A chiral halide perovskite single crystal and its preparation method and application

Abstract

The present invention discloses a chiral halide perovskite single crystal and its preparation method and application, belonging to the technical fields of chiral perovskite material synthesis and optoelectronic devices. In the chiral halide perovskite single crystal, an organic chiral molecule replaces the A-site cation in the perovskite, the B-site metal ion is fixed as Pb<supgt;2+< / supgt>, the X-site halogen atom is Cl<supgt;‑< / supgt>, Br<supgt;‑< / supgt> or I<supgt;‑< / supgt>, and the highly distorted [MX6] octahedral chains are surrounded by chiral cations that form a stacking framework. This perovskite single crystal not only retains the original dimension-adjustable characteristics and excellent photophysical properties of perovskite, but also has circular dichroism, circularly polarized photoluminescence, nonlinear optics, and ferroelectricity due to the introduction of chiral molecules with an intrinsic inversion symmetry structure. The circularly polarized photodetector prepared based on this perovskite single crystal has excellent response sensitivity, stability, and response frequency.

Description

Technical Field

[0001] The present invention belongs to the technical field of optoelectronic functional materials and devices, and in particular relates to a chiral halide perovskite single crystal and a preparation method and application thereof. Background Art

[0002] Chiral materials usually contain chiral molecules or chiral structural units, which have specific symmetry in space, so that their mirror images cannot be overlapped with the original structure by simple rotation or translation. It is precisely because of their uniqueness that they cannot overlap with their mirror images that they have broad application prospects in optics, electronics, chemistry and biology. One of the most striking properties of chiral materials is their optical activity, that is, they can rotate the polarization plane of polarized light, which makes chiral materials have important applications in circular dichroism spectroscopy, optically active devices and chiral catalysis. In the biomedical field, chiral materials have important applications due to their specific interactions with biomolecules, such as drug delivery, biosensing and tissue engineering. With the continuous deepening of chiral material research, the discovery and application of new chiral materials and chiral functions will continue to expand. These materials have broad application prospects in optoelectronic devices, biomedicine, catalysis and environmental science. Through interdisciplinary cooperation and innovation, chiral materials are expected to play a greater role in future technological progress.

[0003] Perovskite materials have received extensive attention and research in the fields of photovoltaics, light-emitting diodes, lasers and sensors in recent years due to their excellent optoelectronic properties. Among them, chiral perovskite materials have become one of the frontiers of materials science and optoelectronics research due to their unique chiral structure and optical properties. These materials not only have the excellent optoelectronic properties of traditional perovskite materials, but also show unique optical activities such as circular dichroism, ferroelectricity and optical rotation. In recent years, researchers have prepared a variety of chiral perovskite materials through chemical synthesis and physical methods, and have conducted in-depth research on their structures, properties and applications. Studies have found that chiral perovskite materials have significant advantages in improving photoelectric conversion efficiency, achieving high-sensitivity detection and enhancing optical activity. In addition, the chiral properties of these materials also provide new ideas and methods for the development of new optical and electronic devices. Therefore, it is of great significance to continuously search for new chiral perovskite materials so that they can be better applied to optoelectronic devices such as circularly polarized photodetectors, circularly polarized light-emitting diodes, three-dimensional displays, bioimaging, quantum computing, quantum communication, memory and self-selected transistors. Summary of the invention

[0004] In order to solve the above technical problems, the present invention proposes a chiral halide perovskite single crystal and its preparation method and application. The present invention introduces chiral molecules or chiral groups into non-chiral materials to form a highly distorted [MX 6] The octahedral chain is surrounded by chiral cations that form a stacking framework, giving it chiral properties to achieve precise control of the properties of chiral materials. Not only does it retain the original dimensional tunable characteristics and excellent photophysical properties of perovskite, but it also introduces chiral molecules with intrinsic inversion symmetry, giving the material circular dichroism, circularly polarized photoluminescence, nonlinear optics, and ferroelectricity. The chiral halide perovskite circularly polarized photodetector prepared with it as raw material can better distinguish the near-ultraviolet spectra of left-handed and right-handed circularly polarized light, and has excellent photoelectric properties such as high responsivity, detection rate, and fast response time.

[0005] To achieve the above object, the present invention provides a chiral halide perovskite single crystal, wherein the chiral halide perovskite single crystal is an ABX having an overlapping structure of organic molecules and inorganic octahedral layers. 3 Perovskite single crystal, in which the A-position cation in the perovskite is replaced by a chiral organic molecule and the B-position is Pb 2+ , X is Cl - Br - or I - .

[0006] Furthermore, the chiral organic molecule is (S)- / (R)-2-aminomethyl-1-ethylpyrrolidine (C 7 H 16 N 2 )(S- / R-AMEPY), (S)- / (R)-2-amino-1-phenylethanol (C 8 H 11 NO)(S- / R-AMPE) and (S)- / (R)-2-methylpyrrolidine (C 5 H 11 N)(S- / R-MPY).

[0007] Furthermore, the chiral halide perovskite single crystal uses lead halide as an octahedral inorganic framework, and the chiral organic molecules and the inorganic framework are connected by a multi-hydrogen bond structure.

[0008] The present invention also proposes a method for preparing the chiral halide perovskite single crystal, comprising the following steps:

[0009] (1) dissolving lead halide and chiral organic molecules in hydrohalic acid, stirring and mixing until the lead halide powder is completely dissolved and the solution is clear, and then filtering to obtain a perovskite precursor solution;

[0010] (2) cooling and crystallizing the perovskite precursor solution after reaction to obtain a chiral halide perovskite micro single crystal;

[0011] (3) Re-preparing a perovskite precursor solution according to the method of step (1), placing the chiral halide perovskite micro single crystal in the re-prepared perovskite precursor solution, and heating at a constant temperature to obtain the chiral halide perovskite single crystal.

[0012] Furthermore, in step (1), the hydrohalic acid is one or more of hydroiodic acid, hydrobromic acid and hydrochloric acid, and the hydrohalic acid is a hydrohalic acid aqueous solution with a mass concentration of 0.1%-65%, preferably 30-60%, and most preferably 40%.

[0013] Furthermore, in step (1), the halogen in the lead halide is the same as the halogen in the hydrohalic acid.

[0014] Furthermore, in step (1), the molar ratio of the lead halide to the chiral organic molecule is 2:1, and the concentration of the chiral organic molecule in the perovskite precursor solution is 0.1-2 mol / L, preferably 0.7-1.3 mol / L, and more preferably 0.12 mol / L.

[0015] Furthermore, in step (1), the stirring and mixing temperature is 60-140°C and the time is 0.5-10 hours. More preferably, the stirring and mixing temperature is 100°C and the time is 4 hours.

[0016] Furthermore, in step (2), the cooling crystallization is a gradient cooling, specifically cooling to 40-80°C at a rate of 0.1-10°C / h, and then cooling to room temperature at a rate of 1-10°C / h after keeping warm for 24 hours.

[0017] More preferably, the temperature is lowered to 80°C at a rate of 1°C / h, kept at that temperature for 24 hours, and then cooled to room temperature at a rate of 1°C / h.

[0018] The specific cooling crystallization step is conducive to the production of microcrystalline nuclei, and the obtained single crystal has a stable structure, fewer impurity defects, and a high yield.

[0019] Furthermore, in step (3), the concentration of the chiral organic molecules in the re-prepared perovskite precursor solution is 0.1-0.2 mol / L lower than the concentration of the chiral organic molecules in the perovskite precursor solution obtained in step (1).

[0020] Furthermore, in step (3), the temperature of the constant temperature heating is 80°C.

[0021] The present invention also proposes the application of the chiral halide perovskite single crystal in the preparation of a chiral photoelectric detector.

[0022] Compared with the prior art, the present invention has the following advantages and technical effects:

[0023] (1) In the chiral halide perovskite single crystal synthesized by the present invention, the organic molecules and the inorganic skeleton are connected by a multi-hydrogen bond structure, and the overall highly twisted [MX6] octahedral chain is surrounded by chiral cations that constitute the stacking framework. This structure enables the material to have excellent carrier transport properties. The photodetector prepared based on this perovskite structure has good switching performance, high responsiveness and detection rate, and the rise time and decay time are 156-415μs and 201-375μs respectively, with a fast response time.

[0024] (2) The circularly polarized photodetector based on the chiral halide perovskite single crystal obtained by the present invention produces a significant current difference under the irradiation of left-handed and right-handed circularly polarized light, which reflects the excellent ability of the material to distinguish left-handed and right-handed circularly polarized light, and has the potential to be actually applied in the detection of circularly polarized light in the commercial market.

[0025] (3) The present invention provides a method for preparing a chiral halide inorganic perovskite single crystal. By introducing a chiral molecule with an intrinsic inversion symmetric structure, the interaction with the perovskite lattice endows the perovskite material with unique optical activities of chiral molecules such as circular dichroism and optical rotation, so that traditional perovskite materials can be better applied to circularly polarized photodetectors, circularly polarized light-emitting diodes, three-dimensional displays, bioimaging, quantum computing, quantum communications, spin transistors and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0027] Figure 1 The chiral halide perovskite single crystal (S-AMEPY)Pb prepared in Example 1 of the present invention 2 Br 6 Physical picture;

[0028] Figure 2 The chiral halide perovskite single crystal (R-AMEPY)Pb prepared in Example 2 of the present invention 2 Br 6 Physical picture;

[0029] Figure 3 The chiral halide perovskite single crystal (S-AMEPY)Pb prepared in Example 1 2 Br 6 X-ray polycrystal diffraction spectrum;

[0030] Figure 4 The chiral halide perovskite single crystal (R-AMEPY)Pb prepared in Example 2 2 Br6 X-ray polycrystal diffraction spectrum;

[0031] Figure 5 The chiral halide perovskite single crystal (S-AMEPY)Pb prepared in Example 1 2 Br 6 The chiral halide perovskite single crystal (R-AMEPY)Pb prepared in Example 2 2 Br 6 Circular dichroism spectrum of ;

[0032] Figure 6 Schematic diagram of the structure of a circular polarization photodetector;

[0033] Figure 7 (S-AMEPY)Pb of Example 1 2 Br 6 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light;

[0034] Figure 8 (R-AMEPY)Pb of Example 2 2 Br 6 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light;

[0035] Fig. 9 (S-AMEPY)Pb of Example 1 2 Br 6 The responsivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0036] Fig.10 (S-AMEPY)Pb of Example 1 2 Br 6 The detectivity measurement results of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0037] Fig.11 (R-AMEPY)Pb of Example 2 2 Br 6 The responsivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0038] Fig.12 (R-AMEPY)Pb of Example 2 2 Br 6 The detectivity measurement results of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0039] Fig.13 (S-AMPE)Pb of Example 3 2 Br 5 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light;

[0040] Fig.14 (R-AMPE)Pb of Example 4 2 Br 5 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light;

[0041] Fig.15 (S-MPY)Pb of Example 5 2 Br 5 The current-voltage curve of the prepared circularly polarized photodetector in the dark state and under 365nm light.

[0042] Fig.16 (R-MPY)Pb of Example 6 2 Br 5 The current-voltage curve of the prepared circularly polarized photodetector in the dark state and under 365nm light.

[0043] Fig.17 (S-AMEPY)Pb of Example 7 2 Cl 6 The responsivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0044] Fig.18 (S-AMEPY)Pb of Example 7 2 Cl 6 The detection rate of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0045] Fig.19 (R-AMEPY)Pb of Example 7 2 Cl 6 The responsivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0046] Fig. 20 (R-AMEPY)Pb of Example 7 2 Cl 6 The detection rate of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0047] Fig.21 (S-AMEPY)Pb of Example 9 2 I 6 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light;

[0048] Fig. 22 (S-AMEPY)Pb of Comparative Example 1 2 Br 6 The responsivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation;

[0049] Fig.23 (S-AMEPY)Pb of Comparative Example 1 2 Br 6 The detectivity measurement results of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light. DETAILED DESCRIPTION

[0050] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0051] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0052] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0053] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0054] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0055] The embodiment of the present invention provides a chiral halide perovskite single crystal, wherein the chiral halide perovskite single crystal is an ABX having an overlapping structure of organic molecules and inorganic octahedral layers. 3 Perovskite single crystal, in which the A-position cation in the perovskite is replaced by a chiral organic molecule and the B-position is Pb 2+ , X is Cl - Br - or I - ;

[0056] The chiral halide perovskite single crystal uses lead halide as an octahedral inorganic framework, and the chiral organic molecules and the inorganic framework are connected by a multi-hydrogen bond structure.

[0057] In a preferred embodiment of the present invention, the chiral organic molecule is (S)- / (R)-2-aminomethyl-1-ethylpyrrolidine (C 7 H 16 N 2 )(S- / R-AMEPY), (S)- / (R)-2-amino-1-phenylethanol (C 8 H 11 NO)(S- / R-AMPE) and (S)- / (R)-2-methylpyrrolidine (C 5 H 11 N)(S- / R-MPY).

[0058] The embodiment of the present invention further provides a method for preparing the chiral halide perovskite single crystal, comprising the following steps:

[0059] (1) dissolving lead halide and chiral organic molecules in hydrohalic acid, stirring and mixing until the lead halide powder is completely dissolved and the solution is clear, and then filtering to obtain a perovskite precursor solution;

[0060] (2) cooling and crystallizing the perovskite precursor solution after reaction to obtain a chiral halide perovskite micro single crystal;

[0061] (3) Re-preparing a perovskite precursor solution according to the method of step (1), placing the chiral halide perovskite micro single crystal in the re-prepared perovskite precursor solution, and heating at a constant temperature to obtain the chiral halide perovskite single crystal.

[0062] In a preferred embodiment of the present invention, in step (1), the hydrohalic acid is one or more of hydroiodic acid, hydrobromic acid and hydrochloric acid, and the hydrohalic acid is a hydrohalic acid aqueous solution with a mass concentration of 0.1%-65%, preferably 30-60%, and more preferably 40%.

[0063] In a preferred embodiment of the present invention, in step (1), the halogen in the lead halide is the same as the halogen in the hydrohalic acid.

[0064] In a preferred embodiment of the present invention, in step (1), the molar ratio of the lead halide to the chiral organic molecule is 2:1, and the concentration of the chiral organic molecule in the perovskite precursor solution is 0.1-2 mol / L, preferably 0.7-1.3 mol / L, and more preferably 0.12 mol / L.

[0065] In a preferred embodiment of the present invention, in step (1), the stirring and mixing is performed at a temperature of 60-140° C. for a time of 0.5-10 h. More preferably, the stirring and mixing is performed at a temperature of 100° C. for a time of 4 h.

[0066] In a preferred embodiment of the present invention, in step (2), the cooling crystallization is a gradient cooling, specifically cooling to 40-80°C at a rate of 0.1-10°C / h, and cooling to room temperature at a rate of 1-10°C / h after keeping warm for 24 hours. More preferably, cooling to 80°C at a rate of 1°C / h, and cooling to room temperature at a rate of 1°C / h after keeping warm for 24 hours. The above-mentioned specific cooling crystallization step is conducive to the generation of microcrystalline nuclei, and the obtained single crystal structure is stable, has fewer impurity defects, and has a high yield.

[0067] In a preferred embodiment of the present invention, in step (3), the concentration of the chiral organic molecules in the re-formulated perovskite precursor solution is 0.1-0.2 mol / L lower than the concentration of the chiral organic molecules in the perovskite precursor solution obtained in step (1).

[0068] In a preferred embodiment of the present invention, in step (3), the constant temperature heating temperature is 80° C. If the size of the single crystal is not large enough to evaporate the interdigital electrode onto the surface of the single crystal (the size of the interdigital electrode is 3 mm×3 mm), the heating time can be appropriately extended to promote its crystallization.

[0069] In order to better understand the structural composition of the chiral halide perovskite single crystal in the present invention, taking the chiral organic molecule as S-AMEPY and the lead halide as lead bromide as an example, the chiral halide perovskite single crystal structure formula is (S-AMEPY)Pb 2 Br 6 Taking the chiral organic molecule as R-AMEPY and the lead halide as lead bromide as an example, the chiral halide perovskite single crystal structure formula is (R-AMEPY)Pb 2 Br6 The structural composition of the chiral halide perovskite single crystal of the present invention includes but is not limited to the above structure.

[0070] In the embodiments of the present invention, "normal temperature" refers to "25±3°C".

[0071] The technical solution of the present invention is further illustrated by the following embodiments.

[0072] Example 1

[0073] Preparation of chiral halide perovskite single crystals with organic chiral molecule (S)-2-aminomethyl-1-ethylpyrrolidine (S-AMEPY) as the A-site molecule (S-AMEPY)Pb 2 Br 6 , the preparation method comprises the following steps:

[0074] (1) Weigh 176.4 μL (1.2 mmol) of S-AMEPY and 889.2 mg (2.4 mmol) of PbBr 2 Dissolve them together in 1 mL of hydrobromic acid (mass fraction 40%) to obtain (S-AMEPY)Pb 2 Br 6 Mixing solutions;

[0075] (2) Place the prepared mixed solution on a heating table at 100°C, stir and mix well, and heat for 4 hours until PbBr 2 The powder is completely dissolved. Observe whether the solute is fully dissolved. If not, shake it appropriately to promote its dissolution or extend the heating time to promote its dissolution. The completely dissolved solution is a clear light brown liquid, which is (S-AMEPY)Pb 2 Br 6 Perovskite precursor solution;

[0076] (3) After the perovskite precursor solution is completely dissolved and becomes clear, the crystallization process begins. It is first kept at 100°C for 2 hours, then cooled to 80°C at a rate of 1°C / h, kept at this temperature for 24 hours, and then cooled to room temperature at a rate of 1°C / h to obtain a large amount of (S-AMEPY)Pb 2 Br 6 ;

[0077] (4) Weigh 147 μL (1 mmol) S-AMEPY and 741 mg (2 mmol) PbBr 2 Dissolve them together in 1 mL of hydrobromic acid (mass fraction 40%) to obtain (S-AMEPY)Pb 2 Br 6 Mix the solution, and treat the mixed solution according to the above step (2) to obtain a clear light brown solution;

[0078] (5) The (S-AMEPY)Pb obtained in step (3) above 2 Br 6 The micro single crystals were slowly placed in the clear light brown solution obtained in step (4) and heated at a constant temperature of 80°C for 48 h to obtain centimeter-scale chiral halide perovskite single crystals (S-AMEPY)Pb 2 Br 6 If the size of the single crystal is not large enough to evaporate the interdigital electrode onto the surface of the single crystal (the size of the interdigital electrode is 3 mm×3 mm), the heating time can be appropriately extended to promote its crystallization, the same below.

[0079] The chiral halide perovskite single crystal (S-AMEPY) Pb prepared in Example 1 of the present invention 2 Br 6 See the actual picture Figure 1 , it can be seen that its size is 13mm×5mm×4mm.

[0080] Example 2

[0081] Preparation of chiral halide perovskite single crystals with organic chiral molecule (R)-2-aminomethyl-1-ethylpyrrolidine (R-AMEPY) as the A-site molecule (R-AMEPY)Pb 2 Br 6 The preparation method is the same as that of Example 1, except that S-AMEPY is replaced by R-AMEPY in equal moles.

[0082] The chiral halide perovskite single crystal (R-AMEPY)Pb prepared in Example 2 of the present invention 2 Br 6 See the actual picture Figure 2 , it can be seen that its size is 10mm×7mm×6mm.

[0083] Example 1 Chiral halide perovskite single crystal (S-AMEPY) Pb 2 Br 6 The X-ray polycrystalline diffraction spectrum of Figure 3 The chiral halide perovskite single crystal (R-AMEPY)Pb prepared in Example 2 2 Br 6 The X-ray polycrystalline diffraction spectrum of Figure 4 ,Depend on Figure 3 , 4 It can be seen that the chiral halide perovskite single crystals prepared in Examples 1 and 2 have good crystal orientation and excellent crystal quality.

[0084] Example 1 Chiral halide perovskite single crystal (S-AMEPY) Pb 2 Br6 The chiral halide perovskite single crystal (R-AMEPY)Pb prepared in Example 2 2 Br 6 The circular dichroism spectrum of Figure 5 .Depend on Figure 5 It can be seen that the organic chiral molecules are fully introduced into the octahedral structure of the perovskite, and the grown single crystals have strong circular dichroism signals.

[0085] Example 3

[0086] Preparation of chiral halide perovskite single crystals with organic chiral molecule (S)-2-amino-1-phenylethanol (S-AMPE) as the A-site molecule (S-AMPE)Pb 2 Br 5 , the preparation method comprises the following steps:

[0087] (1) Weigh 151.8 mg (1.1 mmol) of S-AMPE and 815.1 mg (2.2 mmol) of PbBr 2 Dissolve them together in 1 mL of hydrobromic acid (40% by mass) to obtain (S-AMPE)Pb 2 Br 6 Mixing solutions;

[0088] (2) Place the prepared mixed solution on a heating table at 100°C, stir and mix well, and heat for 4 hours until PbBr 2 The powder is completely dissolved. Observe whether the solute is fully dissolved. If not, shake it appropriately to promote its dissolution or extend the heating time to promote its dissolution. The completely dissolved solution is a clear light brown liquid, which is (S-AMPE)Pb 2 Br 5 Perovskite precursor solution;

[0089] (3) After the perovskite precursor solution is completely dissolved and becomes clear, the crystallization process begins. It is first kept at 100°C for 2 hours, then cooled to 80°C at a rate of 1°C / h, kept at this temperature for 24 hours, and then cooled to room temperature at a rate of 1°C / h to obtain a large amount of (S-AMPE)Pb 2 Br 5 ;

[0090] (4) Weigh 147 μL (1 mmol) S-AMPE and 741 mg (2 mmol) PbBr 2 Dissolve them together in 1 mL of hydrobromic acid (40% by mass) to obtain (S-AMPE)Pb 2 Br 5 Mix the solution, and treat the mixed solution according to the above step (2) to obtain a clear light brown solution;

[0091] (5) The (S-AMPE)Pb obtained in step (3) above 2 Br 5 The micro single crystals were slowly placed in the clear light brown solution obtained in step (4) and heated at a constant temperature of 80°C for 48 h to obtain centimeter-scale chiral halide perovskite single crystals (S-AMPE) Pb 2 Br 5 If the single crystal size is not large enough, the heating time can be appropriately extended to promote its crystallization.

[0092] Example 4

[0093] Preparation of chiral halide perovskite single crystals with organic chiral molecule (R)-2-amino-1-phenylethanol (R-AMPE) as the A-site molecule (R-AMPE)Pb 2 Br 5 The preparation method is the same as that of Example 3, except that S-AMPE is replaced by R-AMPE in equal moles.

[0094] Example 5

[0095] Preparation of chiral halide perovskite single crystals with organic chiral molecule (S)-2-methylpyrrolidine (S-MPY) as the A-site molecule (S-MPY)Pb 2 Br 5 , the preparation method comprises the following steps:

[0096] (1) Weigh 86 mg (1 mmol) of S-MPY and 741 mg (2 mmol) of PbBr 2 Dissolve them together in 1 mL of hydrobromic acid (40% by mass) to obtain (S-MPY)Pb 2 Br 6 Mixing solutions;

[0097] (2) Place the prepared mixed solution on a heating table at 100°C, stir and mix well, and heat for 4 hours until PbBr 2 The powder is completely dissolved. Observe whether the solute is fully dissolved. If not, shake it appropriately to promote its dissolution or extend the heating time to promote its dissolution. The completely dissolved solution is a clear light brown liquid, which is (S-MPY)Pb 2 Br 5 Perovskite precursor solution;

[0098] (3) After the perovskite precursor solution is completely dissolved and becomes clear, the crystallization process begins. It is first kept at 100°C for 2 hours, then cooled to 80°C at a rate of 1°C / h, kept at this temperature for 24 hours, and then cooled to room temperature at a rate of 1°C / h to obtain a large amount of (S-MPY)Pb 2 Br 5;

[0099] (4) Weigh 147 μL (1 mmol) S-MPY and 741 mg (2 mmol) PbBr 2 Dissolve them together in 1 mL of hydrobromic acid (40% by mass) to obtain (S-MPY)Pb 2 Br 5 Mix the solution, and treat the mixed solution according to the above step (2) to obtain a clear light brown solution;

[0100] (5) The (S-MPY)Pb obtained in step (3) above 2 Br 5 The micro single crystals were slowly placed in the clear light brown solution obtained in step (4) and heated at a constant temperature of 80°C for 48 h to obtain centimeter-scale chiral halide perovskite single crystals (S-MPY)Pb 2 Br 5 If the single crystal size is not large enough, the heating time can be appropriately extended to promote its crystallization.

[0101] Example 6

[0102] Preparation of chiral halide perovskite single crystals with organic chiral molecule (R)-2-methylpyrrolidine (R-MPY) as the A-site molecule (R-MPY)Pb 2 Br 5 The preparation method is the same as that of Example 5, except that S-MPY is replaced by R-MPY in equal moles.

[0103] Example 7

[0104] Preparation of chiral halide perovskite single crystals with organic chiral molecule (S)-2-aminomethyl-1-ethylpyrrolidine (S-AMEPY) as the A-site molecule (S-AMEPY)Pb 2 Cl 6 , the preparation method comprises the following steps:

[0105] (1) Weigh 176.4 μL (1.2 mmol) of S-AMEPY and 667.2 mg (2.4 mmol) of PbCl 2 Dissolve them together in 1 mL of hydrochloric acid (mass fraction 30%) to obtain (S-AMEPY)Pb 2 Cl 6 Mixing solutions;

[0106] (2) Place the prepared mixed solution on a 100°C heating table, stir and mix well, and heat for 4 hours until PbCl 2The powder is completely dissolved. Observe whether the solute is fully dissolved. If not, shake it appropriately to promote its dissolution or extend the heating time to promote its dissolution. The completely dissolved solution is a clear light brown liquid, which is (S-AMEPY)Pb 2 Br 6 Perovskite precursor solution;

[0107] (3) After the perovskite precursor solution is completely dissolved and becomes clear, the crystallization process begins. It is first kept at 100°C for 2 hours, then cooled to 80°C at a rate of 1°C / h, kept at this temperature for 24 hours, and then cooled to room temperature at a rate of 1°C / h to obtain a large amount of (S-AMEPY)Pb 2 Cl 6 ;

[0108] (4) Weigh 147 μL (1 mmol) S-AMEPY and 741 mg (2 mmol) PbCl 2 Dissolve them together in 1 mL of hydrochloric acid (mass fraction 30%) to obtain (S-AMEPY)Pb 2 Cl 6 Mix the solution, and treat the mixed solution according to the above step (2) to obtain a clear light brown solution;

[0109] (5) The (S-AMEPY)Pb obtained in step (3) above 2 Cl 6 The micro single crystals were slowly placed in the clear light brown solution obtained in step (4) and heated at a constant temperature of 80°C for 48 h to obtain centimeter-scale chiral halide perovskite single crystals (S-AMEPY)Pb 2 Cl 6 If the single crystal size is not large enough, the heating time can be appropriately extended to promote its crystallization.

[0110] Example 8

[0111] Preparation of chiral halide perovskite single crystals with organic chiral molecule (R)-2-aminomethyl-1-ethylpyrrolidine (R-AMEPY) as the A-site molecule (R-AMEPY)Pb 2 Cl 6 The preparation method is the same as that of Example 7, except that S-AMEPY is replaced by R-AMEPY in equal moles.

[0112] Example 9

[0113] Preparation of chiral halide perovskite single crystals with organic chiral molecule (S)-2-aminomethyl-1-ethylpyrrolidine (S-AMEPY) as the A-site molecule (S-AMEPY)Pb 2 I 6 , the preparation method comprises the following steps:

[0114] (1) Weigh 147 μL (1 mmol) S-AMEPY and 922 mg (2 mmol) PbI 2 Dissolve them together in 1 mL of hydrogen iodide (mass fraction 40%) to obtain (S-AMEPY)Pb 2 I 6 Mixing solutions;

[0115] (2) The prepared mixed solution was placed on a heating table at 100°C and heated for 4 h until PbI 2 The powder is completely dissolved. Observe whether the solute is fully dissolved. If not, shake it appropriately to promote its dissolution or extend the heating time to promote its dissolution. The completely dissolved solution is a clear light brown liquid, which is (S-AMEPY)Pb 2 I 6 Perovskite precursor solution;

[0116] (3) After the perovskite precursor solution is completely dissolved and becomes clear, the crystallization process begins. It is first kept at 100°C for 2 hours, then cooled to 40°C at a rate of 10°C / h, kept at this temperature for 24 hours, and then cooled to room temperature at a rate of 10°C / h to obtain a large amount of (S-AMEPY)Pb 2 Br 6 ;

[0117] (4) Weigh 117.6 μL (0.8 mmol) of S-AMEPY and 737.6 mg (1.6 mmol) of PbI 2 Dissolve them together in 1 mL of hydrobromic acid (mass fraction 40%) to obtain (S-AMEPY)Pb 2 I 6 Mix the solution, and treat the mixed solution according to the above step (2) to obtain a clear light brown solution;

[0118] (5) The (S-AMEPY)Pb obtained in step (3) above 2 I 6 The micro single crystals were slowly placed in the clear light brown solution obtained in step (4) and heated at a constant temperature of 80°C for 48 h to obtain centimeter-scale chiral halide perovskite single crystals (S-AMEPY)Pb 2 I 6 If the single crystal size is not large enough, the heating time can be appropriately extended to promote its crystallization.

[0119] Comparative Example 1

[0120] The same as Example 1, except that in step (3), the process of cooling and crystallizing is specifically as follows:

[0121] First, keep it at a constant temperature of 100℃ for 2h, then cool it to 80℃ at a rate of 20℃ / h, keep it at that temperature for 24h, and then cool it to room temperature at a rate of 20℃ / h.

[0122] Performance Testing

[0123] The chiral halide perovskite single crystals prepared in Examples 1-9 and Comparative Example 1 were used as raw materials to prepare circularly polarized photodetectors (see the schematic diagram of the structure). Figure 6 ), the specific preparation method is: use an interdigital electrode mask to plate a layer of gold electrode with a thickness of 100 nm on the upper surface of the chiral halide perovskite single crystal; after the interdigital electrode is plated, connect the two probes of the probe station to the electrodes at both ends of the photodetector to perform relevant photoelectric performance tests.

[0124] (S-AMEPY)Pb of Example 1 2 Br 6 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light are shown in the figure. Figure 7 .Depend on Figure 7 It can be seen that when the photodetector is irradiated with ultraviolet light, the photocurrent rise time is 156 μs and the fall time is 201 μs, indicating that the circularly polarized photodetector exhibits a rapid response to ultraviolet light.

[0125] (R-AMEPY)Pb of Example 2 2 Br 6 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light are shown in the figure. Figure 8 , it can be seen that when the photodetector is irradiated by ultraviolet light, the photocurrent rise time is 215μs and the fall time is 234μs, indicating that the circularly polarized photodetector exhibits a fast response to ultraviolet light.

[0126] Fig. 9 and Fig.10 (S-AMEPY)Pb of Example 1 2 Br 6 The responsivity and detectivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation are measured. Fig. 9 , 10 It can be seen that under the irradiation of left-handed and right-handed circularly polarized light, the detector's responsivity and detection rate have obvious differences, which reflects the material's excellent ability to distinguish left-handed and right-handed circularly polarized light. 2 At an illumination intensity of 100 nm, the detector has a responsivity of 102 A / W and 56 A / W to left-handed and right-handed circularly polarized light, respectively, and a detection rate of 4.5×10 15 Jones and 2.5×10 15Jones, showing the detector's high sensitivity to circularly polarized light and excellent photoelectric conversion efficiency.

[0127] Fig.11 and Fig.12 (R-AMEPY)Pb of Example 2 2 Br 6 The responsivity and detectivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation are measured. Fig.11 , 12 It can be seen that under the irradiation of left-handed and right-handed circularly polarized light, the detector's responsivity and detection rate have obvious differences, which reflects the material's excellent ability to distinguish left-handed and right-handed circularly polarized light. 2 Under the illumination intensity of , the detector has a responsivity of 41A / W and 81A / W to left-handed and right-handed circularly polarized light, and the detection rate is 9.2×10 14 Jones and 1.8×10 15 Jones, showing the detector's high sensitivity to circularly polarized light and excellent photoelectric conversion efficiency.

[0128] (S-AMPE)Pb of Example 3 2 Br 5 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light are shown in the figure. Fig.13 .Depend on Fig.13 It can be seen that when the photodetector is irradiated with ultraviolet light, the photocurrent rise time is 209 μs and the fall time is 253 μs, indicating that the circularly polarized photodetector exhibits a rapid response to ultraviolet light.

[0129] (R-AMPE)Pb of Example 4 2 Br 5 The test results of the prepared circular polarization photodetector's response speed to 365nm ultraviolet light are shown in the figure. Fig.14 .Depend on Fig.14 It can be seen that when the photodetector is irradiated with ultraviolet light, the photocurrent rise time is 297 μs and the fall time is 334 μs, indicating that the circularly polarized photodetector exhibits a rapid response to ultraviolet light.

[0130] (S-MPY)Pb of Example 5 2 Br 5 The curve of the current versus voltage of the prepared circularly polarized photodetector in the dark state and under 365nm light is shown in Fig.15 It can be seen that the response of the photodetector is significantly enhanced when the light intensity increases. When the voltage is 4V, the on / off ratio is 183.

[0131] (R-MPY)Pb of Example 6 2 Br 5 The curve of the current versus voltage of the prepared circularly polarized photodetector in the dark state and under 365nm light is shown in Fig.16 It can be seen that the response of the photodetector is significantly enhanced when the light intensity increases. When the voltage is 4V, the on / off ratio is 161.

[0132] (S-AMEPY)Pb of Example 7 2 Cl 6 The responsivity and detectivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation are shown in Fig.17 and Fig.18 It can be seen that under the irradiation of left-handed and right-handed circularly polarized light, the detector's responsivity and detection rate have obvious differences, which reflects the material's excellent ability to distinguish left-handed and right-handed circularly polarized light. At the same time, it also has a high responsivity and detection rate.

[0133] (R-AMEPY)Pb of Example 8 2 Cl 6 The responsivity and detectivity of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light irradiation are shown in Fig.19 and Fig. 20 It can be seen that under the irradiation of left-handed and right-handed circularly polarized light, the detector's responsivity and detection rate have obvious differences, which reflects the material's excellent ability to distinguish left-handed and right-handed circularly polarized light. At the same time, it also has a high responsivity and detection rate.

[0134] (S-AMEPY)Pb of Example 9 2 I 6 The test results of the circular polarization photodetector prepared for the response speed of the circular polarization photodetector to 365nm ultraviolet light are shown in the figure below. Fig.21 As shown by Fig.21 It can be seen that when the photodetector is irradiated with ultraviolet light, the photocurrent rise time is 415 μs and the fall time is 375 μs, indicating that the circularly polarized photodetector exhibits a rapid response to ultraviolet light.

[0135] (S-AMEPY)Pb of Comparative Example 1 2 Br 6 Preparation of circularly polarized photodetector The response and detection rate of the prepared circularly polarized photodetector under 365nm left-handed (LCP) and right-handed (RCP) circularly polarized light are shown as follows: Fig. 22 and Fig.23 As shown. Fig. 22 ,23 It can be seen that at 2.3μW / cm 2 At an illumination intensity of , the detector's responsivity to left-handed and right-handed circularly polarized light is 12A / W and 3A / W, respectively, and the detection rate is 2.7×10 14 Jones and 6.8×10 13 Jones, compared with Example 1, its responsivity and detection rate are 1 to 2 orders of magnitude lower. The reason is that the cooling rate of the single crystal grown in Example 1 is too fast, and the drastic change in the environment causes a large number of crystal seeds to precipitate during the crystallization process. In addition, twins will precipitate on the surface of the single crystal during the precipitation process. The centimeter-level single crystal grown based on this crystal seed has poor internal crystallinity, which hinders the transmission of photogenerated carriers and ultimately leads to poor photoelectric performance of the device.

[0136] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A chiral halide perovskite single crystal, characterized in that: The chiral halide perovskite single crystal is an ABX3 perovskite single crystal having an overlapping structure of organic molecules and inorganic octahedral layers, wherein the chiral organic molecule replaces the A-position cation in the perovskite and the B-position is Pb 2+ , X is Cl - Br - or I - ; The chiral halide perovskite single crystal uses lead halide as an octahedral inorganic framework, and the chiral organic molecules and the inorganic framework are connected by a multi-hydrogen bond structure; The chiral organic molecule is one of (S)- / (R)-2-aminomethyl-1-ethylpyrrolidine, (S)- / (R)-2-amino-1-phenylethanol and (S)- / (R)-2-methylpyrrolidine; The method for preparing the chiral halide perovskite single crystal comprises the following steps: (1) dissolving lead halide and chiral organic molecules in hydrohalic acid, stirring and mixing, and filtering to obtain a perovskite precursor solution; (2) cooling and crystallizing the perovskite precursor solution after reaction to obtain a chiral halide perovskite micro single crystal; (3) preparing a perovskite precursor solution according to the method of step (1), placing the chiral halide perovskite micro single crystal in the prepared perovskite precursor solution, and heating at a constant temperature to obtain the chiral halide perovskite single crystal; In step (2), the cooling crystallization is a gradient cooling, specifically cooling to 40-80°C at a rate of 0.1-10°C / h, and then cooling to room temperature at a rate of 1-10°C / h after keeping warm for 24 hours.

2. The chiral halide perovskite single crystal according to claim 1, characterized in that: In step (1), the halogen in the lead halide is the same as the halogen in the hydrohalic acid.

3. The chiral halide perovskite single crystal according to claim 1, characterized in that: In step (1), the molar ratio of the lead halide to the chiral organic molecule is 2:1, and the concentration of the chiral organic molecule in the perovskite precursor solution is 0.1-2 mol / L.

4. The chiral halide perovskite single crystal according to claim 1, characterized in that: In step (1), the stirring and mixing is performed at a temperature of 60-140° C. and for a time of 0.5-10 h.

5. The chiral halide perovskite single crystal according to claim 1, characterized in that: In step (3), the constant temperature heating temperature is 80°C.

6. Use of the chiral halide perovskite single crystal according to any one of claims 1 to 5 in the preparation of a chiral photodetector.

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