Sb < 3 + >-doped zinc-based organic-inorganic halide perovskite crystal with double lattice sites and preparation method of Sb < 3 + >-doped zinc-based organic-inorganic halide perovskite crystal

Abstract

The invention discloses a double-lattice Sb < 3 + > doped zinc-based organic-inorganic halide perovskite crystal and a preparation method thereof. The main component of the crystal is (ETBT) 2ZnBr4. The crystal is synthesized by a hydrothermal method and has two lattice sites of Zn1 and Zn2. After Sb < 3 + > is doped, under the excitation of 310 nm light, the emission peak is located between 450 nm and 850 nm, and two obvious emission peaks of 530 nm and 670 nm correspond to different luminescence centers. By changing the excitation wavelength, the light emitting color can be changed among green, yellow and red. Under excitation of 365nm light, the emission peak covers 500-900nm, and the material contains a near-infrared light part and can be used for night vision observation when combined with a 365nm ultraviolet chip. In addition, the material has different light emitting colors under different excitation wavelengths, has obvious contrast under a near-infrared camera, and can be used for anti-counterfeiting, art display and the like. The preparation method is simple and beneficial to large-scale production.

Description

Technical Field

[0001] The present invention relates to the field of crystal material technology, and in particular to a Sb 3+ A zinc-doped organic-inorganic halide perovskite crystal and a preparation method thereof, wherein the crystal has important application value in the fields of luminescent display, night vision technology, anti-counterfeiting and artistic display. Background Art

[0002] In recent years, organic-inorganic hybrid perovskite materials have attracted widespread attention in the optoelectronic field due to their excellent optoelectronic properties and adjustable luminescence characteristics. However, most existing perovskite materials are limited to a single luminescence center, making it difficult to achieve multi-color luminescence regulation. In addition, traditional phosphor materials have problems such as uneven particle size and severe agglomeration in LED applications, which limits their performance in practical applications. Therefore, it is of great significance to develop an organic-inorganic hybrid perovskite material with multi-color luminescence characteristics.

[0003] The luminescence properties of various organic-inorganic hybrid perovskite materials have been reported in the literature, such as Zhang et al. (C 6 H 5 CH 2 NH 3 ) 2 PbB 4 The blue light emission of the material (Adv. Mater., 2020, 32, 1907052), and Wang et al. (C 4 H 9 NH 3 ) 2 PbI 4 The red light emission of the material (J.Am.Chem.Soc.,2019,141,12352-12356). However, most of these materials are limited to a single luminescent center, making it difficult to achieve multi-color luminescence regulation. Therefore, it is of great significance to develop a perovskite material with a dual-site luminescent center. Summary of the invention

[0004] Purpose of the Invention

[0005] The object of the present invention is to provide a Sb with double lattice 3+ Doped zinc-based organic-inorganic halide perovskite crystal and its preparation method. The crystal can achieve precise multi-color luminescence under different excitation wavelengths, has significant emission in the near-infrared region, and can be widely used in luminous display, night vision observation, anti-counterfeiting and art display. At the same time, the preparation method is simple, low-cost, and easy to large-scale industrial production.

[0006] Technical Solution

[0007] The main component of the crystal of the present invention is (ETBT) 2 ZnBr 4 , Sb was introduced by hydrothermal method 3+ Doping forms a structure with two lattice sites, Zn1 and Zn2. Under 310nm light excitation, (ETBT) 2 ZnBr 4 :Sb 3+ The material exhibits an emission peak range of 450–850 nm, with two obvious emission peaks at 530 nm and 670 nm corresponding to different luminescence centers. This is due to the Sb 3+ Occupying Zn1 and Zn2 sites respectively.

[0008] When the excitation wavelength is changed, the luminescent color of the crystal can continuously change between green, yellow and red. This unique luminescent property provides broad prospects for its application in the display field. According to DFT theoretical calculations, the matrix material (ETBT) 2 ZnBr 4 The band gap of Sb is 2.82eV. 3+ When doped with Zn1, the band gap of the material becomes 2.27eV, corresponding to 530nm green light emission; when Sb 3+ When doped with Zn2 sites, the band gap is 1.66eV, corresponding to red light emission at 670nm, which theoretically explains the reason for the change in luminescent color.

[0009] Under 365nm light excitation, (ETBT) 2 ZnBr 4 :Sb 3+ The emission peak range of the crystal is extended to 500-900nm, covering the near-infrared part. By combining the crystal with a 365nm UV chip, LED devices suitable for night vision observation and other fields can be prepared. In addition, the material can be applied to anti-counterfeiting, art display and other fields by taking advantage of the characteristics of different luminous colors under different excitation wavelengths and obvious contrast under near-infrared cameras. For example, when drawing specific patterns, different effects are presented under different light excitations, and unique visual effects are achieved under near-infrared cameras.

[0010] The preparation method adopts hydrothermal method to react ETBTBr, ZnBr 2 and SbBr 3 Add a certain volume of hydrobromic acid according to a specific molar ratio and react at a suitable temperature for a certain time. This method is easy to operate, has low requirements on equipment, and provides the possibility for large-scale production.

[0011] Beneficial Effects

[0012] The crystal of the present invention realizes precise multi-color luminescence, can significantly improve the display effect in the display field, meet the needs of high-resolution and multi-color display, and is expected to promote the development of display technology.

[0013] Its good near-infrared luminescence performance makes the LED device combined with the UV chip have important application value in the field of night vision observation, which can improve the performance and imaging quality of night vision equipment.

[0014] In terms of anti-counterfeiting and artistic display, the material's unique luminescence properties and high contrast under near-infrared cameras provide new means and material options for anti-counterfeiting technology innovation and artistic creation.

[0015] The hydrothermal preparation process is simple and low-cost, which is conducive to large-scale industrial production, reduces product costs, and promotes the widespread application of related technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 :(ETBT) 2 ZnBr 4 :Sb 3+ XRD pattern of the crystal and single crystal fitting diagram.

[0017] Figure 2 :(ETBT) 2 ZnBr 4 :Sb 3+ Excitation and emission spectra of the crystal.

[0018] Figure 3 :(ETBT) 2 ZnBr 4 :Sb 3+ Graph showing the color changes of the crystal at different excitation wavelengths.

[0019] Figure 4 :(ETBT) 2 ZnBr 4 :Sb 3+ Electroluminescence spectrum of LED device composed of crystal and 365nm UV chip. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with embodiments and drawings, but the scope of protection claimed by the present invention is not limited to the scope shown in the embodiments.

[0021] Example 1

[0022] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of hydrogen bromide and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 24 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 60°C for 5 hours to obtain the final product. Use an XRD powder diffractometer (Bruker D8 Advance) to detect the physical phase of the product at room temperature. Figure 1 As shown, XRD characterization shows that the crystal synthesized by the present invention is pure phase (ETBT) 2 ZnBr 4 :Sb 3+ The luminescence properties of the materials were studied using a Fluoromax-4 fluorescence spectrometer (HORIBA Jobin Yvon Inc.). Figure 2 As shown, (ETBT) 2 ZnBr 4 :Sb 3+ The excitation spectrum of the nanostructured carbon nanotubes is in the range of 200 to 500 nm. Figure 3 As shown, Sb doped 3+ After that, under 310nm light excitation, the emission peak is located between 450-850nm, with two obvious emission peaks at 530nm and 670nm, corresponding to the luminescence centers of the two lattice sites of Zn1 and Zn2. Figure 4 It is a 365nm UV chip with (ETBT) 2 ZnBr 4 :Sb 3+ Electroluminescence spectrum of the composed LED device.

[0023] Example 2

[0024] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 36 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0025] Example 3

[0026] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 48 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 5 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0027] Example 4

[0028] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10mL of hydrobromic acid and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 48 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 60°C for 10 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0029] Example 5

[0030] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water, stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 24 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0031] Example 6

[0032] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 36 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 7 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0033] Example 7

[0034] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10mL of hydrobromic acid and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 36 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 60°C for 9 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0035] Example 8

[0036] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 48 hours. After the reaction is completed, naturally cool to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0037] Example 9

[0038] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 24 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 7 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0039] Example 10

[0040] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10mL of hydrobromic acid and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 24 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 60°C for 5 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0041] Embodiment 11

[0042] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 36 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0043] Example 12

[0044] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 48 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 7 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0045] Embodiment 13

[0046] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10mL of hydrobromic acid and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 48 hours. After the reaction is completed, naturally cool to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 60°C for 5 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0047] Embodiment 14

[0048] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 24 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0049] Embodiment 15

[0050] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 36 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 7 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0051] Example 16

[0052] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10mL of hydrobromic acid and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 36 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 60°C for 5 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0053] Embodiment 17

[0054] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 48 hours. After the reaction is completed, naturally cool to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0055] Embodiment 18

[0056] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 24 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 7 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0057] Embodiment 19

[0058] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10mL of hydrobromic acid and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 150°C, and the reaction time to 24 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol, and then dry them at 60°C for 5 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0059] Embodiment 20

[0060] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3 , mixed in a stoichiometric ratio. Dissolve the above raw materials in 10 mL of deionized water and stir evenly to form a uniform solution. Place the mixed solution in a hydrothermal reactor, set the temperature to 160°C, and the reaction time to 36 hours. After the reaction is completed, cool naturally to room temperature and obtain a crystalline product by centrifugation. Wash the crystals three times with ethanol and then dry them at 65°C for 6 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

[0061] Embodiment 21

[0062] Accurately weigh 2mmol of organic molecule ETBTBr and 0.97mmol of zinc salt ZnBr 2 and SbBr 3, mixed in a stoichiometric ratio. The above raw materials were dissolved in 10 mL of a mixed solvent of hydrobromic acid and deionized water (volume ratio 1:1), stirred evenly to form a uniform solution. The mixed solution was placed in a hydrothermal reactor, the temperature was set to 170°C, and the reaction time was 48 hours. After the reaction was completed, it was naturally cooled to room temperature and a crystalline product was obtained by centrifugation. The crystals were washed three times with ethanol and then dried at 70°C for 7 hours to obtain the final product. The XRD pattern and fluorescence spectrum of the product in this embodiment are basically similar to those in Example 1.

Claims

1. A Sb with double lattice 3+ Doped zinc-based organic-inorganic halide perovskite crystal, characterized in that The chemical formula is (ETBT)2ZnBr4:Sb 3+ , where ETBT is 3-ethylbenzothiazol-3-ammonium bromide, ZnBr4 is a zinc-based halide matrix, Sb 3 + For doping ions.

2. The perovskite crystal according to claim 1, characterized in that This material has two different lattices: Zn1 and Zn2. 3+ They can occupy these two lattice sites respectively, resulting in the material producing two obvious emission peaks under ultraviolet light excitation, located at 530nm and 670nm respectively.

3. The perovskite crystal according to claim 1, characterized in that Under 310nm light excitation, the emission peak of the material ranges from 450 to 850nm, and there are two obvious emission peaks, located at 530nm and 670nm respectively.

4. The perovskite crystal according to claim 1, characterized in that By changing the excitation wavelength, the material's emission color can be changed from green to yellow to red.

5. The perovskite crystal according to claim 1, characterized in that: The fluorescence lifetime values ​​at 530nm and 670nm are both in the microsecond range, indicating that the two characteristic emission peaks come from Sb 3+ The triplet emission from Sb 3+ Occupies different lattice sites of Zn1 and Zn2.

6. The perovskite crystal according to claim 1, characterized in that: The band gap of the matrix material (ETBT) 2ZnBr4 is 2.82 eV, when all Sb 3+ When doped with Zn1, the band gap of the material is 2.27eV, corresponding to 530nm green light emission; when all Sb 3+ When doped with Zn2 sites, the band gap of the material is 1.66eV, corresponding to red light emission at 670nm.

7. The perovskite crystal according to claim 1, characterized in that: Under 365nm light excitation, the material's emission peak ranges from 500 to 900nm, including the near-infrared part.

8. A method for preparing a perovskite crystal according to claims 1-7, characterized in that: The method comprises the following steps: weighing 3-ethylbenzothiazol-3-ammonium bromide (ETBTBr), ZnBr2 and SbBr2 according to a stoichiometric ratio, dissolving them in a hydrobromic acid solution, and stirring them evenly.

9. The preparation method according to claim 8, characterized in that: The mixed solution is transferred to a hydrothermal reactor, sealed, and reacted at 120-180° C. for 12-48 hours.

10. The preparation method according to claim 8, characterized in that: After the reaction was completed, the mixture was naturally cooled to room temperature and filtered to obtain (ETBT)2ZnBr4 crystals.

11. The preparation method according to claim 8, characterized in that: The crystalline product obtained by centrifugation is dried at 60-70°C for 5-10 hours to obtain the final product.

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