Method for regulating and controlling multicolor luminescence of manganese-based perovskite luminescent material

Abstract

The invention is applicable to the technical field of zero-dimensional perovskite luminescent materials, and provides a method for regulating and controlling multicolor luminescence of a manganese-based perovskite luminescent material, 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 method comprises the following steps: placing a manganese-containing perovskite crystal into a pressure cavity, adding mineral oil as a pressure transmission medium, pressurizing, adopting ruby as a calibration pressure substance in the pressurizing process, and pressurizing the pressure from room temperature and normal pressure to 15 GPa; at different pressure points, liquid nitrogen is used for low-temperature treatment, and the temperature is reduced to 130K from the room temperature. The crystal field intensity of the manganese-based perovskite material is changed through external stimulation such as temperature and pressure, the light-emitting color gamut of the material is effectively tuned, and a perovskite photoelectric device with higher application value can be designed.

Description

Technical Field

[0001] The present invention belongs to the technical field of zero-dimensional perovskite luminescent materials, and in particular relates to a method for regulating the multi-color luminescence of a manganese-based perovskite luminescent material. Background Art

[0002] Perovskite luminescent materials are attracting increasing attention in display technology, solid-state lighting, quantum dot technology, and other fields due to their high photoelectric conversion efficiency, tunable spectral characteristics, high color purity and wide color gamut, and excellent carrier mobility. Manganese-based perovskite luminescent materials emit light from dd orbital electron transitions of manganese ions. These transitions manifest as different emission wavelengths, typically broadband emission. The characteristics of this broadband emission are affected by different coordination environments and crystal field strengths, resulting in manganese ions exhibiting different luminescence properties in different materials. Therefore, the color of the emitted light can be precisely controlled by adjusting the manganese doping concentration or varying the composition of the perovskite matrix. For example, manganese-doped perovskites can emit light in different wavelength ranges, such as red, orange, and yellow, to meet diverse display and lighting needs.

[0003] Existing technologies have proposed adjusting the emission color gamut of manganese-based perovskites through chemical adjustments, doping, and surface modification. However, while these different control methods improve the emission color gamut, they can also lead to issues such as uneven doping, photodegradation, and stability. Therefore, balancing performance, stability, and cost is a key issue in the current research and application of perovskite luminescent materials. Summary of the Invention

[0004] The purpose of the embodiments of the present invention is to provide a method for regulating the multi-color luminescence of a manganese-based 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 regulating the multi-color luminescence of a manganese-based perovskite luminescent material, comprising 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] Manganese-containing perovskite crystals are placed in a pressure chamber, and mineral oil is added as a pressure transmission medium for pressurization. Ruby is used as a pressure calibration material during the pressurization process, and the pressure is increased from room temperature to 15GPa.

[0008] Preferably, the manganese-containing perovskite crystal is Mn 2+ Doped (C8H 20 N)4MnBiCl9 crystals.

[0009] Preferably, the Mn 2+ Doped (C8H20 The N)4MnBiCl9 crystals are micrometer-sized and the initial crystal structure is orthorhombic phase.

[0010] Preferably, the Mn 2+ Doped (C8H 20 N)4MnBiCl9 crystal has dual emission peaks at room temperature and pressure with central wavelengths of 455nm and 516nm, corresponding to CIE chromaticity coordinates of (0.162, 0.223).

[0011] Preferably, during the pressurization process, the luminescent color range of the manganese-containing perovskite crystal changes from blue light emission in the initial state to green light emission and finally to orange-red light emission.

[0012] Preferably, the method further comprises the following steps: performing cryogenic treatment using liquid nitrogen at different pressure points to reduce the temperature from room temperature to 130K.

[0013] Preferably, when the temperature of the manganese-containing perovskite crystal decreases from room temperature to 130K under normal pressure, the luminescence color range changes from blue light emission in the initial state to cyan-blue light emission.

[0014] An embodiment of the present invention provides a method for regulating the multicolor luminescence of a manganese-based perovskite luminescent material. Considering that the luminescence of divalent manganese ions and the tetrahedral groups formed by them is affected by their coordination environment and crystal field strength, and the crystal field strength changes with changes in pressure and temperature, the crystal field strength of the manganese-based perovskite material is changed by external stimuli such as temperature and pressure, thereby effectively tuning the luminescence color range of the material. In addition, by using clean means such as pressure and temperature stimulation, the crystal structure of the material can be precisely controlled without introducing other components, changing the energy transfer pathway between different excited states of the material, affecting the energy transfer between the host and the guest, thereby achieving effective and precise tuning of the luminescence color range, so that the luminescence color range of the material changes from the initial blue light emission (CIE chromaticity coordinates (0.162, 0.223)) to green light emission (CIE chromaticity coordinates (0.269, 0.436)), and finally to orange-red light emission (CIE chromaticity coordinates (0.577, 0.380)), thereby designing perovskite optoelectronic devices with greater application value.

[0015] The material of the embodiment of the present invention is stable under ambient conditions and exhibits dual emission. The emission covers a wide color gamut at room temperature and pressure. The method of the embodiment of the present invention is used to improve the photoluminescence intensity of this material under fixed excitation light, effectively adjusting its luminescence color gamut. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A schematic diagram of a device used in a method for regulating multi-color luminescence of a manganese-based perovskite light-emitting material provided in an embodiment of the present invention;

[0017] Figure 2 Mn provided in Examples 1 and 2 of the present invention 2+ Doped (C8H 20 N) Optical photographs of 4MnBiCl9 crystal samples taken under 355nm laser irradiation, high pressure stimulation, and low temperature stimulation;

[0018] Figure 3 Mn provided in Example 1 of the present invention 2+ Doped (C8H 20 N) Fluorescence spectrum and CIE chromaticity diagram of 4MnBiCl9 crystal sample during pressurization, as well as chromaticity evolution trend;

[0019] Figure 4 Mn provided in Example 1 of the present invention 2+ Doped (C8H 20 N) Variation of the wavelength of the emission peak corresponding to manganese ions with pressure during the pressurization process of 4MnBiCl9 crystal sample;

[0020] Figure 5 Mn provided in Example 2 of the present invention 2+ Doped (C8H 20 Fluorescence spectra of N4MnBiCl9 crystal samples after low-temperature treatment at different pressures, as well as the changes in the central wavelength and peak intensity of the fluorescence emission peak with temperature. DETAILED DESCRIPTION

[0021] 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.

[0022] The specific implementation of the present invention is described in detail below with reference to specific embodiments.

[0023] Example 1: A method for regulating the multi-color luminescence of a manganese-based perovskite luminescent material, using Figure 1 The device shown comprises the following steps:

[0024] (1) Using T301 stainless steel as the sealing metal gasket, first use a diamond anvil press with an anvil diameter of 400-430 μm to pre-press it to a thickness of 42-45 μm, and then use a drill bit to drill a hole with a diameter of 150-160 μm in the center of the pre-pressed position as the pressure cavity;

[0025] (2) Mn with a diameter of 50-100 μm 2+ Doped (C8H 20A 4MnBiCl9 crystal sample and a ruby with a diameter of 2-5 μm were placed in a pressure cavity. Mineral oil with a viscosity coefficient of 10 cst was used as the pressure transmission medium to seal the cavity and increase the pressure from room temperature to 15 GPa.

[0026] During the pressurization process, the in-situ optical property test of the sample was carried out simultaneously. Specifically, during the pressurization to 15 GPa, a 355 nm laser was used as the excitation light source, and optical photos were taken with a camera under the condition of an exposure time of 2 s. Figure 2 As shown in a; At the same time, the sample fluorescence signal was collected using the Ocean Optics QEPro spectrometer, and the results were as follows Figure 3 As shown in a and b, Mn 2+ Doped (C8H 20 In the dual emission fluorescence peaks of the N4MnBiCl9 perovskite sample, the initial blue part of the fluorescence peak position remains basically unchanged, while the initial green part of the fluorescence peak continues to redshift. Both fluorescence peaks first enhance and then weaken during the pressurization process. The CIE chromaticity diagram obtained during the pressurization process is as follows Figure 3 As shown in c, the arrows in the figure indicate the changing trend; the wavelength of the emission peak corresponding to the manganese ion changes with pressure during the pressurization process as shown in Figure 4 As shown;

[0027] 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 15 GPa, the luminous color range of this manganese-based perovskite material can be effectively tuned from the initial blue light emission (CIE chromaticity coordinates (0.162, 0.223)) to green light emission (CIE chromaticity coordinates (0.269, 0.436)), and finally to orange-red light emission (CIE chromaticity coordinates (0.577, 0.380)).

[0028] Example 2: A method for regulating the multi-color luminescence of a manganese-based perovskite luminescent material, using Figure 1 The device shown comprises the following steps:

[0029] (1) Using T301 stainless steel as the sealing metal gasket, first use a diamond anvil press with an anvil diameter of 400-430 μm to pre-press it to a thickness of 42-45 μm, and then use a drill bit to drill a hole with a diameter of 150-160 μm in the center of the pre-pressed position as the pressure cavity;

[0030] (2) Mn with a diameter of 50-100 μm 2+ Doped (C8H 20A 4MnBiCl9 crystal sample and a ruby (a standard pressure material) with a diameter of 2-5 μm were placed in a pressure chamber. A mineral with a viscosity coefficient of 10 cst was used as a pressure transmission medium to seal the chamber. The chamber was pressurized to 1.6 GPa, 3.4 GPa, and 6.2 GPa and maintained at this pressure. A 355 nm laser was used as the excitation light under normal pressure and in the other three processes. Liquid nitrogen was used to lower the press temperature from room temperature to 130 K.

[0031] Set the exposure time to 2s and shoot the Mn at different pressures as the temperature continues to decrease. 2+ Doped (C8H 20 N) Optical photograph of 4MnBiCl9 crystal sample, such as Figure 2 As shown in b; at the same time, the sample fluorescence signal was collected using the Ocean Optics QEPro spectrometer, and the results were as follows Figure 5 As shown in a, Mn was analyzed by this spectrum. 2+ Doped (C8H 20 The changes in the emission peak center wavelength and peak intensity of the N4MnBiCl9 crystal sample under the stimulation of different pressures and temperatures are shown in the following table. Figure 5 As shown in b, Mn 2+ Doped (C8H 20 During the cooling process, the N4MnBiCl9 crystal sample achieved tuning of the luminescence color range from blue light emission to cyan-blue light emission and a significant enhancement of the luminescence intensity.

[0032] 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 regulating the multicolor luminescence of a manganese-based 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. Manganese-containing perovskite crystals are placed in a pressure chamber, and mineral oil is added as a pressure transmission medium for pressurization. Ruby is used as a pressure calibration material during the pressurization process, and the pressure is increased from room temperature to 15GPa.

2. The method for regulating multicolor luminescence of a manganese-based perovskite luminescent material according to claim 1, characterized in that: The manganese-containing perovskite crystal is Mn 2+ Doped (C8H 20 N)4MnBiCl9 crystals.

3. The method for regulating multicolor luminescence of a manganese-based perovskite luminescent material according to claim 2, characterized in that: The Mn 2+ Doped (C8H 20 The N)4MnBiCl9 crystals are micrometer-sized and the initial crystal structure is orthorhombic phase.

4. The method for regulating multicolor luminescence of a manganese-based perovskite luminescent material according to claim 2, characterized in that: The Mn 2+ Doped (C8H 20 N)4MnBiCl9 crystal has dual emission peaks at room temperature and pressure with central wavelengths of 455nm and 516nm, corresponding to CIE chromaticity coordinates of (0.162, 0.223).

5. The method for regulating multicolor luminescence of a manganese-based perovskite luminescent material according to claim 1, characterized in that: During the pressurization process, the luminescent color range of the manganese-containing perovskite crystal changes from blue light emission in the initial state to green light emission and finally to orange-red light emission.

6. The method for regulating multicolor luminescence of a manganese-based perovskite luminescent material according to claim 1, characterized in that: The method further comprises the following steps: performing cryogenic treatment using liquid nitrogen at different pressure points to reduce the temperature from room temperature to 130K.

7. The method for regulating multicolor luminescence of a manganese-based perovskite luminescent material according to claim 2, characterized in that: The manganese-containing perovskite crystal emits light in a color range from blue light in the initial state to cyan-blue light in the process of decreasing the temperature from room temperature to 130K under normal pressure.

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