CN113817467A - Method for preparing doped double perovskite fluorescent powder by ball milling - Google Patents
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 8
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- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7428—Halogenides
- C09K11/7435—Halogenides with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Abstract
The invention discloses a method for preparing doped double perovskite fluorescent powder by ball milling, belonging to the field of nano luminescent materials. According to the invention, cesium salt, silver salt, sodium salt, indium salt and bismuth salt with specific dosage ratios are used as raw materials and added into a ball milling tank, then ball milling balls are added, and the raw materials are placed on a ball mill to be ball milled for matching with specific ball milling time, so that the doped double perovskite fluorescent powder is obtained. The method is simple, efficient, low in cost and environment-friendly; the doped double perovskite fluorescent powder has a novel specific cubic phase, produces excellent luminous performance, and can be packaged on an ultraviolet LED chip to prepare a warm white LED device.
Description
Technical Field
The invention relates to a method for preparing doped double perovskite fluorescent powder by ball milling, belonging to the field of nano luminescent materials.
Background
Lead perovskite halide (CsPbX)3X ═ Cl, Br, and I) has been one of the research hotspots because of its advantages such as high absorption coefficient, high carrier mobility, adjustable band gap, and easy solution processing. But on the other hand, lead (Pb)2+) The toxicity of such perovskites and the instability of such perovskites to radiation, moisture and heat have been major obstacles to commercialization. Therefore, lead-free perovskites have attracted considerable attention in this field as alternatives to lead-based perovskites. Most of the work is devoted to the exploration of Sn2+And Ge2+Cation as Pb2+However, these ions are easily oxidized into high-valent ions in an air environment, and thus their applications are also limited (s.ghosh, b.pradhan, chemnano mat 2019,5, 300-. In addition, relatively less toxic trivalent cations (e.g. Bi) are used3+，Sb3+) Substitution for Pb2+Forming a vacancy ordered perovskite of the formula A3M2X9(A ═ Cs; M ═ Bi, Sb, etc.; (X ═ Cl, Br, I), but this structure is comparable to the standard CsPbX3Perovskites have low symmetry and low dimensional connectivity of metal halide octahedra, resulting in low electron mobility and are therefore not well suited for photovoltaic applications (q.a. akkerman, l.manna, ACS Energy lett.2020,5,604-.
Recent studies have found that 2 Pb can be substituted with monovalent cations and trivalent cations2+Cationic, forming charge-ordered double perovskites is effectiveA process for substituting lead ions, formula A2B+B3+X6(a ═ Cs; X ═ Cl, Br, I) (k.dave, m.h.fang, z.bao, h.t.fu, r.s.liu, chem.asian j.2020,15, 242-. Wherein, the double perovskite Cs2AgInCl6The structure has wide attention due to the wide spectrum luminescence caused by the self-trapping exciton emission, direct band gap characteristic and longer carrier life, and the characteristic that the luminescence property can be optimized by various doping elements in the structure leads to the extensive research of a large number of researchers (Angew. chem. int. Ed.2021,60, 11592-11603).
Cs2AgInCl6The following methods are mainly used for synthesizing the double perovskite: thermal injection methods, supersaturated crystallization methods and solvothermal methods. The methods belong to liquid phase chemical synthesis methods, the reaction process is long in time consumption and complex in operation, organic reagents are required to be added, ligand-assisted synthesis is also required, and the environment friendliness is poor. In the liquid phase method synthesis process, a solvent capable of forming a precursor homogeneous solution is difficult to find, and particularly AgCl in the solvent is difficult to dissolve, so that a product with a target element proportion is difficult to obtain, precursor impurities are also remained in the product, a single phase is difficult to obtain, and the luminescence property of the product is reduced. The crystallization process of the liquid phase method product is strictly controlled, the grain size of the product is easily influenced, and the grain size is an important factor influencing the luminescence performance of the product. In general, the liquid phase method has poor raw material utilization rate and repeatability, and the control condition of the product crystallization condition is strict.
Disclosure of Invention
The technical problem is as follows:
Cs2AgInCl6the following methods are mainly used for synthesizing the double perovskite: thermal injection methods, supersaturated crystallization methods and solvothermal methods. The methods belong to liquid phase chemical synthesis methods, the reaction process is long in time consumption and complex in operation, organic reagents need to be added, ligand-assisted synthesis is also needed, the environment friendliness is poor, the utilization rate and repeatability of raw materials are poor, and the control condition of the product crystallization process is strict. In order to solve the problems, the invention provides a novel method for preparing doped double perovskite fluorescent powder by ball milling. In the absence of solution and ligandUnder the environment of (2), in a short period of time, the energy transfer is generated by utilizing the actions of extrusion, collision, shearing, friction and the like generated in the ball milling process, so that the raw materials are subjected to chemical reaction, the steps are simple, the consumed time is short, the influence of the solubility of the raw materials on a synthetic product is avoided, the utilization rate of the raw materials is high, the environmental conditions of the crystallization process do not need to be strictly controlled, the repeatability is good, and the large-scale production is easy.
The technical scheme is as follows:
in order to solve the problems in the prior art, the invention firstly provides a method for preparing doped double perovskite fluorescent powder by ball milling, which comprises the following steps:
adding cesium salt, silver salt, sodium salt, indium salt and bismuth salt serving as raw materials into a ball milling tank, adding ball milling balls, placing the ball milling balls on a ball mill for ball milling, and obtaining the doped double perovskite fluorescent powder after the ball milling is finished.
In one embodiment of the present invention, the molar ratio of each metal in cesium salt, silver salt, sodium salt, indium salt, and bismuth salt is 2: (1-x): x: (1-y): y; wherein the value range of x and y is 0-1 and is not 0.
In one embodiment of the invention, neither x, y is 1.
In one embodiment of the invention, the cesium salt is CsCl.
In one embodiment of the invention, the silver salt is AgCl.
In one embodiment of the invention, the sodium salt is NaCl.
In one embodiment of the invention, the indium salt is InCl3。
In one embodiment of the invention, the bismuth salt is BiCl3。
In one embodiment of the present invention, the molar ratio of each metal in the cesium salt, the silver salt, the sodium salt, the indium salt, and the bismuth salt is specifically preferably 2: 0.7: 0.3: 0.9: 0.1.
in one embodiment of the invention, the mass ratio of the ball milling balls to the total mass of the raw materials is (5-25): 1. further preferably (20-25): 1. particularly most preferably 20: 1.
in one embodiment of the invention, the time of ball milling is 10-40 min. Further preferably 30-40 min. Particularly preferably 30 min.
In one embodiment of the present invention, the ball mill used is a QM-3B high-speed vibratory ball mill.
In an embodiment of the present invention, the method specifically includes the following steps:
1) weighing Na and Bi doped double perovskite Cs2AgInCl6The raw material of (1), the raw material comprises CsCl, AgCl, NaCl and InCl3、BiCl3Placing the raw materials in a ball milling tank;
2) adding ball grinding balls into the ball grinding tank in the step 1);
3) and (3) mounting the ball milling tank in the step 2) on a ball mill, and carrying out ball milling for a period of time to obtain the doped double perovskite fluorescent powder.
The invention also provides doped double perovskite fluorescent powder based on the preparation method.
In one embodiment of the invention, the product doped double perovskite phosphor has a cubic phase.
The invention also provides an LED device containing the doped double perovskite fluorescent powder.
In one embodiment of the invention, polydimethylsiloxane is used as an encapsulant, and the doped double perovskite fluorescent powder is encapsulated on a 365nm excited ultraviolet LED chip to prepare a warm white LED device.
In one embodiment of the present invention, the phosphor and encapsulant are present in a 1:10 mass ratio.
In one embodiment of the invention, the LED device has color coordinates of (0.44,0.41), a color temperature of 2953K, a color rendering index of 88.7, and warm white.
The invention also provides application of the doped double perovskite fluorescent powder in the photoelectric field.
Has the advantages that:
1) the method has the advantages that the steps of the synthetic process are short, the operation is simple, all reaction processes are completed in a ball mill, products are obtained after the ball milling is completed, and the subsequent purification treatment operation is not needed;
2) the method does not need organic solvent and ligand assistance, does not produce waste liquid in the whole process, and is green and pollution-free;
3) the raw materials of the method are proportioned according to the accurate stoichiometric ratio, the obtained product has high purity, and the stoichiometric ratio of the doping elements is easy to control.
4) The reaction does not need any inert gas protection, and the product stability is high.
Generally speaking, the method is simple and efficient, low in cost and environment-friendly, and the method is simple and efficient, is suitable for industrial large-scale production and can promote industrial development.
The product synthesized by the method has the central wavelength of the luminescence spectrum of 620nm and the full width at half maximum of 229nm, covers the whole visible light range (the central wavelength of similar products is reported within 560 nm-630 nm, and the full width at half maximum of 140nm), so that the LED color coordinates prepared by the product synthesized by the method are (0.44,0.41), the color temperature is 2953K, and the product is closer to the standards of warm white color coordinates (0.440,0.403) and the color temperature of 3000K. The quantum yield of the product synthesized by the method reaches 32 percent, which is higher than the reported quantum yield (10 to 25 percent) of similar products.
Drawings
FIG. 1 is a photoluminescence spectrum of the lead-free double perovskite phosphors prepared in examples 1, 2, 3 and 4;
FIG. 2 is an XRD pattern of the lead-free double perovskite phosphors prepared in examples 1, 5,6, 7, 8;
FIG. 3 is an XRD pattern of the lead-free double perovskite phosphor prepared in examples 9, 10 and 11;
FIG. 4 is an SEM image of a lead-free double perovskite phosphor prepared in example 1;
FIG. 5 is an SEM image of a lead-free double perovskite phosphor prepared in example 1;
FIG. 6 is a TEM image of the lead-free double perovskite phosphor prepared in example 1;
FIG. 7 is a HRTEM image of the lead-free double perovskite phosphor prepared in example 1;
FIG. 8 is a photograph of a warm white LED prepared from the lead-free double perovskite phosphor prepared in example 1.
Detailed Description
Example 1
1) 0.6mmol CsCl, 0.21mmol AgCl, 0.09mmol NaCl, 0.27mmol InCl were weighed out30.03mmol of BiCl3Placing the mixture in a clean ball milling tank;
2) placing ball-milling balls into a ball-milling tank according to the mass ratio of the ball-milling balls to the raw materials in the step 1) of 20: 1;
3) installing the ball milling tank in the step 2) on a QM-3B high-speed vibration ball mill, setting the ball milling time to be 30 minutes, and preparing Cs2Ag0.7Na0.3In0.9Bi0.1Cl6Lead-free double perovskite fluorescent powder.
The quantum yield of the obtained product reaches 32%.
Fluorescence detection is carried out on the product powder, and under the excitation of 365nm ultraviolet light, the central wavelength of a luminescence spectrum is 620nm, and the full width at half maximum is 229nm, as shown in figure 1.
XRD analysis is carried out on the product, the diffraction peak of the product is in accordance with the reported diffraction peak (ICSD number: 244519) of the perovskite series, the grain size calculated according to the Sherle formula is 32.9nm, the product is a cubic phase and belongs to Fm
Space group, as shown in fig. 2.
SEM pictures of the products show that the products consist of irregular blocks with uncertain shapes and sizes, the diameters of the irregular blocks are 1-5 mu m, as shown in figure 4, and the surfaces of the irregular blocks consist of spherical particles (20-40nm) with smaller sizes through amplification, as shown in figure 5. SEM pictures of the liquid phase process product have been reported to show that the liquid phase process product consists of octahedral grains, and a clear distinction can be observed compared to the present product.
TEM images of the product show that the product is formed by polymerizing irregular spherical nanoparticles, and the particle size of the nanoparticles is within the range of 20-40nm, as shown in FIG. 6. The perovskite lattice can be clearly observed by HRTEM examination of the product, as shown in fig. 7.
The lead-free double perovskite fluorescent powder prepared in example 1 is packaged on a 365nm excited ultraviolet LED chip by polydimethylsiloxane, so that a warm white LED device with color coordinates of (0.44,0.41), color temperature of 2953K and color rendering index of 88.7 can be prepared, as shown in FIG. 8.
Example 2
The only difference between this example and example 1 is that 0.21mmol of AgCl and 0.09mmol of NaCl were weighed out in step 1) and changed to 0.3mmol of AgCl, and the photoluminescence spectrum is shown in FIG. 1.
Example 3
The only difference between this example and example 1 is that 0.27mmol of InCl was weighed out in step 1)30.03mmol of BiCl3Changed to 0.3mmol of InCl3The photoluminescence spectrum is shown in figure 1.
Example 4
The only difference between this example and example 1 is that 0.21mmol of AgCl, 0.09mmol of NaCl and 0.3mmol of AgCl were weighed in step 1), and 0.27mmol of InCl was weighed in step 1)30.03mmol of BiCl3Changed to 0.3mmol of InCl3The photoluminescence spectrum is shown in figure 1.
The results of the products obtained in examples 1 to 4 are compared in Table 1.
TABLE 1 Performance results for the products obtained in examples 1-4
| Product of | nCs:nAg:nNa:nIn:nBi | Quantum yield |
| Example 1Cs2Ag0.7Na0.3In0.9Bi0.1Cl6 | 2:0.7:0.3:0.9:0.1 | 32％ |
| Example 2Cs2AgIn0.9Bi0.1Cl6 | 2:1:0:0.9:0.1 | 14％ |
| Example 3Cs2Ag0.7Na0.3InCl6 | 2:0.7:0.3:1:0 | 11％ |
| Example 4Cs2AgInCl6 | 2:1:0:1:0 | 1％ |
As a result, it was found that: undoped product Cs2AgInCl6The luminescence property of (A) is poor, and the quantum yield is only 1%. Partial Ag is replaced by Na, so that the quantum yield of the product can be improved, and the Na is optimal when 30% of Ag is replaced by Na; bi replaces part of In to improve the quantum yield of the product, and Bi replaces 10% of In optimally. Product Cs from example 12Ag0.7Na0.3In0.9Bi0.1Cl6The quantum yield is the highest and the luminescence property is the best.
Example 5
The only difference between this example and example 1 is that the mass ratio of the ball milling ball in step 2) to the raw material in step 1) is 15:1, and the XRD detection result is shown in fig. 2.
Example 6
The only difference between this example and example 1 is that the mass ratio of the ball milling ball in step 2) to the raw material in step 1) is 10:1, and the XRD detection result is shown in fig. 2.
Example 7
The only difference between this example and example 1 is that the mass ratio of the ball milling ball in step 2) to the raw material in step 1) is 5:1, and the XRD detection result is shown in fig. 2.
Example 8
The only difference between this example and example 1 is that the mass ratio of the ball milling ball in step 2) to the raw material in step 1) is 25:1, and the XRD detection result is shown in fig. 2.
A comparison of the XRD results of the products obtained in examples 5-8 is shown in Table 2:
TABLE 2 XRD results of the products obtained in examples 5 to 8
| Product of | Mass ratio of ball grinding ball to raw material | Main characteristic peak intensity value of product |
| Example 1 | 20:1 | 139 |
| Example 5 | 15:1 | 73 |
| Example 6 | 10:1 | 55 |
| Example 7 | 5:1 | 29 |
| Example 8 | 25:1 | 103 |
The higher the intensity value of the characteristic peak of the product, the higher the crystallinity of the product of this example, the better the luminescence property. As a result, it was found that: the ball milling method needs to be matched with a specific and proper ball-material ratio. When the number of ball milling balls is too small, the ball milling capacity of a single ball milling ball is fully exerted, but the overall ball milling effect is poor; when the number of ball-milling balls is too large, the probability of mutual collision between the ball-milling balls increases, and the ball-milling capability of each ball-milling ball cannot be fully exerted. The product synthesized by the ball milling method disclosed by the invention takes the ball milling ball to raw material mass ratio of 20:1 as the optimum.
Example 9
The only difference between this example and example 1 is that the ball milling time in step 3) is 40 minutes, and the XRD detection results are shown in fig. 3.
Example 10
The only difference between this example and example 1 is that the ball milling time in step 3) is 20 minutes, and the XRD detection results are shown in fig. 3.
Example 11
The only difference between this example and example 1 is that the ball milling time in step 3) is 10 minutes, and the XRD detection results are shown in fig. 3.
The XRD results of the products obtained in examples 1, 9 to 11 are compared in Table 3.
TABLE 3 XRD results of the products obtained in examples 1, 9 to 11
| Product of | Ball milling time (min) | Main characteristic peak intensity value of product |
| Example 9 | 40 | 122 |
| Example 1 | 30 | 139 |
| Example 10 | 20 | 75 |
| Example 11 | 10 | 40 |
The higher the intensity value of the characteristic peak of the product, the higher the crystallinity of the product of this example, the better the luminescence property. As a result, it was found that: the ball milling method requires matching with a specific and appropriate ball milling time. When the ball milling time is too short, the raw materials cannot be thoroughly ground, and the raw materials cannot be in full contact reaction; when the ball milling time is too long, the crystallinity of the product cannot be further improved, and the energy consumption is increased. The ball milling method reported by the invention is used for synthesizing the product, and the ball milling time is the optimal time of 30 minutes.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing doped double perovskite fluorescent powder by ball milling is characterized by comprising the following steps:
adding cesium salt, silver salt, sodium salt, indium salt and bismuth salt serving as raw materials into a ball milling tank, adding ball milling balls, placing the ball milling balls on a ball mill for ball milling, and obtaining the doped double perovskite fluorescent powder after the ball milling is finished.
2. The method of claim 1, wherein the molar ratio of each metal in the cesium salt, silver salt, sodium salt, indium salt, bismuth salt is 2: (1-x): x: (1-y): y; wherein the value range of x and y is 0-1 and is not 0.
3. The process according to claim 1, wherein the molar ratio of the metals cesium salt, silver salt, sodium salt, indium salt and bismuth salt is preferably 2: 0.7: 0.3: 0.9: 0.1.
4. the method according to claim 1, wherein the mass ratio of the ball milling balls to the total mass of the raw materials is (5-25): 1; further preferably (20-25): 1.
5. the method of claim 1, wherein the time of ball milling is 10-40 min; further preferably 30-40 min.
6. The method of any one of claims 1-5, wherein the cesium salt is CsCl; the silver salt is AgCl; the sodium salt is NaCl; the indium salt being InCl3(ii) a The bismuth salt being BiCl3。
7. A doped double perovskite phosphor prepared by the method of any one of claims 1 to 6.
8. An LED device comprising the doped double perovskite phosphor of claim 7.
9. The LED device of claim 8, wherein the doped double perovskite phosphor is encapsulated on a 365nm excited ultraviolet LED chip using polydimethylsiloxane as an encapsulant to produce a warm white LED device.
10. The doped double perovskite phosphor of claim 7 for use in the field of optoelectronics.
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