Green-emitting metal halide luminescent material and preparation method thereof
The Mn2+-doped Cs3ZnCl5 material was prepared by a solvothermal method, which solved the problem of low efficiency of existing Mn(II)-doped luminescent materials and obtained efficient green light-emitting materials suitable for optoelectronic devices and biological imaging.
Patent Information
- Application Number
- CN202410257159.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-07
- Publication Date
- 2025-09-09
AI Technical Summary
The luminescence efficiency of existing Mn(II)-doped luminescent materials is low, which makes it difficult to meet the application requirements in fields such as high-efficiency optoelectronic devices and biological imaging.
Mn2+-doped Cs3ZnCl5 material was prepared by a solvothermal method. By replacing the crystal lattice sites of Zn in the Cs3ZnCl5 lattice with a doping amount of 0.5% to 20%, preferably 15%, the reaction was carried out at 160-200°C for 12 hours, and the material was washed with a low-polarity organic solvent and vacuum dried to obtain a highly crystalline Cs3ZnCl5:Mn2+ green light emitting material.
The highest fluorescence quantum efficiency of green light emitting materials reached 53.7%. The material has high stability, simple operation and low cost, and is suitable for optoelectronic devices and biological imaging.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of inorganic semiconductor luminescent materials and relates to a Cs3ZnCl5:Mn 2+ Luminescent materials and preparation methods provide new ideas and directions for the research and development of new luminescent materials. Background Art
[0002] In recent years, with the rapid advancement of science and technology, research into exogenous ion doping in luminescent materials has achieved remarkable results. This method offers a novel approach for inducing new luminescent centers and regulating photoluminescence properties, and has become a key research tool for the development and optimization of luminescent materials. Among these, Mn(II) ion-doped luminescent materials have garnered significant attention, possessing significant research value in both scientific research and practical applications due to their unique luminescent properties and excellent application potential.
[0003] Mn(II) is an activator ion whose luminescence properties depend on the host lattice, local coordination environment, and distribution. This provides an ideal system for studying the effects of ion doping on luminescence properties. By studying different hosts, coordination environments, and distributions, we can reveal the mechanisms of ion-doped luminescence and further optimize the properties of luminescent materials. This has important theoretical implications for a deeper understanding of luminescence phenomena and the exploration of new luminescent materials.
[0004] Accordingly, Mn(II)-doped luminescent materials have the advantages of large Stokes shift, high luminescence efficiency, and easily adjustable luminescence color. These characteristics make Mn(II)-doped luminescent materials have broad application prospects in optoelectronic devices, photocatalysis, bioimaging and other fields.
[0005] In summary, the research on Mn(II)-doped luminescent materials has broad development prospects and is expected to bring more breakthroughs and innovations to my country's luminescent materials field with the rapid development of science and technology. Summary of the Invention
[0006] The purpose of the present invention is to provide a Cs3ZnCl5:Mn 2+ Green light emitting material and preparation method thereof.
[0007] The purpose of the present invention is achieved through the following technical solutions:
[0008] A green light emitting material, Mn 2+ Doped Cs3ZnCl5 material, Mn 2+ Doped into the Cs3ZnCl5 lattice and replace the crystal lattice site of Zn, among which Mn 2+The doping amount is 0.5% to 20% of the Zn lattice number (stoichiometric ratio) in the Cs3ZnCl5 crystal structure, and the preferred doping amount is 15%.
[0009] The preparation method of the green light emitting material comprises the following steps: 1) weighing CsCl, ZnCl2 and MnCl2 raw materials according to the stoichiometric ratio of the luminescent materials, adding methanol, and stirring uniformly in a reactor; 2) sealing the reactor, placing it in a forced air drying oven, and reacting at a certain temperature for a certain time; 3) washing the reaction product and vacuum drying it to obtain Cs3ZnCl5:Mn 2 + Material.
[0010] Preferably, the luminescent material emits bright green light under ultraviolet light excitation, and its maximum fluorescence quantum efficiency is up to 53.7%.
[0011] Preferably, in step 1), in order to ensure the purity and luminous efficiency of the material, the stoichiometric ratio of the metal chloride raw materials is CsCl: (ZnCl2 + MnCl2) = 3:1, wherein MnCl2: (ZnCl2 + MnCl2) = (0.005~0.2): 1, preferably 0.15.
[0012] Preferably, in step 1), the amount of methanol used is 20% of the reactor capacity.
[0013] Preferably, in step 2), the certain temperature is 160-200°C, preferably 180°C.
[0014] Preferably, in step 3), the certain time is 2 to 24 hours, preferably 12 hours.
[0015] Preferably, in step 4), the reaction product is washed, and the solvent used to wash the product is a pure low-polarity organic solvent.
[0016] Compared with the prior art, the present invention has the following beneficial effects:
[0017] (1) The solvent thermal preparation method adopted in the present invention is simple to operate and can be synthesized in batches in one step. The entire experimental operation is completed under ambient conditions, has low requirements on experimental conditions, and the cost of required experimental equipment and raw materials is low.
[0018] (2) The preparation method adopted by the present invention can successfully convert Mn 2+ It is incorporated into the Cs3ZnCl5 lattice and replaces the Zn site to generate Cs3ZnCl5:Mn 2+ Luminescent material with a maximum fluorescence quantum efficiency of 53.7%.
[0019] (3) The green light emitting material of the present invention is obtained by reaction under high temperature and high pressure conditions, which not only makes the material highly crystallizable, but also helps to improve the stability of the material. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 Cs3ZnCl5:0.15Mn synthesized under the conditions shown in Example 4 of the present invention 2+ X-ray diffraction (XRD) patterns of the samples.
[0021] Figure 2 Preparation of Cs3ZnCl5:0.15Mn for Example 4 of the present invention 2+ Excitation and emission spectra of the samples. DETAILED DESCRIPTION
[0022] Comparative Example 1:
[0023] Weigh 3mmol of CsCl and 1mmol of ZnCl2, pour them into a 25ml polytetrafluoroethylene-lined reactor, add 5ml of methanol, stir for at least 30min to mix the reaction materials evenly, and remove the stirrer. Seal the reactor containing the above reaction materials and place it in a 180℃ forced air drying oven for 12h. After the reaction is completed, allow the reactor to cool naturally to room temperature. Open the reactor, pour out the supernatant, add 4ml of n-butanol solution and centrifuge and wash at 5000rpm for 5min, repeat the washing twice, then replace n-butanol with n-hexane and wash once using the same washing method. Place the washed sample in a vacuum oven at 60℃ and dry for 12h. After the temperature drops to room temperature, collect the sample in a reagent bottle for subsequent testing. XRD testing proves that the product is Cs3ZnCl5. Excitation and emission spectra and fluorescence quantum efficiency tests show that the reaction product obtained in this comparative example does not emit light.
[0024] Example 1:
[0025] 3 mmol of CsCl, 0.995 mmol of ZnCl₂, and 0.005 mmol of MnCl₂ were weighed and poured into a 25 ml polytetrafluoroethylene-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced-air drying oven at 180°C for 12 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 11.6%.
[0026] Example 2:
[0027] 3 mmol of CsCl, 0.99 mmol of ZnCl₂, and 0.01 mmol of MnCl₂ were weighed and poured into a 25 ml polytetrafluoroethylene-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced-air drying oven at 180°C for 12 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 23.2%.
[0028] Example 3:
[0029] 3 mmol of CsCl, 0.9 mmol of ZnCl₂, and 0.1 mmol of MnCl₂ were weighed and poured into a 25 ml Teflon-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced-air drying oven at 180°C for 12 hours. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reactor was opened, the supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 45.3%.
[0030] Example 4:
[0031] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml polytetrafluoroethylene-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced-air drying oven at 180°C for 12 hours. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reactor was opened, the supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 53.7%.
[0032] The 15% Mn prepared in this example 2+ The XRD patterns of Cs3ZnCl5 metal halide luminescent materials are as follows: Figure 1 As shown in Figure 2, all diffraction peaks match those of Cs3ZnCl5 with COD number 2213127, proving that the synthesized material is a pure Cs3ZnCl5 phase. Figure 2 shown.
[0033] Example 5:
[0034] 3 mmol of CsCl, 0.8 mmol of ZnCl₂, and 0.2 mmol of MnCl₂ were weighed and poured into a 25 ml Teflon-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced-air drying oven at 180°C for 12 hours. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reactor was opened, the supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 47.7%.
[0035] Example 6:
[0036] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml polytetrafluoroethylene-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced air drying oven at 180°C for 6 hours. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reactor was opened, the supernatant was discarded, and 4 ml of n-butanol solution was added and washed by centrifugation at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 40.3%.
[0037] Example 7:
[0038] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml polytetrafluoroethylene-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a forced-air drying oven at 180°C for 24 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 50.5%.
[0039] Example 8:
[0040] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml Teflon-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a 160°C forced air drying oven for 12 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 36.5%.
[0041] Example 9:
[0042] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml Teflon-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a 170°C forced air drying oven for 12 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 49.7%.
[0043] Example 10:
[0044] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml Teflon-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a 190°C forced air drying oven for 12 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 47.3%.
[0045] Example 11:
[0046] 3 mmol of CsCl, 0.85 mmol of ZnCl₂, and 0.15 mmol of MnCl₂ were weighed and poured into a 25 ml Teflon-lined reactor. 5 ml of methanol was added and stirred for at least 30 minutes to thoroughly mix the reaction materials. The stirring bar was then removed. The reactor containing the reaction materials was sealed and placed in a 200°C forced air drying oven for 12 hours. After the reaction was completed, the reactor was allowed to cool to room temperature. The supernatant was discarded, and 4 ml of n-butanol solution was added. The mixture was centrifuged and washed at 5000 rpm for 5 minutes. This was repeated twice. The n-butanol solution was then replaced with n-hexane and washed once using the same washing method. The washed sample was dried in a vacuum oven at 60°C for 12 hours. After cooling to room temperature, the sample was collected in a reagent bottle for subsequent testing. XRD analysis confirmed that the product was Cs₃ZnCl₅. The sample emitted green light under UV excitation, with a fluorescence quantum efficiency of 44.6%.
[0047] The parts of the embodiment herein that are not exhaustive of the midpoint values of the technical scope claimed for protection by the present invention and the new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope claimed for protection by the present invention; at the same time, in all the embodiments listed or not listed in the solutions of the present invention, each parameter in the same embodiment merely represents an example of its technical solution (i.e., a feasible solution), and there is no strict coordination and limitation relationship between the parameters, wherein the parameters can be replaced with each other without violating the axioms and the claims of the present invention, unless otherwise stated.
[0048] The technical means disclosed in the solutions of the present invention are not limited to the technical means disclosed in the above technical means, but also include technical solutions composed of any combination of the above technical features. The above is a specific embodiment of the present invention. It should be noted that for those skilled in the art, various improvements and modifications can be made without departing from the principles of the present invention, and such improvements and modifications are also considered to be within the scope of protection of the present invention.
[0049] The specific embodiments described herein are merely illustrative of the spirit of the present invention. Persons skilled in the art may make various modifications, additions, or substitutions to the described specific embodiments without departing from the spirit of the present invention or exceeding the scope of the appended claims.
Claims
1. A green light emitting metal halide luminescent material and its preparation method, the chemical composition of which is: Cs3ZnCl5:Mn 2+ The method of the present invention comprises the following steps: 1) CsCl, ZnCl2, and MnCl2 reagents are weighed in sequence according to the stoichiometric ratio of the materials and placed in a polytetrafluoroethylene liner, an appropriate amount of methanol is added, and the mixture is stirred evenly; 2) the reaction vessel is sealed and placed in a forced air drying oven, and the reaction is carried out at a certain temperature for a certain time; 3) the reaction product is washed and vacuum-dried to obtain the metal halide material, which exhibits bright green light emission under ultraviolet light excitation.
2. The method for preparing a green light emitting material according to claim 1, wherein: In step 1), the stoichiometric ratio of the metal chloride raw materials is CsCl:(ZnCl2+MnCl2)=3:1, wherein MnCl2:(ZnCl2+MnCl2)=(0.005-0.2):
1.
3. The method for preparing the green light emitting material according to claim 1, wherein: In step 1), the amount of methanol solvent used is 20% of the reactor capacity.
4. The method for preparing a green light emitting material according to claim 1, wherein: In step 3), the certain temperature is preferably 180°C.
5. The method for preparing the green light emitting material according to claim 1, wherein: In step 3), the certain time is preferably 12 hours.
6. The method for preparing a green light emitting material according to claim 1, wherein: In step 4), the solvent for washing the product is a pure low-polarity organic solvent. The green light emitting material according to claim 1 emits bright green light under ultraviolet light excitation.
8. The use of the green light emitting material according to claim 1, characterized in that: It can be used in technical fields such as lighting display, anti-counterfeiting, and photoelectric detection.