Method for tuning luminescence peak position of antimony-containing double perovskite luminescent material

Abstract

The invention is suitable for the technical field of double perovskite luminescent materials, and provides an antimony-containing double perovskite luminescent material luminescence peak position tuning method, which comprises the following steps: pre-pressing a stainless steel metal sheet by using a diamond anvil cell press, and drilling a hole groove at an indentation as a pressure cavity; the antimony-containing double perovskite crystal is placed in a pressure cavity, silicone oil is added as a pressure transmission medium, pressurization is carried out, ruby is adopted as a calibration pressure substance in the pressurization process, and the pressure is increased to 30.5 GPa from room temperature and normal pressure in the pressurization process. According to the invention, trivalent antimony ions and hexa-coordination groups formed by the trivalent antimony ions are utilized, a new acceptor energy level is inserted into a band gap of a perovskite main body material, yellow light emission is generated, the optical performance of the material is effectively tuned, a pressure means is utilized, other components are not introduced, the inter-atomic distance and interaction inside the material are accurately regulated and controlled, and the performance of the material is improved. The energy transfer pathway between different excited states in the material is optimized, large-range peak position movement is realized, and fluorescence with different chromaticity is obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of double perovskite luminescent materials, and in particular relates to a method for tuning the luminescent peak position of an antimony-containing double perovskite luminescent material. Background Art

[0002] Double perovskite luminescent materials have shown great potential in the fields of wide color gamut display, green energy, pressure sensing and dynamic optical regulation due to their unique dual metal site design, high defect tolerance and tunable exciton luminescence properties. + / Bi 3+ 、Na + / In 3+ ) can achieve continuous coverage of the luminescence peak from visible light to near-infrared in a single lattice, effectively avoiding the phase segregation and defects caused by different halogens in traditional single perovskites, effectively improving the stability of the material and the photoluminescence quantum yield, and is suitable for high-precision full-spectrum lighting and high-voltage sensor technology.

[0003] In the prior art, the double perovskite B-site ion species (such as Sb 3+ Replace Bi 3+ ) or doping concentration to tune the luminescence peak position. However, B-site ion radius mismatch easily induces lattice distortion, leading to increased non-radiative recombination. Furthermore, doping with some high-valence ions easily induces charge imbalance, causing irreversible phase separation. This severely limits the controllable range of the luminescence peak position and the long-term stability of the device. Therefore, a new method for tuning the luminescence peak position is urgently needed. Summary of the Invention

[0004] The purpose of the embodiments of the present invention is to provide a method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material, aiming to solve the problems raised in the above background technology.

[0005] The embodiment of the present invention is implemented as follows: a method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material comprises the following steps:

[0006] A diamond anvil press is used to pre-press a stainless steel sheet, and a hole is drilled at the indentation to serve as a pressure cavity.

[0007] The antimony-containing double perovskite crystal was placed in a pressure chamber, and silicone oil was added as a pressure medium to pressurize the chamber. Ruby was used as a pressure calibration material during the pressurization process. The pressure was increased from room temperature to 30.5 GPa. The antimony-containing double perovskite crystal was 5% doped with Sb. 3+ :(TMA)2NaInCl6 crystals.

[0008] Preferably, the diamond used in the diamond anvil cell press is type IIa diamond.

[0009] Preferably, the diameter of the pressure cavity formed by the drilled hole groove is 100 μm, and the size of the antimony-containing double perovskite crystal is 50-80 μm in diameter.

[0010] Preferably, the antimony-containing double perovskite crystals are micron-sized, and the initial crystal structure is an orthorhombic phase.

[0011] Preferably, the antimony-containing double perovskite crystal has an emission peak with a central wavelength of 590 nm under 355 nm excitation at room temperature and pressure, and the corresponding CIE chromaticity coordinates are (0.481, 0.481).

[0012] Preferably, the antimony-containing double perovskite crystal achieves tuning of the luminous color range from yellow light emission to cyan light emission and then to yellow-green light emission during the pressurization process.

[0013] The embodiment of the present invention provides a method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material. Taking into account the trivalent antimony ion and the hexacoordinate group formed by it, a new acceptor energy level can be inserted into the band gap of the perovskite host material to generate yellow light emission, thereby effectively tuning the optical properties of the material. By using pressure as a cleaning method, the distance and interaction between atoms in the material can be precisely controlled without introducing other components, the energy transfer path between different excited states in the material can be optimized, the band gap of the material can be changed, and a wide range of peak position shifts can be achieved through pressure to obtain different Chromatic fluorescence enables effective and precise tuning of the luminescence peak, changing the material's luminescence color range from yellow emission in its initial state (CIE chromaticity coordinates (0.481, 0.481)) to cyan emission (CIE chromaticity coordinates (0.235, 0.434)) and then to yellow-green emission (CIE chromaticity coordinates (0.366, 0.506)), thereby enabling the design of more valuable perovskite optoelectronic devices; within the pressure range of 0-5GPa, the luminescence peak shows a linear change, and its pressure-induced peak shift sensitivity reaches 15.29nm / GPa;

[0014] The method of the embodiment of the present invention improves the photoluminescence intensity of the material under fixed excitation light, realizes wide-area regulation of performance, and the luminescence peak position of the material shows a linear blue shift characteristic during the pressurization process. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Schematic diagram of a device used in a method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material provided in Example 1 of the present invention;

[0016] Figure 2 The Sb provided in Example 1 of the present invention 3+ Fluorescence spectra of doped (TMA)2NaInCl6 crystal samples at different pressures;

[0017] Figure 3 The Sb provided in Example 1 of the present invention 3+ CIE chromaticity diagram and chromaticity evolution trend of doped (TMA)2NaInCl6 crystal sample during pressurization;

[0018] Figure 4 The Sb provided in Example 1 of the present invention 3+ Peak position change diagram of doped (TMA)2NaInCl6 crystal sample;

[0019] Figure 5 The Sb provided in Example 1 of the present invention 3+ Raman spectrum of doped (TMA)2NaInCl6 crystal sample;

[0020] Figure 6 The Sb provided in Example 1 of the present invention 3+ Absorption spectrum of doped (TMA)2NaInCl6 crystal sample and fluorescence spectrum under 355nm excitation light;

[0021] Figure 7 Sb provided in Example 2 of the present invention 3+ Doped (TMA)2NaInCl6 powder and X-ray diffraction pattern of (TMA)2NaInCl6 powder. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0023] The specific implementation of the present invention is described in detail below with reference to specific embodiments.

[0024] Example 1: A method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material, using Figure 1 The device shown specifically includes the following steps:

[0025] (1) Using T301 stainless steel as the sealing metal gasket, first use a diamond anvil press with an anvil diameter of 300 μm to pre-press it to a thickness of 35-38 μm, and then use a drill bit to drill a hole with a diameter of 100 μm in the center of the pre-pressed position as the pressure cavity;

[0026] (2) Sb with a diameter of 50-80 μm 3+The doped (TMA)2NaInCl6 crystal sample and the standard pressure material ruby with a diameter of 5-10μm were placed in the pressure cavity together, and silicone oil with a viscosity coefficient of 10cst was used as the pressure transmission medium to package the cavity, and the pressure was increased from room temperature to 30.5GPa.

[0027] During the pressurization process, the in-situ optical properties of the samples were tested. Specifically, when the pressure was increased to 30.5 GPa, a 355 nm laser was used as the excitation light source, and the sample fluorescence signal was collected using an Ocean Optics QEPro spectrometer. The results are as follows: Figure 2 As shown, Sb 3+ The emission fluorescence peak of the (TMA)2NaInCl6 perovskite sample first shifts to the blue and then to the red, and first increases and then decreases during the pressurization process. After 16.5 GPa, the fluorescence intensity increases again.

[0028] The CIE chromaticity diagram obtained during the pressurization process is as follows Figure 3 As shown in a, through Figure 2 The fluorescence spectrum curves under different pressures are plotted to show the evolution trend of CIE chromaticity coordinates with pressure. Figure 3 As shown in b, the solid arrows in the figure indicate the changing trend;

[0029] There are no specific requirements for the metal gasket material and the diamond anvil surface used in the embodiment of the present invention. As long as the pressure can be applied to 30.5 GPa, the luminescence peak position of the antimony-containing double perovskite can be effectively tuned from yellow light emission (CIE chromaticity coordinates (0.481, 0.481)) to cyan light emission (CIE chromaticity coordinates (0.235, 0.434)) and then to yellow-green light emission (CIE chromaticity coordinates (0.366, 0.506)).

[0030] pass Figure 2 The fluorescence spectrum curves under different pressures plot the evolution trend of the luminescence peak position with pressure. Figure 4 As shown, in the pressure range of 0-5 GPa, it can be seen that the luminescence peak position changes linearly at a rate of 15.29 nm / GPa;

[0031] During the pressurization process, a 532 nm laser of a Raman spectrometer was used as the excitation light, where ν1 and ν2 were [InCl6] 3- / [SbCl6] 3- The asymmetric and symmetric expansion modes of Figure 5 As shown;

[0032] During the pressurization process, 355nm laser was used as the excitation light to obtain Sb 3+ Fluorescence spectrum of the (TMA)2NaInCl6 perovskite crystal sample, using a halogen lamp as an external light source, to measure the Sb 3+The absorption spectrum of the doped (TMA)2NaInCl6 perovskite crystal sample, such as Figure 6 shown.

[0033] Example 2: The sample (TMA) 2NaInCl6 without trivalent antimony ions and the sample 5% Sb containing trivalent antimony ions were mixed. 3+ :(TMA)2NaInCl6 were fully ground in a mortar as test samples, and a copper target was used as the anode target (X-ray wavelength is 0.15406nm) to conduct X-ray diffraction experiments. The results are as follows Figure 7 As shown, according to Figure 7 It can be seen that the crystal structures of the two samples are orthorhombic phase.

[0034] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material, characterized in that: The following steps are involved: A diamond anvil press is used to pre-press a stainless steel sheet, and a hole is drilled at the indentation to serve as a pressure cavity. The antimony-containing double perovskite crystal was placed in a pressure chamber, and silicone oil was added as a pressure medium to pressurize the chamber. Ruby was used as a pressure calibration material during the pressurization process. The pressure was increased from room temperature to 30.5 GPa. The antimony-containing double perovskite crystal was 5% doped with Sb. 3+ :(TMA)2NaInCl6 crystals.

2. The method for tuning the luminescence peak position of the antimony-containing double perovskite luminescent material according to claim 1, characterized in that: The diamond used in the diamond anvil cell press is type IIa diamond.

3. The method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material according to claim 1, characterized in that: The diameter of the pressure cavity formed by the drilled hole groove is 100 μm, and the size of the antimony-containing double perovskite crystal is 50-80 μm in diameter.

4. The method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material according to claim 1, characterized in that: The antimony-containing double perovskite crystals are micron-sized, and the initial crystal structure is an orthorhombic phase.

5. The method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material according to claim 1, characterized in that: The antimony-containing double perovskite crystal has an emission peak with a central wavelength of 590 nm under 355 nm excitation at room temperature and pressure, and corresponds to a CIE chromaticity coordinate of (0.481, 0.481).

6. The method for tuning the luminescence peak position of an antimony-containing double perovskite luminescent material according to claim 1, characterized in that: During the pressurization process, the antimony-containing double perovskite crystal achieves tuning of the luminous color range from yellow light emission to cyan light emission and then to yellow-green light emission.

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