CN115558489B - High-fluorescence-efficiency zero-dimensional gallium doped metal halide and preparation method thereof - Google Patents
High-fluorescence-efficiency zero-dimensional gallium doped metal halide and preparation method thereof Download PDFInfo
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- CN115558489B CN115558489B CN202211299086.3A CN202211299086A CN115558489B CN 115558489 B CN115558489 B CN 115558489B CN 202211299086 A CN202211299086 A CN 202211299086A CN 115558489 B CN115558489 B CN 115558489B
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- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
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Abstract
The invention relates to a high fluorescence efficiency zero-dimensional gallium doped metal halide and a preparation method thereof, belonging to the technical field of semiconductor material preparation. The preparation method comprises the steps of uniformly mixing rubidium chloride, cadmium chloride and gallium chloride powder, adding 1-5 mL of DMF solution, heating to 80 ℃ to obtain clear and transparent solution, rapidly transferring to a vacuum oven with the temperature of 80 ℃, and cooling to room temperature through a program of 0.2-5 ℃/min to obtain polycrystalline powder. Washing the crystal with isopropanol for 2-3 times, drying at 60-200 ℃ for 20min, and finally cooling the crystal at-10 to-30 ℃ for 1-3 h to obtain the Rb with high purity and enhanced fluorescence efficiency 4 CdCl 6 :10% Ga. The invention synthesizes a brand new Ga 3+ Cadmium-based zero-dimensional metal halide Rb 4 CdCl 6 Shows strong green emission under 302nm excitation.
Description
Technical Field
The invention belongs to the technical field of semiconductor material preparation, and particularly relates to a metal halide material doped with fluorescent efficiency improving substances and a preparation method thereof.
Background
In Cs 4 PbX 6 (X＝Cl - ，Br - And I - ) The zero-dimensional metal halides represented are receiving increasing attention as a new class of photovoltaic materials due to their excellent optical properties and long-term stability. Shared with having angles [ BX ] 6 ] 4- Octahedral three-dimensional CsPbX 3 Perovskite compared with zero-dimensional Cs 4 PbX 6 From totally isolated [ PbX 6 ] 4- Octahedral composition, due to confinement of electron and hole states to a single [ PbX ] 6 ] 4- Octahedra, which results in broadband emission spectra, large stokes shifts, and high exciton binding energies. Although zero-dimensional metal halides have attracted considerable attention as broadband luminescent materials, their fluorescence intensity is generally low.
In solving the problems of wide band gap, tuning optical properties, low fluorescence efficiency, etc., metal ion doping is an effective strategy for activating non-or low-emitting materials. Sb (Sb) 3+ And Mn of 2+ Ions are typically added to the zero-dimensional metal halides to increase their luminous efficiency. In 2022, the Ma Zhiyong group was in the zero-dimensional Cs 4 PbCl 6 Is introduced with Mn 2+ ，Zr 4+ ，Sn 2+ ，Sb 3+ Ions, thereby producing different fluorescent emissions, the emission range covering the entire visible spectrum. Doping has been widely used so far as an effective means to increase the fluorescence efficiency of metal halides. However, the introduction of these dopant ions is extremely prone to quenching of the intrinsic emission of the material, resulting in the formation of doped energy levels that emit different fluorescence. It is therefore a significant effort to find a way to increase the intrinsic emission efficiency of zero-dimensional metal halides.
Disclosure of Invention
The invention aims to solve the technical problems of the background technology and prepare the polycrystalline powder Rb by a slow cooling method 4 CdCl 6 : the fluorescence efficiency after doping is obviously improved after 10 percent of Ga.
The technical problems of the invention are solved by the following technical scheme:
a high-fluorescence-efficiency zero-dimensional gallium doped metal halide is perovskite polycrystalline powder Rb 4 CdCl 6 ：10％Ga。
A preparation method of high fluorescence efficiency zero-dimensional gallium doped metal halide comprises the steps of firstly weighing rubidium chloride, cadmium chloride and gallium chloride powder according to the molar ratio of 4:0.9:0.1, placing the rubidium chloride, cadmium chloride and gallium chloride powder into a glass bottle, adding Dimethylformamide (DMF) solution into the glass bottle according to the dosage of 1-5 mL of cadmium chloride per mmol, heating to 80 ℃ to obtain clear and transparent solution, quickly transferring the clear and transparent solution into a vacuum oven with the temperature of 80 ℃, cooling to room temperature through the procedure of 0.2-5 ℃/min to obtain powder polycrystal, washing the crystal for 2-3 times through isopropanol, drying the crystal at 60-200 ℃ for 20min, finally cooling the crystal at-10 to-30 ℃ for 1-3 h to obtain high-purity zero-dimensional gallium doped metal halide Rb with enhanced fluorescence efficiency 4 CdCl 6 :10% ga polycrystalline powder.
In the preparation method of the high fluorescence efficiency zero-dimensional gallium doped metal halide, 2mL of DMF solution is preferably used per mmol of cadmium chloride in order to improve the crystal yield.
In the preparation method of the high fluorescence efficiency zero-dimensional gallium doped metal halide, the program cooling rate is preferably 0.2 ℃/min in order to improve the crystal yield.
In the preparation method of the high-fluorescence-efficiency zero-dimensional gallium-doped metal halide, the drying temperature is preferably 60 ℃.
In the preparation method of the zero-dimensional gallium doped metal halide with high fluorescence efficiency, the cooling treatment temperature is preferably-15 ℃ in order to improve the crystal yield.
The beneficial effects are that:
the invention synthesizes a brand new Ga 3+ Cadmium-based zero-dimensional metal halide Rb 4 CdCl 6 After doping, the intrinsic luminous efficiency is improved from 23.6% to 57.9%, and the fluorescent material shows strong green light emission under 302nm excitation. The invention expands the recognition of the family of high-efficiency luminescent zero-dimensional fully inorganic materials, and the synthesized materials have potential as lighting application components.
Drawings
FIG. 1 is Rb prepared in example 1 4 CdCl 6 : fluorescence excitation and emission spectra of 10% ga metal halide materials.
FIG. 2 is Rb prepared in example 1 4 CdCl 6 : ultraviolet visible solid absorption spectrum of 10% ga metal halide material.
FIG. 3 is Rb prepared in example 1 4 CdCl 6 : XRD spectrum of 10% ga metal halide material.
FIG. 4 is Rb prepared in example 1 4 CdCl 6 : fluorescence photograph of 10% ga metal halide material under irradiation of 302nm uv lamp.
Detailed Description
Example 1:
in a glove box, firstly weighing 4mmol of rubidium chloride, 0.9mmol of cadmium chloride and 0.1mmol of gallium chloride powder, putting into a 20mL glass bottle, adding 1.8mL of DMF solution, heating to 80 ℃ to obtain clear and transparent solution, and then dissolving the clear solutionThe liquid was rapidly transferred to a vacuum oven at 80℃and the temperature was lowered by a program of 0.2℃per minute to give a polycrystalline powder, the crystals showing green emission at 302nm excitation. Washing the crystal with isopropanol for 2-3 times, oven drying at 60 deg.C for 20min, and cooling at-15deg.C for 1-3 hr to obtain Rb with high purity and enhanced fluorescence efficiency 4 CdCl 6 :10% Ga polycrystal, the crystal yield obtained by this example was 57.9%.
Carrying out solid fluorescence excitation and fluorescence emission test on the product, wherein the fluorescence excitation and emission spectra are shown in figure 1; the ultraviolet-visible absorption spectrum of the product is shown in fig. 2. XRD patterns of the product are shown in FIG. 3, and it can be confirmed from powder X-ray patterns that Rb with high phase purity is obtained in the present invention 4 CdCl 6 :10% Ga metal halide. Rb (Rb) 4 CdCl 6 : a photograph of a 10% ga metal halide material under 302nm uv lamp excitation is shown in figure 4.
Example 2:
in example 1, the DMF usage was changed from 1.8mL in example 1 to 1mL, 3mL and 5mL respectively, the other conditions and steps were unchanged, and the yields of the samples were 53.1%, 48.4% and 37.9% respectively, so that the DMF usage was optimal for 1.8 mL.
Example 3:
the temperature reduction program in the embodiment 1 is changed from 0.2 ℃/min to 1 ℃/min, 3 ℃/min and 5 ℃/min respectively, other conditions and steps are unchanged, and the yield of the measured samples is 56.3%, 49.5% and 42.8% respectively, so that the program temperature reduction speed is optimal when the program temperature reduction speed is 0.2 ℃/min.
Example 4:
in example 1, the drying temperature affects Rb 4 CdCl 6 : the 10% ga metal halide crystal mass may cause its phase change. The drying temperature is changed from 60 ℃ to 100 ℃, 150 ℃ and 200 ℃ respectively, and other conditions are unchanged, so that the yields of products obtained by treatment at different drying temperatures are 54.5%, 49.3% and 0% respectively, and the heat treatment temperature is optimal at 60 ℃.
Example 5:
the cooling temperature in example 1 was changed from-15℃to-10 ℃, -20 ℃, -30 ℃ respectively, and other conditions and steps were unchanged, and the yields of the samples were measured as 55.2%, 46.3%, 40.1%, respectively, so that the cooling temperature was-15 ℃ optimal.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (5)
1. A high-fluorescence-efficiency zero-dimensional gallium doped metal halide is perovskite polycrystalline powder Rb 4 CdCl 6 ：10％Ga。
2. A process for preparing high-fluorescence-efficiency zero-dimensional gallium doped metal halide as defined in claim 1, which comprises the steps of firstly weighing rubidium chloride, cadmium chloride and gallium chloride powder according to the millimole ratio of 4:0.9:0.1, placing the powder into a glass bottle, adding 1-5 mL of dimethylformamide solution into the powder per mmol of cadmium chloride, heating to 80 ℃ to obtain clear and transparent solution, then rapidly transferring the clear and transparent solution into a vacuum oven with the temperature of 80 ℃, cooling to room temperature through the program of 0.2-5 ℃/min to obtain powder polycrystal, washing the crystal for 2-3 times by isopropanol, drying the crystal at 60-200 ℃ for 20min, finally cooling the crystal at-10-30 ℃ for 1 h-3 h to obtain high-purity zero-dimensional gallium doped metal halide Rb with enhanced fluorescence efficiency 4 CdCl 6 :10% ga polycrystalline powder.
3. The method for preparing the high-fluorescence-efficiency zero-dimensional gallium-doped metal halide according to claim 2, wherein the dosage of dimethylformamide is 2mL per mmol of cadmium chloride.
4. The method for preparing the high-fluorescence-efficiency zero-dimensional gallium-doped metal halide according to claim 2, wherein the program cooling rate is 0.2 ℃/min.
5. The method for preparing the high-fluorescence-efficiency zero-dimensional gallium-doped metal halide according to claim 2, wherein the drying temperature is 60 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739798A (en) * | 2018-07-13 | 2021-04-30 | 牛津大学科技创新有限公司 | Preparation method of A/M/X material |
| CN114032091A (en) * | 2021-11-25 | 2022-02-11 | 吉林大学 | Ternary metal halide with ultrahigh fluorescence efficiency and preparation method thereof |
| CN114561209A (en) * | 2022-02-23 | 2022-05-31 | 南京理工大学 | Zero-dimensional zinc-based halide luminescent material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739798A (en) * | 2018-07-13 | 2021-04-30 | 牛津大学科技创新有限公司 | Preparation method of A/M/X material |
| CN114032091A (en) * | 2021-11-25 | 2022-02-11 | 吉林大学 | Ternary metal halide with ultrahigh fluorescence efficiency and preparation method thereof |
| CN114561209A (en) * | 2022-02-23 | 2022-05-31 | 南京理工大学 | Zero-dimensional zinc-based halide luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Bright Green Emission from Self-Trapped Excitons Triggered by Sb3+ Doping in Rb4CdCl6;Jiance Jin et al.;《Chem. Mater.》;第34卷;第5717-5725页 * |
| Effective defect passivation of CsPbBr3 quantum dots using gallium cations toward the fabrication of bright perovskite LEDs;Jiantai Wang et al.;《J. Mater. Chem. C》;第9卷;第11324-11330页 * |
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