Macro preparation method of warm white light emission micron crystal perovskite fluorescent powder
阅读说明：本技术 一种暖白光发射微米晶钙钛矿荧光粉的宏量制备方法 (Macro preparation method of warm white light emission micron crystal perovskite fluorescent powder ) 是由 许银生 李晓曦 赵旭东 田博 章向华 于 2021-02-23 设计创作，主要内容包括：本发明涉及利用熔融-析晶技术制备钙钛矿荧光粉的技术领域,具体涉及一种暖白光发射微米晶钙钛矿荧光粉的宏量制备方法,包括如下步骤：(1)惰性气体保护下分别称取一定量的原料,(2)惰性气体保护下将称量好的原料研磨混合均匀；(3)将得到的混合研磨料抽真空后密封；(4)将密封料在一定温度下熔融,保温一定时间后冷却至室温；(5)将得到的产物研磨后即得到双钙钛矿微米晶荧光粉。本发明的制备方法保证了所制得的双钙钛矿微米晶荧光粉产品的纯度,可得到高纯度且拥有217nm半峰宽和90％量子产率的超宽带暖白光发射微米晶钙钛矿荧光粉。与水热法和固相烧结法相比,获得的荧光粉结晶程度高、均匀性好,可适用于工业化大规模生产。(The invention relates to the technical field of preparing perovskite fluorescent powder by utilizing a melting-crystallization technology, in particular to a macroscopic quantity preparation method of warm white light emission micron crystal perovskite fluorescent powder, which comprises the following steps: (1) respectively weighing a certain amount of raw materials under the protection of inert gas, (2) grinding and uniformly mixing the weighed raw materials under the protection of inert gas; (3) vacuumizing the obtained mixed abrasive and sealing; (4) melting the sealing material at a certain temperature, preserving heat for a certain time, and cooling to room temperature; (5) grinding the obtained product to obtain the double perovskite micron crystal fluorescent powder. The preparation method ensures the purity of the prepared double perovskite micron crystal fluorescent powder product, and can obtain the ultra wide band warm white light emission micron crystal perovskite fluorescent powder with high purity, 217nm half-peak width and 90% quantum yield. Compared with a hydrothermal method and a solid-phase sintering method, the obtained fluorescent powder has high crystallization degree and good uniformity, and is suitable for industrial large-scale production.)
1. A macroscopic quantity preparation method of warm white light emission micron crystal perovskite fluorescent powder is characterized by comprising the following steps:
(1) respectively weighing a certain amount of CsCl, AgCl, NaCl and InCl under the protection of inert gas3、BiCl3，
(2) Grinding and uniformly mixing the raw materials weighed in the step (1) under the protection of inert gas;
(3) vacuumizing the mixed abrasive obtained in the step (2) and sealing;
(4) melting the sealing material in the step (3) at a certain temperature, preserving heat for a certain time, and cooling to room temperature;
(5) grinding the product obtained in the step (4) to obtain the warm white light emission micron crystal perovskite fluorescent powder.
2. The macroscopic quantity preparation method of the warm white light emitting micro-crystalline perovskite fluorescent powder according to claim 1, which is characterized in that: and (3) transferring the abrasive in the step (2) into a clean quartz ampoule bottle, vacuumizing, and welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
3. The macroscopic quantity preparation method of the warm white light emitting micro-crystalline perovskite fluorescent powder according to claim 1, which is characterized in that: in the step (4), the melting temperature is 500-900 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 1-5 h.
4. The macroscopic quantity preparation method of the warm white light emitting micro-crystalline perovskite fluorescent powder according to claim 1, which is characterized in that: in the step (4), the cooling rate is 0.3-10 ℃/min.
5. The macroscopic quantity preparation method of the warm white light emitting micro-crystalline perovskite fluorescent powder according to claim 1, which is characterized in that: in the step (4), in the heat preservation process, the molten liquid is shaken and homogenized, and the material does not need to be shaken in the cooling process.
6. The macroscopic quantity preparation method of the warm white light emitting micro-crystalline perovskite fluorescent powder according to claim 1, which is characterized in that: in the step (5), the chemical formula of the warm white light emitting micron crystal perovskite fluorescent powder is Cs2NaxAg1-xInyBi1-yCl6Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
Technical Field
The invention relates to the technical field of preparation of perovskite fluorescent powder by using a melting-crystallization technology, in particular to a macroscopic preparation method of warm white light emission micron crystal perovskite fluorescent powder.
Background
Metal halide perovskite semiconductors are constantly injecting new activities for chemistry, material science and physics, and adding new sections to the history of optoelectronic devices. It has great application prospect in the fields of photovoltaics, Light Emitting Diodes (LEDs), micro/nano lasers, photoelectric detectors, X-ray imaging and the like. Lead metal halide containing perovskite semiconductors have been a hot topic of research in most of the research work conducted to date. However, the toxicity of lead (Pb) and the poor stability of these materials to radiation, moisture and heat represent major obstacles to their commercialization. Therefore, lead-free perovskites with low toxicity and high stability have attracted a great deal of interest as alternative materials for metal halide perovskite semiconductors.
A new strategy to solve the problem of lead toxicity is to replace every two Pb with one monovalent cation and one trivalent cation2+Cation to form a compound of formula A2BIBIIIX6Of a charged double perovskite of [ B ] co-angularIX6]And [ BIIIX6]Octahedral. Notably, in various compositions having a double perovskite structure, Cs2AgInCl6Because of its direct band gap property, longer carrier lifetime and easy solution method preparation are concerned, but its steric forbidden transition makes its photoluminescence quantum yield very low: (<0.1%). Tang et al [ Luo J, et al Nature 2018; 563[7732]:541-545]By hydrothermal method using Na+And Bi3+Doped pair Cs2AgInCl6Alloying, breaking the space forbidden transition, obtaining the self-trap exciton luminescence with the quantum yield of 86%. Preparation of Cs at present2AgInCl6The perovskite micron crystal method is mainly a hydrothermal method [ CN 107299393A; J.Zhou, et al.J.Mater.chem.A 2017,5,15031-15037]And chemical precipitation methods [ g.volonakis, et al, j.phys.chem.lett.2017,8,772-778]. The perovskite prepared by the two methods has the advantages of high purity, high quantum yield and the like. However, the methods are limited by the aspects of complicated reaction process, difficult purification, high cost, environmental pollution of reaction solvent, long preparation period and the like, and cannot be applied to commercial large-scale mass production.
Disclosure of Invention
The invention aims to provide a macroscopic preparation method of warm white light emission microcrystalline perovskite fluorescent powder, and the obtained fluorescent powder is high in crystallization degree and good in uniformity.
The scheme adopted by the invention for realizing the purpose is as follows: a macroscopic quantity preparation method of warm white light emission micron crystal perovskite fluorescent powder comprises the following steps: (1) respectively weighing a certain amount of CsCl, AgCl, NaCl and InCl under the protection of inert gas3、BiCl3，
(2) Grinding and uniformly mixing the raw materials weighed in the step (1) under the protection of inert gas;
(3) vacuumizing the mixed abrasive obtained in the step (2) and sealing;
(4) melting the sealing material in the step (3) at a certain temperature, preserving heat for a certain time, and cooling to room temperature;
(5) grinding the product obtained in the step (4) to obtain the warm white light emission micron crystal perovskite fluorescent powder.
Preferably, in the step (3), the grinding material in the step (2) is transferred into a clean quartz ampoule bottle, and after vacuum pumping, the mouth of the quartz ampoule bottle is sealed by welding with acetylene flame.
The clean disposable quartz ampoule bottle is used as a reaction container, so that the pollution of the reaction container to raw materials and samples is avoided, the purity of the subsequently obtained double perovskite micron crystal fluorescent powder product is further improved, and further separation and purification are not needed.
Preferably, in the step (4), the melting temperature is 500-900 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 1-5 h.
Preferably, in the step (4), the cooling rate is 0.3-10 ℃/min.
Preferably, in the step (4), the molten liquid is subjected to shaking homogenization treatment during the heat preservation process, and the material is not required to be shaken during the cooling process.
Preferably, in the step (5), the chemical formula of the warm white light emitting micron crystal perovskite fluorescent powder is Cs2NaxAg1- xInyBi1-yCl6Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
The invention has the following advantages and beneficial effects: firstly, the preparation method provided by the invention carries out whole-process vacuum or inert gas protection on the raw materials required for preparing the warm white light emission micro-crystal perovskite fluorescent powder product, avoids the raw materials from being damaged due to moisture absorption or reaction with gas in the air, ensures the high purity of each raw material used for melting, further ensures the purity of the subsequently obtained double perovskite micro-crystal fluorescent powder product, and can obtain the ultra-wideband warm white light emission micro-crystal perovskite fluorescent powder with high purity, 217nm half-peak width and up to 90% quantum yield. Compared with a solid-phase sintering method, the obtained fluorescent powder has high crystallization degree and good uniformity.
Secondly, the melting-crystallization technology can select reaction containers with different sizes as required, so that a kilogram-level fluorescent powder mass production preparation technology can be realized through one-time reaction, the yield which cannot be achieved by other hydrothermal methods and chemical precipitation methods can be achieved, further separation or purification is not needed, and the method is more suitable for industrial large-scale production, so that the preparation cost of the double perovskite micron-crystal fluorescent powder product is reduced.
Drawings
FIG. 1 is a preparation method of the present invention;
FIG. 2 is a macroscopic view of a warm white light emitting microcrystalline perovskite phosphor sample prepared in example 1 under ultraviolet illumination;
FIG. 3 is an excitation and emission spectrum of a warm white light emitting microcrystalline perovskite phosphor sample obtained in example 1;
FIG. 4 is a TEM image of a warm white light emitting microcrystalline perovskite phosphor sample obtained in example 1;
FIG. 5 is an XRD pattern of warm white light emitting microcrystalline perovskite phosphor samples obtained from examples 1-9;
FIG. 6 is a Raman plot of warm white light emitting microcrystalline perovskite phosphor samples obtained from examples 1-9.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.4Ag0.6In0.995Bi0.005Cl6As shown in fig. 1, the preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.4: 0.6: 0.995: 0.005, accurately weighing 2kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 600 ℃ at the heating rate of 1 ℃/min, then keeping the temperature for 5h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 20 hours, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The phosphor prepared according to the above method, as shown in fig. 2, appears bright white under the irradiation of ultraviolet light. Using a xenon lamp as a light source to excite the fluorescent powder, wherein the excitation wave length is as follows: 382nm, the ultra-wide fluorescence of 400-850nm can be observed, the fluorescence peak is located at 610nm, the half-peak width is 217nm, the emission spectrum is shown in figure 3, and the quantum efficiency of the powder sample under the excitation of 375nm reaches 90 percent, as shown in the attached table 1.
The phosphor prepared according to the above method has single crystal particles present and has a size of 2-3 μm, as shown in FIG. 4. The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 2
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.05Ag0.95In0.8Bi0.2Cl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
Second step ofThe method comprises the following steps: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.05: 0.95: 0.8: 0.2, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 550 ℃ at the heating speed of 2 ℃/min, then keeping the temperature for 3h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 13h, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents brighter white under the irradiation of ultraviolet light. The prepared sample is excited by using a xenon lamp as a light source, and the excitation wavelength is as follows: 373nm, the ultra-wide fluorescence of 400-850nm can be observed, the fluorescence peak is located at 608nm, the half-peak width is 213nm, the quantum efficiency is 53.7 percent, and the method is shown in the attached table 1.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 3
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.1Ag0.9In0.85Bi0.15Cl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.1: 0.9: 0.85: 0.15, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 700 ℃ at the heating speed of 1 ℃/min, then keeping the temperature for 5h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 10 hours, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents brighter white under the irradiation of ultraviolet light. The prepared sample is excited by using a xenon lamp as a light source, and the excitation wavelength is as follows: 375nm, the 400-850nm ultra-wide fluorescence can be observed, the fluorescence peak is 609nm, the half-peak width is 211nm, and the quantum efficiency is 58.9 percent, which is shown in the attached table 1.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 4
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.6Ag0.4In0.9Bi0.1Cl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.6: 0.4: 0.9: 0.01, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 500 ℃ at the heating speed of 3 ℃/min, then keeping the temperature for 5h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 10 hours, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents bright white under the irradiation of ultraviolet light. When the prepared sample was deexcited using a xenon lamp as a light source (wavelength: 370nm), 400-850nm ultra-broad fluorescence was observed, with a fluorescence peak at 613nm, a half-peak width at 210nm, and a quantum efficiency of 76.4%, as shown in the attached Table 1.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6Has peak position matched with intensity and no other impuritiesPeaks, indicating that the prepared sample had good purity, are shown in figure 6.
Example 5
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.8Ag0.2In0.9Bi0.1Cl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.8: 0.2: 0.9: 0.1, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 700 ℃ at the heating speed of 2 ℃/min, then keeping the temperature for 3h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step to room temperature slowly after 2 hours, wherein the molten liquid is not shaken any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents bright white under the irradiation of ultraviolet light. A xenon lamp was used as a light source to excite the phosphor, and the excitation wavelength: 375nm, the ultra-wide fluorescence of 400-850nm can be observed, the fluorescence peak is 615nm, the half-peak width is 215nm, and the quantum efficiency is 62.1%.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 6
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.9Ag0.1In0.95Bi0.05Cl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.9: 0.1: 0.95: 0.05, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, and then taking out and quickly filling the quartz ampoule bottleVacuumizing to reach vacuum degree of 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 800 ℃ at the heating speed of 3 ℃/min, then keeping the temperature for 7h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 8 hours, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents brighter white under the irradiation of ultraviolet light. The prepared sample is excited by using a xenon lamp as a light source, and the excitation wavelength is as follows: 377nm, can observe 400-850nm ultra-wide fluorescence, the fluorescence peak is located at 620nm, the half-peak width is 208nm, the quantum efficiency is 56.5 percent, and the method is shown in the attached table 1.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 7
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2Na0.95Ag0.05In0.98Bi0.02Cl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: AgCl: InCl3：BiCl32: 0.95: 0.05: 0.98: 0.02, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to the required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 750 ℃ at the heating speed of 2 ℃/min, then keeping the temperature for 8h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 12 hours, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents brighter white under the irradiation of ultraviolet light. The prepared sample is excited by using a xenon lamp as a light source, and the excitation wavelength is as follows: 375nm, the 400-850nm ultra-wide fluorescence can be observed, the fluorescence peak is 622nm, the half-peak width is 209nm, and the quantum efficiency is 50.8%, which is shown in the attached table 1.
X-ray diffractionThe emission spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 8
In this embodiment, the composition of the double perovskite micron crystal phosphor is Cs2AgInCl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: AgCl: InCl32: 1: 1, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to a required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 800 ℃ at the heating speed of 3 ℃/min, then keeping the temperature for 4h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 15h, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents brighter white under the irradiation of ultraviolet light. The prepared sample is excited by using a xenon lamp as a light source, and the excitation wavelength is as follows: 375nm, the 400-850nm ultra-wide fluorescence can be observed, the fluorescence peak is positioned at 607nm, the half-peak width is 210nm, and the quantum efficiency is 11.7 percent, which is shown in the attached table 1.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the position and intensity of the doped peak of Bi element in the component and Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Example 9
In this example 1, the composition of the double perovskite micro crystal phosphor is Cs2NaBiCl6The preparation method comprises the following steps:
the first step is as follows: selecting a high-quality quartz ampoule bottle as a reaction container, repeatedly cleaning the inner wall of the quartz ampoule bottle by using deionized water ultrasound until no visible impurities exist on the inner wall of the ampoule bottle, and then drying in an oven.
The second step is as follows: selecting a high-purity (5N) raw material, wherein the chemical molar ratio of the raw material CsCl: NaCl: BiCl3：＝2：1：1, accurately weighing 1kg of raw materials in a water-free and oxygen-free glove box by using an electronic balance according to a required proportion.
The third step: and (3) putting the weighed raw materials in the second step into an agate mortar in a glove box, and grinding and mixing uniformly.
The fourth step: filling the mixture in the third step into a quartz ampoule bottle in a glove box, taking out the quartz ampoule bottle, and quickly vacuumizing the quartz ampoule bottle until the vacuum degree reaches 10-3And after Pa, welding and sealing the opening of the quartz ampoule bottle by using acetylene flame.
The fifth step: and (3) putting the sealed quartz ampoule bottle in the fourth step into a muffle furnace (or a swinging furnace), slowly heating to the melting temperature of the raw materials of 600 ℃ at the heating speed of 2 ℃/min, then keeping the temperature for 3h, and shaking the quartz ampoule for multiple times in the heat preservation process to uniformly mix.
A sixth step: and (4) cooling the molten liquid in the fifth step, slowly cooling to room temperature after 10 hours, and not shaking any more in the cooling process.
A seventh step of: and taking the quartz ampoule bottle cooled to room temperature out of the muffle furnace or the rocking furnace, opening the ampoule bottle, taking out the sample, and grinding the sample in an agate mortar to obtain the double perovskite micron crystal fluorescent powder.
The fluorescent powder prepared by the method presents brighter white under the irradiation of ultraviolet light. A xenon lamp is used as a light source to excite the fluorescent powder, the excitation wavelength is 375nm, the ultra-wide fluorescence of 400-850nm can be observed, the fluorescence peak is located at 625nm, the half-peak width is 217nm, the quantum efficiency is 8.1 percent, and the method is shown in the attached table 1.
The X-ray diffraction spectrum shows that the peak position and the intensity of the sample are equal to Cs2AgInCl6The peak position of (a) is matched with the intensity, indicating that the prepared sample has good purity, as shown in figure 5. From the Raman spectrum, 5 clear peak positions, T, can be observedIn 2g，EIn gAnd A1gThree Raman peaks are derived from AgCl6、NaCl6And InCl6Vibration of octahedron, TBi 2gAnd EBi gThe Raman peak is derived from the componentThe position and the intensity of the doping peak of the middle Bi element are equal to Cs2AgInCl6The peak position of (A) is identical with the intensity, and no other miscellaneous peaks exist, which indicates that the prepared sample has good purity, and is shown in figure 6.
Table one: excitation peak, emission peak and quantum yield for samples in examples 1-9
Examples
Composition of
Excitation peak
Emission peak
Quantum yield
1
Cs2Na0.4Ag0.6In0.995Bi0.005Cl6
382
610
90％
2
Cs2Na0.05Ag0.95In0.8Bi0.2Cl6
373
608
53.7％
3
Cs2Na0.1Ag0.9In0.85Bi0.15Cl6
375
609
58.9％
4
Cs2Na0.6Ag0.4In0.9Bi0.1Cl6，
370
613
76.4％
5
Cs2Na0.8Ag0.2In0.9Bi0.1Cl6
375
615
62.1％
6
Cs2Na0.9Ag0.1In0.95Bi0.05Cl6
377
620
56.5％
7
Cs2Na0.95Ag0.05In0.98Bi0.02Cl6
375
622
50.8％
8
Cs2AgInCl6
375
618
11.7％
9
Cs2NaBiCl6
375
625
8.1％
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.