Organic-inorganic hybrid zero-dimensional halide perovskite single crystal material and preparation method thereof

Abstract

The invention discloses an organic-inorganic hybrid zero-dimensional halide perovskite single crystal material and a preparation method thereof. The chemical formula of the organic-inorganic hybrid zero-dimensional halide perovskite single crystal material is PMA4InCl7.H2O, and the chemical formula of the antimony-doped single crystal material is PMA4InCl7.H2O: Sb, the corresponding single crystal material is obtained through the steps of raw material adding, cooling crystallization, suction filtration, drying and the like. The optical band gap of the PMA4InCl7. H2O is determined to be 4-5 eV through an ultraviolet-visible spectrophotometer, and when the PMA4InCl7. H2O is irradiated by a 365 nm portable ultraviolet lamp, the PMA4InCl7. H2O shows light blue; the optical band gap of the PMA4InCl7. H2O: Sb is determined to be 3-4 eV through an ultraviolet-visible spectrophotometer, and when the PMA4InCl7. H2O: Sb is irradiated by a 365 nm portable ultraviolet lamp, the PMA4InCl7. H2O: Sb shows bright yellow. The maximum quantum yield measured by an absolute fluorescence quantum yield spectrometer can reach 72%.

Description

Technical Field

[0001] The invention relates to a non-lead organic-inorganic hybrid zero-dimensional indium-based halide perovskite single crystal, belonging to the technical field of perovskite single crystals. Background Art

[0002] Perovskite single crystals have attracted widespread attention in the optoelectronics field due to their excellent optoelectronic properties and stability. However, the commercial development of traditional lead-based halide perovskites is limited by their toxicity, susceptibility to water decomposition, and poor stability. The development of high-performance non-lead perovskite single crystals is an inevitable trend in the development of perovskite materials. Zero-dimensional materials, due to their unique structural advantages, exhibit excellent optical properties. Therefore, the development of new, efficient and stable zero-dimensional non-lead halide perovskite single crystals is of great significance. Summary of the Invention

[0003] To solve the above problems, the present invention provides an organic-inorganic hybrid zero-dimensional halide perovskite single crystal material and a preparation method thereof.

[0004] In the first aspect, the present invention provides an organic-inorganic hybrid zero-dimensional halide perovskite single crystal material, the chemical formula of which is PMA4InCl7·H2O, wherein PMA + It is a benzyl ammonium cation, chemical formula (C7H 10 N) + .

[0005] Furthermore, the single crystal material belongs to the triclinic space group P-1 and has a 0-dimensional crystal structure with a lattice constant of and In addition, α, β, and γ are 81.0053 degrees, 80.3369 degrees, and 89.9949 degrees, respectively.

[0006] In a second aspect, the present invention provides an antimony-doped organic-inorganic hybrid zero-dimensional halide perovskite single crystal material, whose chemical formula is PMA4InCl7·H2O:Sb. In this single crystal material, antimony ions replace indium ions in indium chloride octahedrons without destroying their crystal structure.

[0007] In a third aspect, the present invention provides a method for preparing the organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to the first aspect, comprising the following steps:

[0008] Benzylamine hydrochloride (PMACl) and indium chloride are added to a container according to the required stoichiometric ratio, and then hydrochloric acid is added. The mixture is reacted at 90-120°C for 5-8 hours. After the reaction is completed, the mixture is naturally cooled to room temperature, filtered, and vacuum dried.

[0009] Furthermore, 0.6-1 mL of concentrated hydrochloric acid is required to synthesize 0.1 mmol of PMA4InCl7·H2O.

[0010] Furthermore, the molar ratio of benzylamine hydrochloride (PMACl) to indium chloride is 6:1.

[0011] Further, vacuum drying was performed in a vacuum oven at 60±10° C. for 18-24 h.

[0012] In a fourth aspect, the present invention provides a method for preparing the antimony-doped organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to the second aspect, comprising the following steps:

[0013] Benzylamine hydrochloride (PMACl), antimony trichloride and indium chloride are added to a container according to the required stoichiometric ratio, and then hydrochloric acid is added. The mixture is reacted at 90-120°C for 5-8 hours. After the reaction is completed, the mixture is naturally cooled to room temperature, filtered and vacuum dried.

[0014] Furthermore, 0.6-1 mL of concentrated hydrochloric acid is required to synthesize 0.1 mmol of PMA4InCl7·H2O.

[0015] Further, vacuum drying was performed in a vacuum oven at 60±10° C. for 18-24 h.

[0016] Furthermore, the molar ratio of benzylamine hydrochloride (PMACl) and indium chloride is 6:1.

[0017] Furthermore, in terms of molar ratio, Sb / (Sb+In) is 0.1-0.4.

[0018] In a fifth aspect, the present invention further provides a use of the organic-inorganic hybrid zero-dimensional halide perovskite single crystal material described in the first aspect or the antimony-doped organic-inorganic hybrid zero-dimensional halide perovskite single crystal material described in the second aspect in a perovskite phosphor material.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] (1) The optical band gap of PMA4InCl7·H2O was determined to be 4-5 eV by UV-visible spectrophotometry, and it appeared light blue when irradiated with a 365 nm portable UV lamp.

[0021] (2) The optical band gap of PMA4InCl7·H2O:Sb was determined to be 3-4 eV by UV-visible spectrophotometry. When irradiated with a 365 nm handheld UV lamp, it appeared bright yellow. The quantum yield, as measured by an absolute fluorescence quantum yield spectrometer, reached a maximum of 72%.

[0022] (3) PMA4InCl7·H2O and PMA4InCl7·H2O:Sb can be stably present at 25°C and 55% relative humidity for more than 50 days. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a crystal structure diagram of the undoped non-lead organic-inorganic zero-dimensional hybrid indium-based halide perovskite single crystal material prepared in Example 1.

[0024] Figure 2 These are powder XRD diffraction spectra of the undoped non-lead organic-inorganic hybrid zero-dimensional indium-based halide perovskite single crystal materials prepared in Example 1 and the antimony-doped non-lead organic-inorganic hybrid zero-dimensional indium-based halide perovskite single crystal materials prepared in Example 4.

[0025] Figure 3 These are powder XRD diffraction patterns of the lead-free organic-inorganic hybrid zero-dimensional indium-based halide perovskite single crystal materials with different antimony doping ratios prepared in Examples 1 to 5. In the figure, x is Sb / (Sb+In).

[0026] Figure 4 These are the steady-state fluorescence excitation spectrum and fluorescence spectrum of the undoped, lead-free organic-inorganic hybrid zero-dimensional indium-based halide perovskite single crystal material prepared in Example 1 at room temperature.

[0027] Figure 5 These are the steady-state fluorescence excitation spectrum and fluorescence spectrum of the antimony-doped lead-free organic-inorganic hybrid zero-dimensional indium-based halide perovskite single crystal material prepared in Example 4 at room temperature. DETAILED DESCRIPTION

[0028] The present application is further described below with reference to specific embodiments.

[0029] It should be noted that the terms such as "upper", "lower", "left", "right", and "middle" cited in this specification are only for the convenience of description and are not used to limit the scope of implementation. Changes or adjustments to their relative relationships should be regarded as the scope of implementation of this application without substantially changing the technical content.

[0030] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0031] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0032] As used herein, the term "about" is used to provide flexibility and imprecision associated with a given term, measurement, or value. One skilled in the art can readily determine the degree of flexibility for a particular variable.

[0033] As used herein, the term "at least one of" is intended to be synonymous with "one or more of." For example, "at least one of A, B, and C" explicitly includes only A, only B, only C, and combinations of each thereof.

[0034] Example 1

[0035] 86.2 mg of benzylamine hydrochloride and 22.1 mg of indium chloride were added to a 10 mL glass bottle in sequence. 0.8 mL of concentrated hydrochloric acid was added to the glass bottle. The glass bottle was moved to an oil bath at a stable temperature of 100 ° C and heated with stirring. After about 10 minutes, the reaction solution was observed to change from turbid to transparent, indicating that the sample was completely dissolved. The oil bath was closed and allowed to cool naturally to room temperature. Small crystals were observed to gradually precipitate. After standing for 6 hours, the flask was removed from the oil bath. The crude product of the solid-liquid mixture was filtered and washed with n-hexane. The resulting colorless transparent crystals were placed in a vacuum oven set at 60 ° C and dried for 24 hours.

[0036] Powder XRD diffraction showed that Figure 2 As shown, the undoped zero-dimensional non-lead organic-inorganic hybrid indium-based halide perovskite single crystal material PMA4InCl7·H2O has high crystallinity and belongs to the triclinic P-1 space group. Figure 1 Showing its crystal structure, isolated [InCl6] 3- Octahedrons are PMA + The optical band gap of the material was determined to be 4-5 eV by UV-visible spectrophotometry. The fluorescence lifetime was confirmed to be 3-4 ns by Edinburgh steady-state transient fluorescence spectrometer FLS1000, and the fluorescence yield was 6% by absolute fluorescence quantum yield spectrometer. Its room temperature steady-state fluorescence excitation spectrum and fluorescence spectrum are shown in Figure 2. Figure 4 As shown, Figure 2 and Figure 4 The intensity is the normalized intensity.

[0037] Example 2

[0038] 86.2 mg of benzylamine hydrochloride, 22.1 mg of indium chloride, and 2.2 mg of antimony trichloride were added sequentially to a 10 mL glass vial. 0.8 mL of concentrated hydrochloric acid was then added to the vial. The vial was then placed in an oil bath at 100°C and heated with stirring. After approximately 10 minutes, the reaction solution turned from turbid to transparent, indicating complete dissolution of the sample. The oil bath was closed and allowed to cool naturally to room temperature. Small crystals were observed to gradually precipitate. After 6 hours of stabilization, the flask was removed from the oil bath. The crude solid-liquid mixture was filtered and washed with n-hexane. The resulting colorless, transparent crystals were dried in a vacuum oven set at 60°C for 24 hours to obtain PMA4InCl7·H2O:Sb, where the doping ratio x = 0.1. The fluorescence yield was 62% as measured by absolute fluorescence quantum yield spectrometry.

[0039] Example 3

[0040] 86.2 mg of benzylamine hydrochloride, 22.1 mg of indium chloride, and 4.6 mg of antimony trichloride were added sequentially to a 10 mL glass vial. 0.8 mL of concentrated hydrochloric acid was then added to the vial. The vial was then placed in an oil bath at 100°C and heated with stirring. After approximately 10 minutes, the reaction solution turned from turbid to transparent, indicating complete dissolution of the sample. The oil bath was closed and allowed to cool naturally to room temperature. Small crystals were observed to gradually precipitate. After 6 hours of stabilization, the flask was removed from the oil bath. The crude solid-liquid mixture was filtered and washed with n-hexane. The resulting colorless, transparent crystals were dried in a vacuum oven set at 60°C for 24 hours to obtain PMA4InCl7·H2O:Sb, where the doping ratio x = 0.2. The fluorescence yield was 70% as measured by absolute fluorescence quantum yield spectrometry.

[0041] Example 4

[0042] 86.2 mg of benzylamine hydrochloride, 22.1 mg of indium chloride, and 6.8 mg of antimony trichloride were added sequentially to a 10 mL glass vial. 0.8 mL of concentrated hydrochloric acid was then added to the vial. The vial was then placed in an oil bath at 100°C and heated with stirring. After approximately 10 minutes, the reaction solution turned from turbid to transparent, indicating complete dissolution of the sample. The oil bath was closed and allowed to cool naturally to room temperature. Small crystals were observed to gradually precipitate. After standing for 6 hours, the flask was removed from the oil bath. The crude solid-liquid mixture was filtered and rinsed with n-hexane. The resulting colorless, transparent crystals were dried in a vacuum oven set at 60°C for 24 hours to obtain PMA4InCl7·H2O:Sb, where the doping ratio x = 0.3.

[0043] The crystals obtained in this embodiment were subjected to powder XRD diffraction, as shown in FIG. Figure 2As shown, the perovskite single crystal material PMA4InCl7·H2O:Sb has high crystallinity. The optical band gap of the material was determined to be 3-4eV by UV-visible spectrophotometry, and the fluorescence lifetime was confirmed to be 3-4μs by Edinburgh steady-state transient fluorescence spectrometer FLS1000. The fluorescence yield was 72% measured by absolute fluorescence quantum yield spectrometer. Its room temperature steady-state fluorescence excitation spectrum and fluorescence spectrum are shown in Figure 2. Figure 5 As shown, Figure 5 The intensity is the normalized intensity.

[0044] Example 5

[0045] 86.2 mg of benzylamine hydrochloride, 22.1 mg of indium chloride, and 9.1 mg of antimony trichloride were added sequentially to a 10 mL glass vial. 0.8 mL of concentrated hydrochloric acid was then added to the vial. The vial was then placed in an oil bath at 100°C and heated with stirring. After approximately 10 minutes, the reaction solution turned from turbid to transparent, indicating complete dissolution of the sample. The oil bath was closed and allowed to cool naturally to room temperature. Small crystals were observed to gradually precipitate. After 6 hours of stabilization, the flask was removed from the oil bath. The crude solid-liquid mixture was filtered and washed with n-hexane. The resulting colorless, transparent crystals were dried in a vacuum oven set at 60°C for 24 hours to obtain PMA4InCl7·H2O:Sb, where the doping ratio x = 0.4. The fluorescence yield was 67% as measured by absolute fluorescence quantum yield spectrometry.

[0046] Examples 1-5 correspond to different gradients of antimony-doped zero-dimensional lead-free organic-inorganic hybrid indium-based halide perovskite single crystal materials, which are tested by powder XRD diffraction. Figure 3 As shown, Figure 3 The intensity is the normalized intensity.

[0047] The examples described above are only preferred solutions of the present invention and are only used to illustrate the present invention but not to limit the scope of the present invention. Any technical solution obtained by adopting or equivalent replacement or equivalent replacement method falls within the scope of protection of the present invention.

Claims

1. An organic-inorganic hybrid zero-dimensional halide perovskite single crystal material, characterized in that: Its chemical formula is PMA4InCl7·H2O, where PMA + It is a benzyl ammonium cation, chemical formula (C7H 10 N) + .

2. The organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to claim 1, wherein: It belongs to the triclinic space group P-1 and has a 0-dimensional crystal structure with lattice constants of 10.6340Å, 10.6721Å, and 17.0199Å. In addition, α, β, and γ are 81.0053 degrees, 80.3369 degrees, and 89.9949 degrees, respectively.

3. An antimony-doped organic-inorganic hybrid zero-dimensional halide perovskite single crystal material, characterized in that: Its chemical formula is PMA4InCl7·H2O: Sb. In this single crystal material, antimony ions replace indium ions in the indium chloride octahedron without destroying its crystal structure.

4. A method for preparing the organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to claim 1 or 2, characterized in that: The steps include: Benzylamine hydrochloride and indium chloride are added to a container according to the required stoichiometric ratio, and then hydrochloric acid is added. The mixture is reacted at 90-120° C. for 5-8 hours. After the reaction is completed, the mixture is naturally cooled to room temperature, filtered, and vacuum dried.

5. A method for preparing the antimony-doped organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to claim 3, comprising the following steps: Benzylamine hydrochloride, antimony trichloride and indium chloride are added to a container according to the required stoichiometric ratio, and then hydrochloric acid is added. The mixture is reacted at 90-120° C. for 5-8 hours. After the reaction is completed, the mixture is naturally cooled to room temperature, filtered and vacuum dried.

6. The method according to claim 4 or 5, characterized in that 0.6-1 mL of concentrated hydrochloric acid is required to synthesize 0.1 mmol of PMA4InCl7·H2O.

7. The method according to claim 4 or 5, characterized in that The molar ratio of benzylamine hydrochloride to indium chloride is 6:

1.

8. The method according to claim 4 or 5, characterized in that Dry in a vacuum oven at 60±10℃ for 18-24h.

9. The method according to claim 5, wherein In terms of molar ratio, Sb / (Sb+In) is 0.1-0.

4.

10. Use of the organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to claim 1 or 2 or the antimony-doped organic-inorganic hybrid zero-dimensional halide perovskite single crystal material according to claim 3 in a perovskite phosphor material.

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