One-dimensional perovskite light-emitting material, light-emitting color gamut tuning method and application thereof

Abstract

The application belongs to the technical field of perovskite luminescent materials, and provides a one-dimensional perovskite luminescent material, which is a one-dimensional zigzag edge-sharing perovskite luminescent material with colorless transparent single crystal structure, and a preparation method thereof, which comprises the following steps: dissolving PbX2 in an HX solution, heating a flask in an oil bath, and stirring until the solid is completely dissolved; neutralizing 4-(aminomethyl)-pyridine with an HX solution, and adding the 4-(aminomethyl)-pyridine into the PbX2 solution and stirring; naturally cooling the solution, without stirring, and drying, and the one-dimensional perovskite luminescent material can be obtained.The application further provides a one-dimensional perovskite luminescent material light-emitting color gamut tuning method.The application further provides a multi-color gamut covering perovskite luminescent material and application thereof in preparation of optoelectronic devices.The material is easy to prepare, emits a relatively wide color gamut at normal temperature and pressure, and its photoelectric properties can be adjusted through high-pressure treatment; the perovskite material exhibits tunability of emission color and significant enhancement of emission intensity under high pressure.

Description

Technical Field

[0001] This invention belongs to the field of perovskite luminescent materials technology, and particularly relates to a one-dimensional perovskite luminescent material and its luminescence color gamut tuning method and application. Background Technology

[0002] One-dimensional perovskite luminescent materials, due to their excellent light absorption, high exciton binding energy, and broadband emission, hold great promise for applications in light-emitting devices, photodetectors, and lasers. However, the performance of these materials in practical applications is limited by their structural characteristics, thus requiring external stimuli to modulate their photoelectric properties. Therefore, finding and designing methods for effectively tuning the color gamut of perovskite luminescence is crucial. This can yield highly efficient and stable perovskite luminescent materials with multi-gamut coverage, enabling them to function effectively in various scenarios, such as tunable lighting and external stimulus response.

[0003] Existing technologies have proposed that the band gap of perovskite materials can be changed and the emission color gamut tuned by adjusting the proportion of different halogen atoms in the perovskite material through gradient adjustment. However, phase segregation and defects caused by different halogens during use lead to poor material stability and reduced photoluminescence quantum yield. Summary of the Invention

[0004] The purpose of this invention is to provide a one-dimensional perovskite luminescent material, aiming to solve the problems mentioned in the background art.

[0005] The present invention is implemented as follows: a one-dimensional perovskite luminescent material, wherein the luminescent material is a one-dimensional zigzag-edge-shared perovskite luminescent material with a colorless and transparent single-crystal structure, and its preparation method includes the following steps:

[0006] (1) Dissolve PbX2 in HX solution, heat the flask in an oil bath, and then stir vigorously until the solid is completely dissolved;

[0007] (2) Neutralize 4-(aminomethyl)-pyridine with HX solution, then slowly add it to PbX2 solution while stirring continuously;

[0008] (3) Allow the solution in step (2) to cool naturally without stirring to obtain needle-shaped colorless precipitate crystals, and then dry them.

[0009] Wherein, PbX2 is PbBr2 or PbCl2. When PbX2 is PbBr2, HX is HBr, and when PbX2 is PbCl2, HX is HCl.

[0010] Preferably, the molar ratio of PbX2 to 4-(aminomethyl)-pyridine is 1:2.

[0011] Preferably, when PbX2 is PbBr2 and HX is HBr, the obtained material is C6H. 10 N₂PbBr₄ crystals, with micrometer-sized crystals, initially have a monoclinic phase structure, C₆H₂O. 10 N2PbBr4 crystal has an emission peak with a central wavelength of 583 nm at room temperature and pressure, corresponding to CIE chromaticity coordinates of (0.45, 0.48).

[0012] When PbX2 is PbCl2 and HX is HCl, the resulting material is C6H. 10 N₂PbCl₄ crystals, micrometer-sized, with an initial crystal structure of orthorhombic phase, C₆H₂O. 10 N2PbCl4 crystal has an emission peak with a central wavelength of 581 nm at room temperature and pressure, corresponding to CIE chromaticity coordinates of (0.39, 0.42).

[0013] Another objective of this invention is to provide a method for tuning the luminous color gamut of a one-dimensional perovskite luminescent material, comprising the following steps:

[0014] (1) Use a diamond anvil press to pre-press a stainless steel metal gasket and drill a groove at the indentation as a pressure chamber.

[0015] (2) The sample of the one-dimensional perovskite luminescent material is placed in the pressure chamber and mineral oil is added as the pressure transmission medium to pressurize it. Ruby is used as the pressure calibration material during the pressurization process.

[0016] Preferably, the samples of the one-dimensional perovskite luminescent material achieved tuning of the emission color gamut from yellow light emission to green light emission during the pressurization process.

[0017] Another objective of this invention is to provide a perovskite luminescent material with multi-color gamut coverage, which is obtained by the above-described method.

[0018] Another objective of this invention is to provide an application of a perovskite luminescent material with multi-color gamut coverage in the fabrication of optoelectronic devices.

[0019] This invention provides a one-dimensional perovskite-based luminescent material. Due to electro-acoustic coupling causing octahedral distortion in the perovskite, defects are generated within the perovskite material, forming self-trapped exciton energy levels. This leads to exciton trapping, resulting in broadband self-trapped exciton emission with a large Stokes shift, thus effectively tuning the material's luminescence color gamut. During luminescence color gamut tuning, pressure is used as a cleaning method to precisely control the interatomic distances and interactions within the material without introducing other components. This alters the material's band gap, optimizes the electro-acoustic coupling strength and lattice relaxation energy, achieving enhanced fluorescence emission and a blue shift, thus realizing effective and precise tuning of the luminescence color gamut, enabling C6H... 10The emission color gamut of N2PbBr4 material changes from yellow emission (CIE chromaticity coordinates (0.45, 0.48)) in its initial state to green emission (CIE chromaticity coordinates (0.16, 0.26)), thus enabling C6H... 10 The emission color gamut of N2PbCl4 material changes from yellow light emission (CIE chromaticity coordinates (0.39, 0.42)) in the initial state to green light emission (CIE chromaticity coordinates (0.29, 0.36)), which allows for the design of more valuable perovskite optoelectronic devices.

[0020] The materials in this invention are easy to prepare, emit a wide color gamut at room temperature and pressure, and their photoelectric properties can be adjusted by high-pressure treatment. Perovskite materials exhibit adjustable emission colors and significantly enhanced emission intensity under high pressure. Attached Figure Description

[0021] Figure 1 The C6H provided in Embodiments 1 and 2 of the present invention 10 N2PbBr4 and C6H 10 X-ray diffraction patterns of N2PbCl4 crystal powder and PDF standard card;

[0022] Figure 2 This is a schematic diagram of the working principle of the device used in the one-dimensional perovskite luminescent material luminescent gamut tuning method provided in Embodiment 3 of the present invention.

[0023] Figure 3 C6H provided in Embodiment 3 of the present invention 10 N2PbBr4 and C6H 10 Fluorescence spectra of N2PbCl4 crystal samples under different pressures;

[0024] Figure 4 C6H provided in Embodiment 3 of the present invention 10 N2PbBr4 and C6H 10 Fluorescence micrographs of N2PbCl4 crystal samples during pressurization, as well as CIE chromaticity diagrams and chromaticity evolution trends;

[0025] Figure 5 C6H provided in Embodiment 4 of the present invention 10 N2PbBr4 and C6H 10 Absorption spectrum of N2PbCl4 crystal sample.

[0026] Figure 6 C6H provided in Embodiment 5 of the present invention 10 N2PbBr4 and C6H 10 Raman spectrum of N2PbCl4 crystal sample. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the 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 merely illustrative and not intended to limit the invention.

[0028] The specific implementation of the present invention will be described in detail below with reference to specific embodiments.

[0029] Example 1: A one-dimensional perovskite luminescent material (C6H 10 The preparation method of N2PbBr4 includes the following steps:

[0030] (1) Dissolve 0.367 g of PbBr2 (1 mmol) in a flask containing 5.0 mL of hydrobromic acid solution. Heat the flask to 120 °C in an oil bath and then stir vigorously until the solid is completely dissolved.

[0031] (2) In a beaker, neutralize 4-(aminomethyl)-pyridine (0.216 g, 2 mmol) with 1 mL of hydrobromic acid solution, and then slowly add the 4-(aminomethyl)-pyridine solution to the PbBr2 solution while stirring continuously;

[0032] (3) Allow the flask to cool naturally without stirring. When it is slowly cooled at room temperature, needle-shaped colorless precipitate crystals will appear. After the precipitate crystals are dried in a vacuum oven at 60°C for 24 hours, no further purification is required.

[0033] Example 2: A one-dimensional perovskite luminescent material (C6H 10 The preparation method of N2PbCl4 includes the following steps:

[0034] (1) Dissolve 0.278 g of PbCl2 (1 mmol) in a flask containing 5.0 mL of hydrochloric acid solution. Heat the flask to 120 °C in an oil bath and then stir vigorously until the solid is completely dissolved.

[0035] (2) In a beaker, neutralize 4-(aminomethyl)-pyridine (0.216 g, 2 mmol) with 1 mL of hydrochloric acid solution, and then slowly add the 4-(aminomethyl)-pyridine solution to the PbCl2 solution while stirring continuously;

[0036] (3) Allow the flask to cool naturally without stirring. When it is slowly cooled at room temperature, needle-shaped colorless precipitate crystals will appear. After the precipitate crystals are dried in a vacuum oven at 60°C for 24 hours, no further purification is required.

[0037] Performance testing:

[0038] The C6H prepared in Example 1 10N2PbBr4 and C6H prepared in Example 2 10 A single crystal sample of N₂PbCl₄ was thoroughly ground in a mortar and pestle to serve as the test sample. X-ray diffraction experiments were conducted using a copper target as the anode (X-ray wavelength: 0.15406 nm), and the results are as follows: Figure 1 As shown, according to Figure 1 As can be seen from the comparison with the PDF standard card, the XRD patterns of both samples show no extra diffraction peaks, indicating good crystallinity and C6H. 10 N2PbBr4 and C6H 10 The crystal structures of N2PbCl4 are monoclinic and orthorhombic phases.

[0039] Example 3: A method for tuning the luminescence color gamut of a one-dimensional perovskite luminescent material, such as... Figure 2 As shown, the specific steps include:

[0040] (1) T301 stainless steel is used as the sealing metal gasket. First, a diamond anvil press with an anvil diameter of 400μm is used to pre-press it to a thickness of 42-45μm. Then, a hole with a diameter of 150μm is drilled in the center of the pre-pressed position as a pressure chamber.

[0041] (2) C6H with a diameter of 50-100μm was respectively 10 N2PbBr4 and C6H 10 The N2PbCl4 crystal sample and the standard pressure material ruby ​​with a diameter of 5-10 μm were placed together in the pressure chamber. The chamber was sealed with mineral oil with a viscosity coefficient of 10 cst as the pressure transmission medium, and the pressure was increased starting from room temperature and atmospheric pressure.

[0042] Performance testing:

[0043] During the pressurization process, in-situ optical property tests were performed on the samples. Specifically, 303nm and 355nm lasers were used as excitation sources during pressurization, and the sample fluorescence signals were acquired using a Marine Optics QEPro spectrometer. The results are as follows: Figure 3 As shown, C6H 10 N2PbBr4 and C6H 10 In the emission fluorescence peaks of the N2PbCl4 perovskite sample, the initial yellow portion of the fluorescence peak continuously blue-shifts, and the fluorescence peak first increases and then decreases during the pressurization process;

[0044] Fluorescence micrographs were obtained during the pressurization process, such as... Figure 4 As shown in a and 4c, through Figure 3 The evolution trend of CIE chromaticity coordinates with pressure was plotted using fluorescence spectrum curves under different pressures. Figure 4 As shown in b and 4d, the dashed arrows in the figure indicate the trend of change;

[0045] The metal gasket material and diamond anvil facet used in the embodiments of the present invention have no specific requirements; both can achieve C6H. 10 The N2PbBr4 perovskite sample exhibits an effective gamut tuning from yellow emission (CIE chromaticity coordinates (0.45, 0.48)) to green emission (CIE chromaticity coordinates (0.16, 0.26)); C6H 10 The emission color gamut of the N2PbCl4 perovskite sample changes from yellow emission (CIE chromaticity coordinates (0.39, 0.42)) in the initial state to green emission (CIE chromaticity coordinates (0.29, 0.36)).

[0046] Example 4: Using T301 stainless steel as the sealing metal gasket, firstly, a diamond anvil press with an anvil diameter of 400μm is used to pre-press it to a thickness of 42-45μm, and then a drill bit is used to drill a hole with a diameter of 150μm in the center of the pre-pressed position as a pressure chamber.

[0047] C6H with diameters of 50-100 μm were respectively 10 N2PbBr4 and C6H 10 N₂PbCl₄ crystal samples and ruby ​​samples with a diameter of 5-10 μm were placed together in a pressure chamber. The chamber was sealed with mineral oil with a viscosity coefficient of 10 cSt as the pressure transmitting medium. Pressure was applied, and the C₆H₂ content was measured under high pressure. 10 N2PbBr4 and C6H 10 The absorption spectrum of the N2PbCl4 perovskite crystal sample, such as Figure 5 As shown.

[0048] Example 5: Using T301 stainless steel as the sealing metal gasket, firstly, a diamond anvil press with an anvil diameter of 400μm is used to pre-press it to a thickness of 42-45μm, and then a drill bit is used to drill a hole with a diameter of 150μm in the center of the pre-pressed position as a pressure chamber.

[0049] C6H with diameters of 50-100 μm were respectively 10 N2PbBr4 and C6H 10 N₂PbCl₄ crystal samples and ruby ​​samples with a diameter of 5-10 μm were placed together in a pressure chamber. The chamber was sealed with mineral oil with a viscosity coefficient of 10 cSt as the pressure-transmitting medium, and pressurization was applied. During pressurization, a 532 nm laser from a Raman spectrometer was used as the excitation light to test C₆H₂O. 10 N2PbBr4 and C6H 10 The low wavenumber Raman spectra of the N2PbCl4 crystal sample are as follows: Figure 6 As shown.

[0050] 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 within the protection scope of the present invention.

Claims

1. A method for tuning the luminescence color gamut of a one-dimensional perovskite luminescent material, characterized in that, Includes the following steps: (1) Use a diamond anvil press to pre-press a stainless steel metal gasket and drill a groove at the indentation as a pressure chamber. (2) The sample of the one-dimensional perovskite luminescent material is placed in the pressure chamber and mineral oil is added as the pressure transmission medium to pressurize it. Ruby is used as the pressure calibration material during the pressurization process. The one-dimensional perovskite luminescent material is a one-dimensional perovskite luminescent material with shared zigzag edges, and has a colorless and transparent single-crystal structure. Its preparation method includes the following steps: (1) Dissolve PbX2 in HX solution, heat the flask in an oil bath, and then stir vigorously until the solid is completely dissolved; (2) Neutralize 4-(aminomethyl)pyridine with HX solution, then slowly add it to PbX2 solution while stirring continuously. The molar ratio of PbX2 to 4-(aminomethyl)pyridine is 1:

2. (3) Allow the solution in step (2) to cool naturally without stirring to obtain needle-shaped colorless precipitate crystals, then dry them. Wherein, PbX2 is PbBr2 or PbCl2. When PbX2 is PbBr2, HX is HBr, and when PbX2 is PbCl2, HX is HCl.

2. The luminous color gamut tuning method according to claim 1, characterized in that, When PbX2 is PbBr2 and HX is HBr, the resulting material is C6H. 10 N₂PbBr₄ crystals, with micrometer-sized crystals, initially have a monoclinic phase structure, C₆H₂O. 10 N2PbBr4 crystal has an emission peak with a central wavelength of 583 nm at room temperature and pressure, corresponding to CIE chromaticity coordinates of (0.45, 0.48). When PbX2 is PbCl2 and HX is HCl, the resulting material is C6H. 10 N₂PbCl₄ crystals, micrometer-sized, with an initial crystal structure of orthorhombic phase, C₆H₂O. 10 N2PbCl4 crystal has an emission peak with a central wavelength of 581 nm at room temperature and pressure, corresponding to CIE chromaticity coordinates of (0.39, 0.42).

3. The luminous color gamut tuning method according to claim 1, characterized in that, The samples of the one-dimensional perovskite luminescent material all achieved tuning of the emission color gamut from yellow light emission to green light emission during the pressurization process.

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