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

Abstract

The invention is applicable to the technical field of perovskite luminescent materials, and provides a one-dimensional perovskite method luminescent material which is a one-dimensional zigzag edge shared perovskite luminescent material and has a colorless transparent single crystal structure, and a preparation method comprises the following steps: dissolving PbX2 in an HX solution, and heating and stirring a flask in an oil bath until a solid is completely dissolved; neutralizing 4-(aminomethyl)-pyridine with an HX solution, adding the neutralized 4-(aminomethyl)-pyridine into the PbX2 solution, and stirring; and naturally cooling the solution, and drying without stirring. The invention further provides a one-dimensional perovskite method luminescent material luminescent color gamut tuning method. The invention also provides a multi-color-gamut-covered perovskite luminescent material and an application of the multi-color-gamut-covered perovskite luminescent material in preparation of photoelectric devices. The material is easy to prepare, emission covers a wide color gamut at normal temperature and normal pressure, the photoelectric characteristic of the material can be adjusted through high-pressure treatment, and the adjustability of the emission color and the emission intensity of the perovskite material under high pressure are remarkably enhanced.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite luminescent materials, and in particular relates to a one-dimensional perovskite luminescent material and a luminescent color gamut tuning method and application thereof. Background Art

[0002] One-dimensional perovskite luminescent materials have potential applications in light-emitting devices, photodetectors, and lasers due to their excellent light absorption properties, large exciton binding energy, and broadband emission. However, the performance of these materials in practical applications is limited by their structural properties, so their optoelectronic properties need to be regulated by external stimuli. In view of this goal, it is extremely important to find and design methods to effectively tune the color gamut of perovskite luminescence, so that efficient and stable perovskite luminescent materials with multi-color gamut coverage can be obtained and play a role in different scenarios, such as tunable lighting, external stimulus response, etc.

[0003] The prior art proposes that the proportion of different halogen atoms in perovskite materials can be adjusted through gradient, thereby changing the band gap of the material and tuning the emission color gamut. However, the 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 the embodiments of the present invention is to provide a one-dimensional perovskite light-emitting material, aiming to solve the problems raised in the above background technology.

[0005] The embodiment of the present invention is implemented as follows: a one-dimensional perovskite luminescent material, wherein the luminescent material is a one-dimensional zigzag edge-sharing perovskite luminescent material, which is a colorless and transparent single crystal structure, and the preparation method thereof comprises the following steps:

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

[0007] (2) neutralizing 4-(aminomethyl)-pyridine with HX solution, and then slowly adding it to the PbX2 solution with continuous stirring;

[0008] (3) cooling the solution in step (2) naturally without stirring to obtain needle-shaped colorless precipitated crystals, and then drying;

[0009] Wherein, the PbX2 is PbBr2 or PbCl2, when PbX2 is PbBr2, HX is HBr, 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, which are micrometer-sized, have a monoclinic initial crystal structure, C6H 10 N2PbBr4 crystal has an emission peak with a central wavelength of 583nm at room temperature and pressure, and the corresponding CIE chromaticity coordinates are (0.45, 0.48);

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

[0013] Another object of the embodiment of the present 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) Pre-press the stainless steel gasket using a diamond anvil press, and drill holes at the indentation as a pressure cavity;

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

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

[0017] Another object of an embodiment of the present invention is to provide a perovskite light-emitting material covering multiple color domains, which is obtained by the above method.

[0018] Another object of an embodiment of the present invention is to provide a perovskite light-emitting material with multi-color domain coverage for use in preparing optoelectronic devices.

[0019] The one-dimensional perovskite luminescent material provided by the embodiment of the present invention can generate defects in the perovskite material due to the distortion of the perovskite octahedron caused by electro-acoustic coupling, form self-trapped exciton energy levels, and cause exciton self-trapping, thereby generating broadband self-trapped exciton emission with a large Stokes shift, thereby effectively tuning the luminescent color range of the material; when tuning the luminescent color range, pressure, a cleaning means, can be used to accurately control the distance and interaction between atoms inside the material without introducing other components, change the material band gap, optimize the electro-acoustic coupling strength and lattice relaxation energy, achieve fluorescence emission enhancement and emission blue shift, and achieve effective and accurate tuning of the luminescent color range, so that C6H 10The luminescent color range of the N2PbBr4 material changes from yellow light emission (CIE chromaticity coordinates (0.45, 0.48)) in the initial state to green light emission (CIE chromaticity coordinates (0.16, 0.26)), making C6H 10 The luminescent color range of N2PbCl4 material changes from yellow light emission in the initial state (CIE chromaticity coordinates (0.39, 0.42)) to green light emission (CIE chromaticity coordinates (0.29, 0.36)), which can then design perovskite optoelectronic devices with greater application value;

[0020] The materials of the embodiments of the present invention are easy to prepare, and their emission covers a wide color range at room temperature and pressure. Their photoelectric properties can be adjusted by high-pressure treatment. The perovskite material shows adjustable emission color and significant enhancement of emission intensity under high pressure. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0022] Figure 2 A working principle diagram of a device used in a method for tuning the luminescent color gamut of a one-dimensional perovskite-based luminescent material provided in Example 3 of the present invention;

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

[0024] Figure 4 C6H provided in Example 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 Example 4 of the present invention 10 N2PbBr4 and C6H 10 Absorption spectrum of N2PbCl4 crystal sample.

[0026] Figure 6 C6H provided in Example 5 of the present invention 10 N2PbBr4 and C6H 10 Raman spectrum of N2PbCl4 crystal sample. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with 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.

[0028] The specific implementation of the present invention is described in detail below in conjunction with specific embodiments.

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

[0030] (1) Dissolve 0.367 g of PbBr2 (1 mmol) in 5.0 mL of hydrobromic acid solution in a flask, 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, 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 slowly cooled at room temperature, needle-shaped colorless precipitate crystals will appear. The precipitated crystals are dried in a vacuum oven at 60°C for 24 hours without further purification.

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

[0034] (1) Dissolve 0.278 g of PbCl2 (1 mmol) in 5.0 mL of hydrochloric acid solution in a flask, 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, 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 slowly cooled at room temperature, needle-shaped colorless precipitate crystals will appear. The precipitated crystals are dried in a vacuum oven at 60°C for 24 hours without further purification.

[0037] Performance Test:

[0038] The C6H prepared in Example 1 10N2PbBr4 and C6H prepared in Example 2 10 The N2PbCl4 single crystal sample was fully ground in a mortar as a test sample, and a copper target was used as the anode target (X-ray wavelength is 0.15406nm) for X-ray diffraction experiments. The results are as follows Figure 1 As shown, according to Figure 1 It can be seen that compared with the PDF standard card, there are no extra diffraction peaks in the XRD patterns of the two samples, indicating that the crystallinity is good. 10 N2PbBr4 and C6H 10 The crystal structures of N2PbCl4 are monoclinic phase and orthorhombic phase respectively.

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

[0040] (1) Using T301 stainless steel as the sealing metal gasket, first use a diamond anvil press with an anvil diameter of 400 μm to pre-press it to a thickness of 42-45 μm, and then use a drill to drill a hole with a diameter of 150 μm in the center of the pre-pressing position as the pressure cavity;

[0041] (2) C6H with a diameter of 50-100 μm 10 N2PbBr4 and C6H 10 The N2PbCl4 crystal sample and the standard pressure material ruby ​​with a diameter of 5-10μm are placed in the pressure cavity together, and the cavity is packaged with mineral oil with a viscosity coefficient of 10cst as the pressure transmission medium, and pressurization is started from room temperature and normal pressure.

[0042] Performance Test:

[0043] During the pressurization process, the in-situ optical property test of the sample was carried out simultaneously. Specifically, during the pressurization process, 303nm and 355nm lasers were used as excitation light sources, and the sample fluorescence signal was collected by an Ocean Optics QEPro spectrometer. The results are as follows: Figure 3 As shown, C6H 10 N2PbBr4 and C6H 10 In the emission fluorescence peak of the N2PbCl4 perovskite sample, the fluorescence peak of the initial yellow part 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. Figure 4 a, 4c, through Figure 3 The fluorescence spectrum curves under different pressures are plotted to show the evolution trend of CIE chromaticity coordinates with pressure. Figure 4 b, 4d, the dotted arrows in the figure indicate the changing trend;

[0045] The metal gasket material and the diamond anvil surface used in the embodiment of the present invention have no specific requirements, and both can achieve C6H 10 The luminescence color range of the N2PbBr4 perovskite sample is effectively tuned from yellow emission (CIE chromaticity coordinates (0.45, 0.48)) to green emission (CIE chromaticity coordinates (0.16, 0.26)); C6H 10 The luminescent color range of the N2PbCl4 perovskite sample changes from yellow light emission in the initial state (CIE chromaticity coordinates (0.39, 0.42)) to green light emission (CIE chromaticity coordinates (0.29, 0.36)).

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

[0047] C6H 10 N2PbBr4 and C6H 10 The N2PbCl4 crystal sample and the standard pressure material ruby ​​with a diameter of 5-10μm were placed in the pressure chamber, and the cavity was sealed with mineral oil with a viscosity coefficient of 10cst as the pressure transmission medium. The pressure was increased and the C6H 10 N2PbBr4 and C6H 10 The absorption spectrum of N2PbCl4 perovskite crystal sample, such as Figure 5 shown.

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

[0049] C6H 10 N2PbBr4 and C6H 10 The N2PbCl4 crystal sample and the standard pressure material ruby ​​with a diameter of 5-10μm were placed in the pressure chamber, and the cavity was encapsulated with mineral oil with a viscosity coefficient of 10cst as the pressure transmission medium. During the pressurization process, the 532nm laser of the Raman spectrometer was used as the excitation light to test the C6H 10 N2PbBr4 and C6H 10 The low wavenumber Raman spectrum of N2PbCl4 crystal sample shows Figure 6 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 in the protection scope of the present invention.

Claims

1. A one-dimensional perovskite luminescent material, characterized in that: The luminescent material is a one-dimensional zigzag edge-sharing perovskite luminescent material, which is a colorless and transparent single crystal structure. The preparation method thereof comprises the following steps: (1) Dissolve PbX2 in HX solution, heat the flask in an oil bath, and stir vigorously until the solid is completely dissolved; (2) neutralizing 4-(aminomethyl)-pyridine with HX solution, and then slowly adding it to the PbX2 solution with continuous stirring; (3) cooling the solution in step (2) naturally without stirring to obtain needle-shaped colorless precipitated crystals, and then drying; Wherein, the PbX2 is PbBr2 or PbCl2, when PbX2 is PbBr2, HX is HBr, when PbX2 is PbCl2, HX is HCl.

2. The one-dimensional perovskite luminescent material according to claim 1, characterized in that: In step (2), the molar ratio of PbX2 to 4-(aminomethyl)-pyridine is 1:

2.

3. The one-dimensional perovskite luminescent material according to claim 1, characterized in that: When PbX2 is PbBr2 and HX is HBr, the resulting material is C6H 10 N2PbBr4 crystals, which are micrometer-sized, have a monoclinic initial crystal structure, C6H 10 N2PbBr4 crystal has an emission peak with a central wavelength of 583nm at room temperature and pressure, and the corresponding CIE chromaticity coordinates are (0.45, 0.48); When PbX2 is PbCl2 and HX is HCl, the resulting material is C6H 10 N2PbCl4 crystals, which are micrometer-sized, with an initial crystal structure of orthorhombic phase, C6H 10 N2PbCl4 crystal has an emission peak with a central wavelength of 581nm at room temperature and pressure, and the corresponding CIE chromaticity coordinates are (0.39, 0.42).

4. A method for tuning the luminescence color gamut of a one-dimensional perovskite luminescent material as claimed in any one of claims 1 to 3, characterized in that: The following steps are involved: (1) Pre-press the stainless steel gasket using a diamond anvil press, and drill holes at the indentation as a pressure cavity; (2) A sample of the one-dimensional perovskite luminescent material is placed in a pressure chamber, and mineral oil is added as a pressure transmission medium to perform pressurization. Ruby is used as a pressure calibration material during the pressurization process.

5. The method for tuning the luminous color gamut according to claim 4, characterized in that: The samples of the one-dimensional perovskite luminescent material all achieved tuning of the luminescent color range from yellow light emission to green light emission during the pressurization process.

6. A perovskite luminescent material with multi-color domain coverage, characterized in that: It is obtained by the method according to claim 4.

7. Use of the multi-color domain covered perovskite luminescent material as claimed in claim 6 in the preparation of optoelectronic devices.

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