 rpm / min for 30 s.

[0029] (3) The prepared film is placed in a three-target high vacuum magnetron sputtering apparatus to sputter a gold electrode, thereby obtaining a photodetector based on a Dion-Jacobson type organic-inorganic hybrid chiral perovskite film.

[0030] The benign solvent is one or both of N,N-dimethylformamide and dimethyl sulfoxide. The concentration of the precursor solution is 0.5-2 mmol / mL. The substrate is soda-lime glass, SiO 2 / Si, Si or PET and other common substrates.

[0031] The present invention provides the application of the above-mentioned Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal in circularly polarized luminescence, nonlinear optics, remote communication or information processing.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The invention provides a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal. The preparation method of the single crystal is simple, and the obtained crystal has high crystal quality.

[0034] The Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal of the present invention has a non-centrosymmetric structure and intrinsic chirality. Compared with the Ropper-Ruddlesden type perovskite, it has better stability and stronger carrier transport ability, exhibits excellent circularly polarized light differentiation ability, and the anisotropy factor can reach 0.6. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 (R-3AMPY)PbBr 4 Single crystal picture.

[0036] Figure 2 (R-3AMPY)PbBr 4 (a) and (S-3AMPY)PbBr 4 (b) Crystal structure diagram.

[0037] Figure 3 (R-3AMPY)PbBr 4 (a) and (R-3AMPY)PbI 4 (b) XRD pattern of.

[0038] Figure 4 (R-3AMPY)PbBr 4 (a) and (R-3AMPY)PbI 4 (b) SEM image of the interior of the crystal.

[0039] Figure 5 (R-3AMPY)PbBr 4 (a) and (R-3AMPY)PbI 4 (b) Thermogravimetric analysis diagram of .

[0040] Figure 6 Schematic diagram of performance test of circularly polarized photodetectors obtained in Examples 1, 3 and 5 of the present invention.

[0041] Figure 7 Based on (R-3AMPY)PbBr 4 The circularly polarized photodetector has a wavelength of 325 nm and a light intensity of 20 μW / cm 2 IV curves under circularly polarized light.

[0042] Figure 8 Based on (R-MBA) 2 PbI 4 The circularly polarized photodetector has a wavelength of 532nm and a light intensity of 20μW / cm 2 IV curves under circularly polarized light.

[0043] Fig. 9 (R / S-3AMPY)PbBr 4 (a), (R / S-3AMPY)PbI 4 (b) and (R / S-4AMPY)PbI 4 (c) Circular dichroism spectrum.

[0044] Fig.10 This is the circular dichroism spectrum of R / S-3AMPY.

[0045] Fig.11 (R-3AMPY)PbI 4 Single crystal picture.

[0046] Fig.12 (R-3AMPY)PbI 4 (a) and (S-3AMPY)PbI 4 (b) Crystal structure diagram.

[0047] Fig.13 Based on (R-3AMPY)PbI 4 The circularly polarized photodetector has a wavelength of 532nm and a light intensity of 20μW / cm 2 IV curves under circularly polarized light.

[0048] Fig.14 (R-4AMPY)PbI 4 Single crystal picture.

[0049] Fig.15(R-4AMPY)PbI 4 (a) and (S-4AMPY)PbI 4 (b) Crystal structure diagram.

[0050] Fig.16 (R-4AMPY)PbI 4 (a) and (S-4AMPY)PbI 4 (b) XRD pattern of.

[0051] Fig.17 (R-4AMPY)PbI 4 Fluorescence spectra under RCP and LCP irradiation.

[0052] Fig.18 Based on (R-4AMPY)PbI 4 The circularly polarized photodetector has a wavelength of 532nm and a light intensity of 20μW / cm 2 IV curves under circularly polarized light.

[0053] Fig.19 (S-4AMPY)PbI 4 Fluorescence spectra under RCP and LCP irradiation.

[0054] Fig. 20 Chiral perovskite (R-3AMPY)PbI 4 SHG spectra under 1064 nm femtosecond laser excitation. DETAILED DESCRIPTION

[0055] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution in the embodiment of the present invention will be clearly described below in conjunction with the drawings in the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0056] In the following examples, all the raw materials used are commercially available products that can be directly purchased. Room temperature refers to 25±5°C.

[0057] Example 1

[0058] In this example, Dion-Jacobson type (R-3AMPY) PbBr was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals and circularly polarized photodetectors.

[0059] 1. (R-3AMPY)PbBr 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0060] 0.5mmol of lead bromide was added to 2mL of 48% hydrobromic acid aqueous solution, and heated and stirred on a 150℃ heating table to completely dissolve it, and a colorless transparent liquid was obtained; then 0.5mmol of R-3AMPY was added to the obtained hot solution, and a large amount of white smoke was emitted. Continue to heat and stir at 150℃ for 2h to completely dissolve it, let it stand for 2h, and cool it down to room temperature at a cooling rate of 3℃ / h, and light yellow block crystals precipitated ( Figure 1 ).

[0061] The block crystals were taken out, rinsed repeatedly with n-hexane, and then dried in a 60°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (R-3AMPY)PbBr 4 .

[0062] The (R-3AMPY)PbBr prepared above 4 Organic-inorganic hybrid chiral perovskite single crystal, the crystal structure of which was analyzed by single crystal X-ray diffraction (see Figure 2 a), the crystal is an orthorhombic system, which is a non-centrosymmetric P2 1 2 1 2 1 The space group, whose unit cell parameters are: α=90°,β=90°,γ=90°. In this crystal, Pb 2+ ion and the six adjacent Br - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by Br - The inorganic octahedral layer and the diamine organic cation R-3AMPY interact with each other through hydrogen bonds.

[0063] Figure 3 a is the prepared (R-3AMPY)PbBr 4 XRD pattern of chiral perovskite single crystal. The diffraction peaks at 9.2°, 15.35°, 23.59°, 27.45°, 30.08°, and 32.73° represent chiral perovskite single crystal (R-3AMPY)PbBr 4 The (002), (121), (124), (006), (241), and (160) crystal planes completely coincide with the diffraction peaks of the theoretical simulation, indicating that (R-3AMPY)PbBr 4 Successful preparation of chiral perovskite single crystals.

[0064] In order to further observe the morphological characteristics of the crystal at the microscopic scale, we used Scotch tape to mechanically peel the single crystal, and the SEM image of the peeled single crystal showed that the surface of the single crystal was smooth and flat, with no obvious cracks ( Figure 4 a).

[0065] The prepared (R-3AMPY)PbBr 4 The thermal stability of chiral perovskite single crystals was analyzed, such as Figure 5 a Thermogravimetric analysis (TGA) shows that (R-3AMPY)PbBr 4 Continuous structural cracking occurs from 307°C until complete decomposition. Their thermal decomposition temperature is significantly higher than that of Ruddlesden-Popper hybrid chiral perovskites with van der Waals gaps reported in the literature, such as (R-MPEA) 2 CuCl 4 , and its thermal decomposition temperature is only 177°C (Chem. Mater. 2020, 32, 8914-8920). This shows that the Dion-Jacobson type hybrid chiral perovskite structure has significant advantages in thermal stability, which is related to its unique molecular arrangement and compact crystal structure.

[0066] 2. Based on (R-3AMPY)PbBr 4 Preparation of circular polarization photodetector:

[0067] (a) Preparation of precursor solution: Weigh 130 mg of (R-3AMPY)PbBr prepared in step 1 above 4 The chiral perovskite single crystal was dissolved in 200 μL of a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (volume ratio of 1:1), stirred at 70 °C for 1 h until completely dissolved, and a clear solution was obtained, which was the desired precursor solution;

[0068] (b) Preparation of thin films: The glass substrate was ultrasonically cleaned with acetone, anhydrous ethanol and deionized water respectively, and then treated with a vacuum plasma cleaner for 20 min. 40 μL of the precursor solution was dropped on the cleaned substrate surface and spin-coated at a low speed of 1000 rpm / min for 10 s, and then at a high speed of 5000 rpm / min for 30 s. After the spin coating, the sample was immediately placed on a 120 °C heating table for annealing for 15 min.

[0069] (c) Preparation of electrodes: The film was placed in a high vacuum three-target magnetron sputtering instrument with a vacuum degree of 5.0×10 -5 Pa, gold was sputtered onto the surface of the prepared film, and the effective area of ​​the electrode was 0.02 cm 2 .

[0070] Circular polarization photodetector performance characterization:

[0071] like Figure 6As shown, a 325nm laser is used as the light source, and a λ / 4 and λ / 2 glass slide are combined to convert the linear polarized light into circular polarized light. The light source is irradiated on the surface of the device, and a high-precision electrometer (Keithley 6517B) is used to test the IV curve of the photodetection device.

[0072] Based on (R-3AMPY)PbBr 4 The IV curve of a circularly polarized photodetector is shown in Figure 7 As shown in the figure, it can be seen that its responsivity anisotropy factor can reach 0.55, which is significantly higher than the traditional Ruddlesden-Popper type (R-MBA) 2 PbI 4 Hybrid chiral perovskite (0.1, Figure 8 ), indicating that the (R-3AMPY)PbBr 4 The circularly polarized photodetector has the ability to detect circularly polarized light with high efficiency and selectivity.

[0073] Example 2

[0074] In this example, Dion-Jacobson type (S-3AMPY) PbBr was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals and circularly polarized photodetectors.

[0075] (S-3AMPY)PbBr 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0076] Add 0.5mmol of lead bromide to 2mL of 48% hydrobromic acid aqueous solution, heat and stir on a 150℃ heating table to completely dissolve it, and obtain a colorless transparent liquid; then add 0.5mmol of S-3AMPY to the obtained hot solution. Continue to heat and stir at 150℃ for 2h to completely dissolve it, let it stand for 2h, and cool it down to room temperature at a cooling rate of 3℃ / h, and light yellow block crystals will precipitate.

[0077] The block crystals were taken out, rinsed repeatedly with n-hexane, and then dried in a vacuum oven at 60 °C for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (S-3AMPY)PbBr 4 .

[0078] The (S-3AMPY)PbBr prepared above 4 Organic-inorganic hybrid chiral perovskite single crystal, the crystal structure of which was analyzed by single crystal X-ray diffraction (see Figure 2 b), the crystal is an orthorhombic system, which is a non-centrosymmetric P2 1 2 1 2 1The space group, whose unit cell parameters are: α=90°,β=90°,γ=90°. In this crystal, Pb 2+ ion and the six adjacent Br - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by Br - The inorganic octahedral layer and the diamine organic cation S-3AMPY interact with each other through hydrogen bonds.

[0079] like Fig. 9 As shown in a, the (R / S-3AMPY)PbBr obtained in Example 1 and Example 2 4 The single crystal was characterized by circular dichroism spectroscopy. In the range of 250-800 nm, the circular dichroism spectral signals of R and S configurations appeared in the same position but opposite signs before the absorption exciton peak, which was different from the signal position of the chiral molecule R / S-3AMPY ( Fig.10 ), indicating that the chirality has been successfully transferred from the chiral molecular ligands to the perovskite framework, proving that the obtained single crystal has intrinsic chirality.

[0080] Example 3

[0081] In this example, Dion-Jacobson type (R-3AMPY) PbI was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals and circularly polarized photodetectors.

[0082] 1. (R-3AMPY)PbI 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0083] First, add 500 μL of 50% hypophosphorous acid solution to 2 mL of 55% to 58% hydroiodic acid aqueous solution. After stirring, the deep red HI aqueous solution gradually becomes lighter, and finally a colorless solution is obtained. 2 Add to the above solution, heat and stir on a 150℃ heating table to completely dissolve it, and obtain a light yellow transparent liquid; then add 0.5mmol R-3AMPY to the obtained hot solution, continue heating and stirring for 2h to completely dissolve it, let it stand for 2h, and cool it down to room temperature at a cooling rate of 3℃ / h, and red block crystals will precipitate ( Fig.11 ).

[0084] The block crystals were taken out, rinsed repeatedly with n-hexane, and then dried in a 60°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (R-3AMPY)PbI 4 .

[0085] The (R-3AMPY)PbI prepared above 4Organic-inorganic hybrid chiral perovskite single crystal, the crystal structure of which was analyzed by single crystal X-ray diffraction (see Fig.12 a), the crystal is an orthorhombic system, which is a non-centrosymmetric P2 1 2 1 2 1 The space group, whose unit cell parameters are: α=90°,β=90°,γ=90°. In this crystal, Pb 2+ ion and the six adjacent I - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by sharing vertices. - The inorganic octahedral layer and the diamine organic cation R-3AMPY interact with each other through hydrogen bonds.

[0086] Figure 3 b is the prepared (R-3AMPY)PbI 4 XRD pattern of chiral perovskite single crystal. The diffraction peaks at 13.98°, 17.42°, 18.27°, 19.51°, 26.55°, and 28.59° represent chiral perovskite single crystal (R-3AMPY)PbI 4 The (112), (113), (014), (040), (006), and (241) crystal planes of (R-3AMPY)PbI 4 The chiral perovskite single crystal was successfully prepared. Its strong signal intensity and narrow half-width indicate its high crystal quality and low defect density. We used Scotch tape to mechanically peel the single crystal, and the SEM image of the peeled single crystal showed that the surface of the single crystal was smooth and flat, with no obvious cracks ( Figure 4 b). The prepared (R-3AMPY)PbI 4 The thermal stability of chiral perovskite single crystals was analyzed, such as Figure 5 b Thermogravimetric analysis (TGA) shows that (R-3AMPY)PbI 4 and (R-3AMPY)PbBr 4 exhibited similar thermal decomposition behavior, but (R-3AMPY)PbI 4 Continuous structural cracking occurs from 290°C until complete decomposition, which is significantly higher than the Ruddlesden-Popper hybrid chiral perovskite with van der Waals gap reported in existing literature, showing excellent thermal stability.

[0087] 2. Based on (R-3AMPY)PbI 4 Preparation of circular polarization photodetector:

[0088] (a) Preparation of precursor solution: Weigh 130 mg of (R-3AMPY)PbI prepared in step 1 above 4 The single crystal was dissolved in 200 μL of a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (volume ratio of 1:1), stirred at 70°C for 1 h until completely dissolved, to obtain a clear solution, which is the desired precursor solution; (b~c) The operation process is the same as in Example 1.

[0089] Circularly polarized light detection performance characterization:

[0090] A 532nm laser was used as the light source, and the linear polarized light was converted into circular polarized light in combination with λ / 4 and λ / 2 glass slides. The circular polarized light detection performance of the photoelectric detection device was evaluated using the method in Example 1. (R-3AMPY)PbI 4 The responsivity anisotropy factor can reach 0.6 ( Fig.13 ), which is significantly higher than the traditional Ruddlesden-Popper type (R-MBA) 2 PbI 4 Hybrid chiral perovskite (0.1, Figure 8 ), indicating that it has efficient and highly selective circularly polarized light detection capabilities.

[0091] Example 4

[0092] In this example, Dion-Jacobson type (S-3AMPY) PbI was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals.

[0093] (S-3AMPY)PbI 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0094] First, add 500 μL of 50% hypophosphorous acid solution to 2 mL of 55% to 58% hydroiodic acid aqueous solution. After stirring, the deep red HI aqueous solution gradually becomes lighter, and finally a colorless solution is obtained. 2 Add to the above colorless solution, heat and stir on a 150℃ heating table to completely dissolve it to obtain a light yellow transparent liquid; then add 0.5mmol S-3AMPY to the obtained hot solution, continue heating and stirring for 2h to completely dissolve it, let it stand for 2h, cool to room temperature at a cooling rate of 3℃ / h, and red block crystals will precipitate.

[0095] The block crystals were taken out, rinsed repeatedly with n-hexane, and then dried in a 60°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (S-3AMPY)PbI 4 .

[0096] The (S-3AMPY)PbI prepared above 4 Organic-inorganic hybrid chiral perovskite single crystal, the crystal structure of which was analyzed by single crystal X-ray diffraction (see Fig.12 b), the crystal is an orthorhombic system, which is a non-centrosymmetric P2 1 2 1 2 1 The space group, whose unit cell parameters are: α=90°,β=90°,γ=90°. In this crystal, Pb 2+ ion and the six adjacent I - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by sharing vertices. - The inorganic octahedral layer and the diamine organic cation S-3AMPY interact with each other through hydrogen bonds.

[0097] like Fig. 9 As shown in b, the (R / S-3AMPY)PbI 4 The single crystal was characterized by circular dichroism spectroscopy, and the same phenomenon as in Examples 1 and 2 occurred, proving that the obtained single crystal had intrinsic chirality.

[0098] Example 5

[0099] In this example, Dion-Jacobson type (R-4AMPY) PbI was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals.

[0100] 1. (R-4AMPY)PbI 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0101] First, add 500 μL of 50% hypophosphorous acid solution to 2 mL of 47% hydroiodic acid aqueous solution. After stirring, the deep red HI aqueous solution gradually becomes lighter, and finally a colorless solution is obtained. Add 0.5 mmol PbO to the above solution, heat and stir on a 120°C heating table to completely dissolve it, and obtain a light yellow transparent liquid; then add 0.5 mmol R-4AMPY to the obtained hot solution, continue heating and stirring for 4 hours to completely dissolve it, let it stand for 6 hours, and cool it down to room temperature at a cooling rate of 1°C / h. Red block crystals will precipitate ( Fig.14 ).

[0102] The block crystals were taken out, rinsed repeatedly with isopropanol, and then dried in a 60°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (R-4AMPY)PbI 4 .

[0103] The (R-4AMPY)PbI prepared above 4 Organic-inorganic hybrid chiral perovskite single crystal, the crystal structure of which was analyzed by single crystal X-ray diffraction (see Fig.15 a), the crystal is an orthorhombic system, which is a non-centrosymmetric P2 1 2 1 2 1 The space group, whose unit cell parameters are: α=90°,β=90°,γ=90°. In this crystal, Pb 2+ ion and the six adjacent I - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by sharing vertices. - The inorganic octahedral layer and the diamine organic cation R-4AMPY interact with each other through hydrogen bonds.

[0104] Fig.16 a is the prepared (R-4MPY)PbI 4 XRD pattern of chiral perovskite single crystal. The diffraction peaks at 8.76°, 14.02°, 14.69°, and 17.59° represent chiral perovskite single crystal (R-4AMPY)PbI 4 The (002), (210), (211), and (004) crystal planes completely coincide with the diffraction peaks of the theoretical simulation, indicating that (R-4AMPY)PbI 4 The chiral perovskite single crystal was successfully prepared. Its strong signal intensity and narrow half-width indicate its high crystal quality and low defect density.

[0105] Fig.17 The prepared (R-4MPY)PbI 4 The fluorescence spectra of the chiral perovskite single crystal under RCP and LCP irradiation show that its circular polarization degree (P) is as high as 31.5%, indicating its excellent circularly polarized light luminescence ability.

[0106] 2. Based on (R-4AMPY)PbI 4 Preparation of circular polarization photodetector:

[0107] (a) Preparation of precursor solution: Weigh 100 mg of (R-4AMPY)PbI prepared in step 1 above 4 The single crystal was dissolved in 200 μL of a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (volume ratio of 1:1), stirred at 70°C for 1 h until completely dissolved, to obtain a clear solution, which is the desired precursor solution; (b~c) The operation process is the same as in Example 1.

[0108] Circularly polarized light detection performance characterization:

[0109] A 532nm laser was used as the light source, and the linear polarized light was converted into circular polarized light in combination with λ / 4 and λ / 2 glass slides. The circular polarized light detection performance of the photoelectric detection device was evaluated using the method in Example 1. (R-4AMPY)PbI 4 The responsivity anisotropy factor can reach 0.59 ( Fig.18 ), which is significantly higher than the traditional Ruddlesden-Popper type (R-MBA) 2 PbI 4 Hybrid chiral perovskite (0.1, Figure 8 ), indicating that it has efficient and highly selective circularly polarized light detection capabilities.

[0110] Example 6

[0111] In this example, Dion-Jacobson type (S-4AMPY) PbI was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals.

[0112] (S-4AMPY)PbI 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0113] First, add 500 μL of 50% hypophosphorous acid solution to 2 mL of 47% hydroiodic acid aqueous solution. After stirring, the deep red HI aqueous solution gradually becomes lighter, and finally a colorless solution is obtained. Add 0.5 mmol PbO to the above colorless solution, heat and stir on a 120°C heating table to completely dissolve it, and obtain a light yellow transparent liquid; then add 0.5 mmol S-4AMPY to the obtained hot solution, continue heating and stirring for 4 hours to completely dissolve it, let it stand for 6 hours, and cool it down to room temperature at a cooling rate of 1°C / h, and red block crystals will precipitate.

[0114] The block crystals were taken out, rinsed repeatedly with ether, and then dried in a 60°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (S-4AMPY)PbI 4 .

[0115] The (S-4AMPY)PbI prepared above 4 Organic-inorganic hybrid chiral perovskite single crystal, the crystal structure of which was analyzed by single crystal X-ray diffraction (see Fig.15 b), the crystal is an orthorhombic system, which is a non-centrosymmetric P2 1 2 1 2 1 The space group, whose unit cell parameters are: α=90°,β=90°,γ=90°. In this crystal, Pb 2+ion and the six adjacent I - The inorganic octahedral structure composed of ions, the inorganic octahedron is connected by sharing vertices. - The inorganic octahedral layer and the diamine organic cation S-4AMPY interact with each other through hydrogen bonds. Fig.16 b is the prepared (S-4MPY)PbI 4 The XRD pattern of the chiral perovskite single crystal completely coincides with the diffraction peaks of the theoretical simulation, indicating that (S-4AMPY)PbI 4 Successful preparation of chiral perovskite single crystals.

[0116] like Fig. 9 As shown in c, the (R / S-4AMPY)PbI 4 The single crystal was characterized by circular dichroism spectroscopy, and the same phenomenon as in Examples 1 and 2 occurred, proving that the obtained single crystal had intrinsic chirality.

[0117] Fig.19 The prepared (S-4MPY)PbI 4 The fluorescence spectra of the chiral perovskite single crystal under RCP and LCP irradiation show that its circular polarization degree (P) is calculated to be 18.2%, indicating its excellent circularly polarized light luminescence ability.

[0118] Example 7

[0119] In this example, Dion-Jacobson type (R-3AMPY) PbI was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals.

[0120] (R-3AMPY)PbI 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0121] First, add 1 mL of 50% hypophosphorous acid solution to 4 mL of 47% hydroiodic acid aqueous solution. After stirring, the deep red HI aqueous solution gradually becomes lighter, and finally a colorless solution is obtained. Add 1 mmol of lead oxide to the above colorless solution, heat and stir on a 135°C heating table to completely dissolve it, and obtain a light yellow transparent liquid. Then add 1 mmol of R-3AMPY to the obtained hot solution, continue heating and stirring for 2 hours to completely dissolve it, let it stand for 2 hours, and cool it down to room temperature at a cooling rate of 3°C / h. Red block crystals will precipitate.

[0122] The block crystals were taken out, rinsed repeatedly with isopropanol, and then dried in a 55°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (R-3AMPY)PbI 4 .

[0123] Through the nonlinear optical SHG test, we once again verified the introduction of chiral chromophores and their impact on the central inversion symmetry of the sample. Here, we used a chiral perovskite single crystal (R-3AMPY) PbI 4 As a representative sample, we obtained its frequency-doubled signal spectrum at 532nm by 1064nm femtosecond laser excitation ( Fig. 20 ).

[0124] Example 8

[0125] In this example, Dion-Jacobson type (R-3AMPY) PbI was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals.

[0126] (R-3AMPY)PbI 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0127] First, add 1 mL of 50% hypophosphorous acid solution to 4 mL of 55% to 58% hydroiodic acid aqueous solution. After stirring, the deep red HI aqueous solution gradually becomes lighter, and finally a colorless solution is obtained. 2 Add to the above colorless solution, heat and stir on a heating table at 135℃ to completely dissolve it, and obtain a light yellow transparent liquid. Then add 2mmol R-3AMPY to the obtained hot solution, continue heating and stirring for 2h to completely dissolve it, let it stand for 2h, and cool it down to room temperature at a cooling rate of 2℃ / h, and red block crystals will precipitate.

[0128] The block crystals were taken out, rinsed repeatedly with isopropanol, and then placed in a 60°C vacuum drying oven to dry for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (R-3AMPY)PbI 4 .

[0129] Example 9

[0130] In this example, Dion-Jacobson type (R-3AMPY) PbBr was prepared by the following steps 4 Organic-inorganic hybrid chiral perovskite single crystals.

[0131] (R-3AMPY)PbBr 4 Preparation of organic-inorganic hybrid chiral perovskite single crystals:

[0132] Add 0.5mmol lead oxide to 2mL of 40% hydrobromic acid aqueous solution, heat and stir on a 130℃ heating table to completely dissolve it, and obtain a light yellow transparent liquid. Then add 0.5mmol R-3AMPY to the obtained hot solution, continue heating and stirring for 2h to completely dissolve it, let it stand for 5h, and cool it down to room temperature at a cooling rate of 1℃ / h, and light yellow block crystals will precipitate.

[0133] The block crystals were taken out, rinsed repeatedly with n-hexane, and then dried in a 60°C vacuum oven for 12 h to obtain an organic-inorganic hybrid chiral perovskite single crystal (R-3AMPY)PbBr 4 .

[0134] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal, characterized in that: The chemical formula of the chiral perovskite is (R / S-3AMPY)PbX4 and (R / S-4AMPY)PbX4, wherein X=I or Br; The crystals are all orthorhombic and non-centrosymmetric P212121 space group; Crystal I, (R-3AMPY)PbI4, has unit cell parameters: α=90°, β=90°, γ=90°. Crystal II, (S-3AMPY)PbI4, its unit cell parameters are: α=90°, β=90°, γ=90°; Crystal III, (R-3AMPY)PbBr4, has unit cell parameters: α=90°, β=90°, γ=90°; Crystal IV, (S-3AMPY)PbBr4, has unit cell parameters: α=90°, β=90°, γ=90°; Crystal V, (R-4AMPY)PbI4, its unit cell parameters are: α=90°, β=90°, γ=90°; Crystal VI, (S-4AMPY)PbI4, has unit cell parameters: α=90°, β=90°, γ=90°.

2. A method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal, characterized in that: The steps include: (1) completely dissolving the lead-based semiconductor in a hydrohalic acid solution; (2) then adding a chiral diamine organic molecule to the solution obtained in (1) to completely dissolve it; (3) After standing, the temperature is gradually lowered to room temperature to precipitate millimeter-sized crystals; (4) The crystal obtained in (3) is washed with a weakly polar solvent and dried to obtain a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal.

3. The method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 2, characterized in that: The lead-based semiconductor is one or two of PbI2, PbBr2 and PbO; the hydrohalic acid solution is one or two of hydroiodic acid solution and hydrobromic acid solution.

4. The method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 3, characterized in that: The concentration of the hydroiodic acid solution is 47-58 wt.%, and the concentration of the hydrobromic acid solution is 33-48 wt.%.

5. The method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 2, characterized in that: The chiral diamine organic molecule is any one of R / S-3AMPY and R / S-4AMPY. The structures of R / S-3AMPY and R / S-4AMPY are shown below:

6. The method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 2, characterized in that: The molar ratio of the chiral diamine organic molecule to the lead-based semiconductor is 1:0.25-4.

7. The method for preparing a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 1, characterized in that: The weak polar solvent is one or more of cyclohexane, n-hexane, isopropanol and ether.

8. Application of the Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 1 in circularly polarized photodetectors, light-emitting diodes, and displays.

9. The use according to claim 8, characterized in that: The method for preparing the circularly polarized photoelectric detector comprises the following steps: (1) dissolving the Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal in a benign solvent and heating to obtain a precursor solution; (2) dropping the precursor solution onto the cleaned substrate surface, and immediately annealing the sample at 120° C. for 15 min after spin coating to obtain an organic-inorganic hybrid chiral perovskite film; (3) A gold electrode is sputtered on the prepared film to obtain a photodetector based on a Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite film.

10. Application of the Dion-Jacobson type two-dimensional organic-inorganic hybrid chiral perovskite single crystal according to claim 1 in circularly polarized luminescence, nonlinear optics, telecommunications or information processing.

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