A kind of chiral hybrid perovskite and its preparation method and application

Abstract

The present invention discloses a two-handed hybrid perovskite and its preparation method and application, which belongs to the technical field of perovskite chiral materials and solves the problem that the asymmetric factor of the light response of two-dimensional chiral perovskite materials in the prior art is not ideal. The two-handed hybrid perovskite has the formula A' x A'' x M y X z A perovskite lattice; wherein A'A'' represents two cations, both of which are selected from R / S ‑3‑Aminobutanol cation, R / S ‑Methylbenzylamine cation, R / S 4-iodobutyl-2-amine cation; M represents one or more metals, all of which are selected from metal elements of Groups IIA to VA; X represents an anion, which is selected from halogen ions, pseudohalogen ions, and chalcogen ions. The bimanual perovskite material provided by the present invention has inherent chirality, and effectively solves the technical problem that the asymmetric factor of the photoresponsivity of the existing two-dimensional chiral perovskite material is not ideal, and exhibits excellent spin carrier selectivity.

Description

Technical Field

[0001] The present invention relates to the technical field of chiral perovskite materials, and more specifically to a chiral hybrid perovskite and a preparation method and application thereof. Background Art

[0002] Chiral organic-inorganic hybrid perovskites have shown great development potential in spin electronic properties due to their inherent chirality and various unique properties, such as circular dichroism (CD), circularly polarized photoluminescence (CPL), chirality-dependent photoelectric effect, chirality-induced spin selectivity effect and chiral phonon-activated spin Seebeck effect, and are widely used in circularly polarized light detectors, circularly polarized light sources, spin light-emitting diodes, spin filters, ferroelectrics, nonlinear optics, etc. Two-dimensional chiral perovskites have broad application prospects in circularly polarized light detection due to their excellent optoelectronic properties, such as band gap tunability, high carrier mobility, high absorption coefficient and long carrier diffusion constant, as well as different absorption of right-handed and left-handed polarized light.

[0003] In recent years, researchers have tried a variety of strategies to optimize the structure and morphology of two-dimensional chiral perovskites and further improve their circularly polarized light detection performance. For example, in patent CN115124432 A, different proportions of tin-lead inorganic components were mixed to adjust their band gap and improve carrier transport, thus improving the (R-MBA)2Pb 0.9 Sn 0.1 I4 response speed; or in patent CN115652406A, (S-NPB)2PbBr4 perovskite single crystal is prepared by melting method, which improves the crystallinity of the material and shows obvious circularly polarized light response.

[0004] However, the asymmetric factor of the photoresponsivity of the synthesized two-dimensional chiral perovskite materials is still difficult to improve. Therefore, it is necessary to explore new perovskite structures to achieve higher performance circularly polarized light detectors and further promote the practical application of perovskite circularly polarized light detectors in optoelectronics, quantum information science, biomedicine and other fields. Summary of the invention

[0005] The present invention provides a two-handed chiral hybrid perovskite and a preparation method and application thereof, so as to solve the problem that the asymmetric factor of the light response of the two-dimensional chiral perovskite material in the prior art is not ideal.

[0006] In a first aspect, the present invention provides a chiral hybrid perovskite, comprising: having a formula A' x A'' x M y X zperovskite lattice; wherein A'A'' represents two cations, both of which are selected from R / S-3-aminobutanol cation, R / S-methylbenzylamine cation, R / S-4-iodobutyl-2-amine cation; M represents one or more metals, both of which are selected from metal elements of Groups IIA~VA; X represents an anion, which is selected from halogen ions, pseudohalogen ions, and sulfide ions.

[0007] As a possible implementation method, its chemical formula is any one of (R-MBA)(R-IBA)PbI4, (R-MBA)(S-IBA)PbI4, (S-MBA)(R-IBA)PbI4, (S-MBA)(S-IBA)PbI4, and the single crystal structure space group is P21; wherein MBA represents α-methylbenzylamine, and IBA represents 4-iodobutyl-2-amine.

[0008] As a possible implementation method, the single crystal has a photoelectric response under 405 nm light; the response asymmetry factor (g res ) is 0.71, the responsiveness asymmetry factor of the (R-MBA)(R-IBA)PbI4 is -0.65, the responsiveness asymmetry factor of the (R-MBA)(S-IBA)PbI4 is 0.58, and the responsiveness asymmetry factor of the (S-MBA)(R-IBA)PbI4 is -0.56.

[0009] In a second aspect, the present invention provides a method for preparing a chiral hybrid perovskite single crystal according to any possible implementation of the first aspect, comprising the following steps: dissolving lead iodide in tetrahydrofuran, adding a chiral organic ammonium salt A and a chiral organic ammonium salt B to completely dissolve them to obtain a precursor solution; allowing the precursor solution to stand in a toluene atmosphere for 72 to 96 hours to obtain a crude product; washing the crude product with ether and then drying it to obtain the chiral hybrid perovskite; wherein the chiral organic ammonium salt A is any one of R-methylbenzyl ammonium iodide and S-methylbenzyl ammonium iodide; and the chiral organic ammonium salt B is any one of R-4-iodobutyl-2-ammonium iodide and S-4-iodobutyl-2-ammonium iodide.

[0010] As a possible implementation manner, the molar ratio of the chiral organic ammonium salt A to the chiral organic ammonium salt B is 1:0.5-2; and / or the molar ratio of the lead iodide to the sum of the two chiral organic ammonium salts is 1:1.5-2.5.

[0011] As a possible implementation manner, the dissolving is to perform an ultrasonic operation; and / or, the dissolving of lead iodide in tetrahydrofuran is to slowly add the tetrahydrofuran into the lead iodide; and / or, the drying is to dry in a vacuum oven at 60° C. for 3 hours.

[0012] In a third aspect, the present invention provides an application of the chiral hybrid perovskite described in any possible implementation of the first aspect or the chiral hybrid perovskite prepared by the preparation method described in any possible implementation of the second aspect in circularly polarized light detection.

[0013] As a possible implementation, the chiral hybrid perovskite is applied to a circularly polarized light detector; the circularly polarized light detector includes the chiral hybrid perovskite, a gold electrode, silicon dioxide, and silicon stacked in sequence from top to bottom.

[0014] In a fourth aspect, the present invention provides a circularly polarized light detector, comprising the chiral hybrid perovskite described in any possible implementation of the first aspect or the chiral hybrid perovskite prepared by the preparation method described in any possible implementation of the second aspect.

[0015] The present invention utilizes two different chiral cations to provide additional degrees of freedom for regulating circular dichroism and spin electron selectivity. In addition, the present invention uses two different chiral ammonium salts as raw materials to develop a circularly polarized light detector with stronger circular polarization discrimination and higher responsivity asymmetry factor. The bifunctional perovskite material provided by the present invention has inherent chirality and excellent spin carrier selectivity, so that when it is applied to a circularly polarized photodetector, it exhibits significantly different light responses under irradiation with left-handed and right-handed circularly polarized light, and produces a significant current difference, which reflects the outstanding circularly polarized light detection ability of the material to distinguish left-handed and right-handed circularly polarized light, and its maximum responsivity asymmetry factor reaches 0.71.

[0016] The synthesis method of the invention is simple, the preparation conditions are mild, high temperature and high pressure are not required, and the prepared two-handed hybrid perovskite has good stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 A single crystal structure diagram of a chiral hybrid perovskite single crystal provided in an embodiment of the present invention.

[0019] Figure 2 Thermogravimetric spectrum of the chiral hybrid perovskite single crystal provided in an embodiment of the present invention.

[0020] Figure 3This is an X-ray diffraction pattern of the chiral hybrid perovskite single crystal provided in an embodiment of the present invention.

[0021] Figure 4 X-ray diffraction pattern of the chiral hybrid perovskite film provided in an embodiment of the present invention.

[0022] Figure 5 Circular dichroism spectrum of the chiral hybrid perovskite film provided in an embodiment of the present invention.

[0023] Figure 6 Ultraviolet-visible absorption spectrum of the chiral hybrid perovskite film provided in an embodiment of the present invention.

[0024] Figure 7 Schematic diagram of using a chiral hybrid perovskite single crystal microwire array prepared by a dewetting method according to an embodiment of the present invention for a circularly polarized light detector.

[0025] Figure 8 Current-voltage (IV) curve of the chiral hybrid perovskite circularly polarized photodetector provided in an embodiment of the present invention, wherein a is RR, b is SS, c is SR, and d is RS.

[0026] Fig. 9 The performance of the two-dimensional perovskite CPL photodetector provided in the embodiments of the present invention. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of 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.

[0028] In order to solve the problem that the asymmetry factor of the photoresponsivity of two-dimensional chiral perovskite materials in the prior art is not ideal, an embodiment of the present invention provides a preparation experiment of a chiral hybrid perovskite single crystal, and verifies the structure of the product prepared by the embodiment of the present invention. It can be seen that the target product is successfully prepared, and the product has high purity and good thermal stability.

[0029] Furthermore, the chiral hybrid perovskite film was characterized in the embodiment of the present invention, and it can be seen that the phase purity of the RR / RS / SR / SS film is very high.

[0030] Furthermore, the embodiment of the present invention provides a performance test experiment of applying the prepared two-handed hybrid perovskite to the preparation of circularly polarized photodetectors. It can be seen that it has significant detection capabilities for RCP and LCP light, and the two-dimensional two-handed perovskite CPL photodetector prepared in this application has good performance.

[0031] The technical solution of the present invention will be further described below in conjunction with specific embodiments.

[0032] Example 1

[0033] This example provides an experiment for preparing a chiral ammonium salt R-IBAI (or S-IBAI).

[0034] In an ice-water bath, add 20 mL of anhydrous ethanol and 5 mL of R-3-aminobutanol (or S-3-aminobutanol) solution into a round-bottom flask. After cooling, add 8 mL of hydroiodic acid (47 wt% aqueous solution) dropwise under magnetic stirring. After reacting for 2 hours, the R-3-aminobutanol hydroiodide precursor solution is obtained, and the solvent is removed at 90°C using a rotary evaporator.

[0035] 8 mL of hydroiodic acid (47 wt% aqueous solution) was added dropwise to the solid after rotary evaporation in an ice-water bath, and heated at 90°C for 2 h. After the reaction, the solvent was removed at 90°C using a rotary evaporator to obtain a solid powder. The obtained solid powder was washed three times with anhydrous ether and recrystallized with anhydrous ethanol. The obtained white powder was dried in a vacuum drying oven for 4 h, namely R-IBAI (or S-IBAI).

[0036] Example 2

[0037] This embodiment provides an experiment for preparing a chiral hybrid perovskite single crystal.

[0038] 0.5 mmol (288.1 mg) of PbI2 was placed in a 4 mL glass bottle, 1.8 mL of tetrahydrofuran was taken with a pipette, and slowly added to the glass bottle, and ultrasonicated for 5 min to completely dissolve PbI2. 0.5 mmol (124.5 mg) of R-MBAI (or S-MBAI) and 0.5 mmol (163.5 mg) of R-IBAI (or S-IBAI) prepared in Example 1 were added, and stirred at room temperature for 20 min to dissolve them to obtain a precursor solution; the precursor solution was placed in a toluene atmosphere, sealed and stored, and left to stand for 3 to 4 days to obtain orange flake single crystals. After drying in a vacuum oven at 60°C for 3 h, the obtained product is a chiral hybrid perovskite single crystal [(R-MBA)(R-IBA)PbI4(RR), (R-MBA)(S-IBA)PbI4(RS), (S-MBA)(R-IBA)PbI4(SR), (S-MBA)(S-IBA)PbI4(SS)].

[0039] Using a single crystal X-ray diffractometer, a Mo target was used to determine the structure of the chiral perovskite single crystal, and the following results were obtained: Figure 1 The results shown. Figure 1 It can be seen that the structures of RR / RS / SR / SS are all monoclinic lattices, crystallized in the P21 space group, in which aromatic and alkyl spacer cations are arranged alternately in each organic layer; RR / SS and RS / SR are arranged in mirror images, respectively.

[0040] The thermal stability of the prepared chiral perovskite single crystal was tested by thermogravimetric analyzer in N2 atmosphere. The results are as follows: Figure 2 As shown in the figure, it can be clearly seen that the two-handed perovskite single crystal has good thermal stability, the decomposition temperature of RS / SR is 228℃, and the decomposition temperature of RR / SS is 231℃.

[0041] The prepared bipolar perovskite single crystal powder was further characterized by X-ray diffractometer, such as Figure 3 As shown. Figure 3 It can be seen that the phase purity of RR / RS / SR / SS is very high.

[0042] Example 3

[0043] This embodiment provides an experiment for preparing a chiral hybrid perovskite film.

[0044] 24.8 mg R-MBAI (or S-MBAI) (0.1 mmol), 32.7 mg R-IBAI (or S-IBAI) (0.1 mmol) prepared in Example 1 and 46.1 mg PbI2 (0.1 mmol) were added to a 2 mL glass bottle containing 0.5 mL N,N-dimethylformamide solvent, stirred at room temperature for 1 hour, filtered with a 0.22 μm polytetrafluoroethylene filter, and the resulting solution was the perovskite precursor solution. The cleaned quartz plate was placed on a spin coater, 110 μL of the perovskite precursor solution was drawn with a pipette and dropped on the quartz plate, and spin coating was started. The spin coating parameters were 2000 rpm and 30 s. After the spin coating was completed, the sample was taken out and placed on a heating table for annealing at 90°C for 10 min. After the annealing was completed, a dense perovskite film was obtained.

[0045] The prepared perovskite film was further characterized by X-ray diffractometer, and the following results were obtained: Figure 4 The results shown. Figure 4 It can be seen that the phase purity of RR / RS / SR / SS films is very high.

[0046] The prepared perovskite film was optically tested using a circular dichroism spectrometer and a UV-visible absorption spectrometer, and the following results were obtained: Figure 5 and Figure 6 The results shown. Figure 5 It can be seen that RR and SS have strong CD signals with opposite signs at 390 and 484 nm, and RS and SR have CD signals with opposite signs at 373 and 480 nm, and the intensity is significantly reduced. Figure 6 It can be seen that the RR / SS and RS / SR absorption edges are at 510 nm and 513 nm respectively, and the absorption exciton peaks are both at 484 nm.

[0047] Example 4

[0048] This embodiment provides a preparation experiment of a circular polarization photodetector.

[0049] Add 24.8 mg R-MBAI (or S-MBAI) (0.1 mmol), 32.7 mg R-IBAI (or S-IBAI) (0.1 mmol) and 46.1 mg PbI2 (0.1 mmol) into a 2 mL glass bottle containing 143 μL N,N-dimethylformamide or dimethyl sulfoxide or N,N-dimethylacetamide solvent, stir at room temperature for 1 h, and filter with a 0.22 μm polytetrafluoroethylene filter to obtain a perovskite precursor solution.

[0050] A silicon wafer with a 300 nm thick silicon dioxide layer was used as the substrate. The Si / SiO2 substrate was ultrasonicated in acetone, isopropanol, ethanol, and deionized water in sequence to clean the substrate surface. Then, Cr (10 nm) and Au (100 nm) were evaporated on the Si / SiO2 substrate as the bottom electrode to form an ohmic contact.

[0051] 7 μL of the precursor solution was dropped onto the prepared substrate, covered with an asymmetric wettability silicon template, and the entire system was placed in a vacuum oven and heated at 70°C for 12 h. After the solvent evaporated, a chiral 2D perovskite single crystal microwire array was prepared on the target substrate.

[0052] Fabrication and characterization of photodetectors: The devices were directly fabricated on Si / SiO2 substrates containing bottom electrodes by a one-step dewetting method, e.g. Figure 7 As shown, the efficient CPL absorption and anisotropic crystal structure of the microwire array can detect both linearly polarized light and circularly polarized light.

[0053] Example 5

[0054] This embodiment provides a performance testing experiment based on a bipolar perovskite circularly polarized photodetector.

[0055] The optoelectronic characterization was performed by a Keithley 4200 semiconductor characterization system and a manual probe station (Lake Shore). The light source used was a 405 nm light-emitting diode, and the incident power was adjusted by an LED controller. The current-voltage (IV) curves of the bipolar perovskite array device under dark, 405 nm RCP, and 405 nm LCP light illumination are shown in Figure 2. Figure 8 The IV curves of the microwire array device show distinct photoresponse differences under 405 nm RCP and LCP illumination, confirming the significant detection capability of CPL for RCP and LCP light.

[0056] The asymmetry factor of the responsivity is defined as g res =2(R L -R R ) / (R L +R R ), where R L and R R Represent the photocurrents under LCP and RCP illumination, respectively. Among them, the responsivity asymmetry factor of RR is -0.65, the responsivity asymmetry factor of SS is 0.71, the responsivity asymmetry factor of SR is -0.56, and the responsivity asymmetry factor of RS is 0.58.

[0057] In order to further highlight the superiority of the chiral two-dimensional perovskite CPL photodetector, the performance of the CPL photodetector based on two-dimensional perovskite was statistically compared, and the results are as follows: Fig. 9 The results shown. Fig. 9 It can be seen that the two-dimensional bipolar perovskite CPL photodetector prepared in this application has good performance.

[0058] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0059] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A chiral hybrid perovskite single crystal, characterized in that: Its chemical formula is ( R -MBA)( R -IBA)PbI4, ( R -MBA)( S -IBA)PbI4, ( S -MBA)( R -IBA)PbI4, ( S -MBA)( S -IBA)PbI4, the single crystal structure space group is P21; Among them, MBA represents α-methylbenzylamine, and IBA represents 4-iodobutyl-2-amine.

2. A method for preparing the chiral hybrid perovskite single crystal according to claim 1, characterized in that: The following steps are involved: Dissolving lead iodide in tetrahydrofuran, adding chiral organic ammonium salt A and chiral organic ammonium salt B to completely dissolve them, thereby obtaining a precursor solution; The precursor solution is placed in a toluene atmosphere for 72 to 96 hours to obtain a crude product; The crude product is washed with ether and then dried to obtain the chiral hybrid perovskite single crystal; Wherein, the chiral organic ammonium salt A is R- Methylbenzylammonium iodide, S- Any one of methylbenzyl ammonium iodide; the chiral organic ammonium salt B is R- 4-iodobutyl-2-ammonium iodide, S -4-iodobutyl-2-ammonium iodide.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the chiral organic ammonium salt A to the chiral organic ammonium salt B is 1:0.5-2; And / or, the molar ratio of the lead iodide to the sum of the two chiral organic ammonium salts is 1:1.5-2.

5.

4. The preparation method according to claim 2, characterized in that: The dissolving is performed by ultrasonic operation; And / or, the step of dissolving the lead iodide in tetrahydrofuran is to slowly add the tetrahydrofuran into the lead iodide; And / or, the drying is drying in a vacuum oven at 60° C. for 3 hours.

5. Use of the chiral hybrid perovskite single crystal according to claim 1 or the chiral hybrid perovskite single crystal prepared by the preparation method according to any one of claims 2 to 4 in circularly polarized light detection.

6. The use according to claim 5, characterized in that: The two-handed hybrid perovskite single crystal is applied to circularly polarized light detectors; The circularly polarized light detector includes the chiral hybrid perovskite single crystal, a gold electrode, silicon dioxide, and silicon stacked in sequence from top to bottom.

7. A circularly polarized light detector, characterized in that: It comprises the chiral hybrid perovskite single crystal according to claim 1 or the chiral hybrid perovskite single crystal prepared by the preparation method according to any one of claims 2 to 4.

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