CN116083086B - Core-shell microcrystal with high water stability and preparation method and application thereof - Google Patents

Core-shell microcrystal with high water stability and preparation method and application thereof Download PDF

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CN116083086B
CN116083086B CN202310042856.4A CN202310042856A CN116083086B CN 116083086 B CN116083086 B CN 116083086B CN 202310042856 A CN202310042856 A CN 202310042856A CN 116083086 B CN116083086 B CN 116083086B
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CN116083086A (en
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汪敏强
施金豆
张晨
王俊楠
周赟
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Xian Jiaotong University
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Abstract

The invention discloses a core-shell microcrystal with high water stability, a preparation method and application thereof, wherein cesium salt and hydrochloric acid solution are mixed to obtain a precursor solution A; mixing sodium salt, bismuth salt and manganese salt with a hydrochloric acid solution to obtain a mixed solution B; adding the precursor solution A into the mixed solution B for reaction, and dispersing the product into absolute ethyl alcohol to obtain a solution C; adding tetraethyl silicate and ultrapure water into the solution C, separating and drying. The method utilizes SiO 2 For Cs 2 NaBiCl 6 :Mn 2+ The microcrystal is coated, the reaction time is short, complex production equipment is not adopted, and all operation steps are carried out at room temperature, so that the requirement of mass production can be met. The obtained core-shell microcrystal has stable structure, shows strong orange-red fluorescence emission, particularly can show long-time structure and optical stability in aqueous solution, and can be widely applied to the fields of illumination display devices and fluorescence anti-counterfeiting.

Description

Core-shell microcrystal with high water stability and preparation method and application thereof
Technical Field
The invention belongs to the field of fluorescent material preparation, and particularly relates to a core-shell micron crystal with high water stability, a preparation method and application thereof.
Background
In recent years, lead halide perovskite is considered as a star material of a next-generation photoelectric device due to the advantages of narrow bandwidth, high carrier mobility, cooperative emission and the like, and has been widely applied to light-emitting diodes, photodetectors, solar cells and the like. Unfortunately, pb 2+ The inherent toxicity and instability under environmental conditions of (a) severely hamper its use in commercial applications, and therefore, the replacement of Pb with low-toxic or non-toxic elements 2+ Become an effective solution and are of great interest. In general, divalent metal cations are used for equivalent substitution of Pb 2+ They are very susceptible to oxidation. Thus, by monovalent (B+) and trivalent (B) 3+ ) Combined aliovalent substitution synthesis stable none of metal cationsLead double perovskite Cs 2 B + Bi 3+ Cl 6 Is considered promising.
At present, different lead-free double perovskite materials are obtained through various synthetic routes. In the existing reports, researchers are more concerned with optimizing their optical properties, and less with their optical stability in aqueous media. Wherein, cs is doped with Mn ions 2 NaBiCl 6 :Mn 2+ The microcrystals exhibit bright orange-red emission under ultraviolet excitation and are suitable for illumination and display devices. However, it has been reported that Bi-based leadless double perovskite may self-passivate to form BiOBr upon immersion in aqueous solution, resulting in fluorescence quenching, which would be detrimental to Cs 2 NaBiCl 6 :Mn 2+ Photovoltaic applications of microcrystals in some high humidity environments.
Disclosure of Invention
The invention aims to overcome Cs in the prior art 2 NaBiCl 6 :Mn 2+ The problem of instability of the microcrystal in a high-humidity environment is solved, and a core-shell microcrystal with low cost, high yield and high water stability is provided, and a preparation method and application thereof, wherein the method not only obtains Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystal can obtain the LED device with high-efficiency orange-red luminescence.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the core-shell microcrystal with high water stability comprises the following steps:
mixing cesium salt with hydrochloric acid solution, and stirring until the cesium salt and the hydrochloric acid solution are dissolved to obtain a precursor solution A;
mixing sodium salt, bismuth salt and manganese salt with hydrochloric acid solution, and stirring until the sodium salt, the bismuth salt and the manganese salt are dissolved to obtain a mixed solution B;
adding the precursor solution A into the mixed solution B for reaction to obtain Cs 2 NaBiCl 6 :Mn 2+ A microcrystal;
cs is processed by 2 NaBiCl 6 :Mn 2+ The micron crystals are dispersed in absolute ethyl alcohol to obtain solution C;
adding tetraethyl silicate and ultrapure water into the solution C, stirring to hydrolyze the tetraethyl silicate, separating and drying to obtain the core-shell micron crystal with high water stability.
Further, the cesium salt is cesium chloride or cesium carbonate.
Further, the dosage ratio of cesium chloride to hydrochloric acid solution is (1-2) mmol: (2-4) mL, the mass concentration of the hydrochloric acid solution is 37%.
Further, the sodium salt is sodium chloride or sodium acetate, the bismuth salt is bismuth chloride or bismuth acetate, and the manganese salt is manganese chloride or manganese acetate.
Further, the ratio of the amounts of substances of sodium salt, bismuth salt and manganese salt is (0.5-1): (0.5-1): (0.01-0.3).
Further, the volume ratio of the precursor solution A to the mixed solution B is 2-4:3-6.
Further, the reaction time is 5-10s.
Further, the dosage ratio of the tetraethyl silicate, the ultrapure water and the solution C is 0.5-2mL:10-50 μl:10-20 and mL.
The core-shell microcrystal with high water stability prepared by the method has the surface of SiO 2 A shell layer.
Use of a core-shell microcrystal according to the high water stability as described above in the field of optoelectronic lighting.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention utilizes SiO for the first time 2 For Cs 2 NaBiCl 6 :Mn 2+ Coating the microcrystal to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals. And conventional Cs 2 NaBiCl 6 :Mn 2+ Compared with microcrystals, the invention utilizes SiO which is high in permeability and stable in water 2 As a surface packaging layer, thereby effectively isolating the immersion of external aqueous solution and avoiding Cs 2 NaBiCl 6 :Mn 2+ The microcrystal self-passivation forms BiOBr without optical effect, ensuring Cs 2 NaBiCl 6 :Mn 2+ The microcrystals exhibit long-term structural and optical stability in aqueous solutions and can be better applied to lighting systems in high humidity environments. Cs in the invention 2 NaBiCl 6 :Mn 2+ The preparation method of the microcrystal is simpler and more convenient, the reaction time is shorter, the long-time reaction process is avoided, and complex production equipment is not adopted.
Furthermore, all the operation steps of the invention are carried out under the room temperature condition, thereby avoiding high-temperature reaction.
Furthermore, the sample cleaning agent used in the invention is absolute ethyl alcohol, and has no pollution to the environment.
Further, siO of the present invention 2 The coating process is carried out in an atmospheric environment, and no special reaction environment is needed.
Stable and highly transparent SiO with water 2 For Cs 2 NaBiCl 6 :Mn 2+ Coating of microcrystals to obtain Cs 2 NaBiCl 6 :Mn 2 + @SiO 2 Core-shell microcrystals, the pair of Cs 2 NaBiCl 6 :Mn 2+ The improvement of the water stability of the microcrystal has important significance, and lays a solid foundation for the commercialized popularization of the leadless double perovskite.
Drawings
Figure 1 is an XRD pattern of example 1.
Fig. 2 is an SEM picture of example 1.
Fig. 3 is a partial enlarged view of fig. 2.
Fig. 4 is an element map picture of embodiment 1. Wherein (a) is a microscopic morphology, (b) is Cs, (c) is Na, (d) is Bi, (e) is Cl, (f) is Mn, (g) is Si, and (h) is O.
Fig. 5 is a high resolution TEM photograph of example 1.
Fig. 6 is a photoluminescence spectrum of example 2.
FIG. 7 is an absorption spectrum of example 2.
Fig. 8 is an XRD pattern of example 3 stored in aqueous solution for ten days.
FIG. 9 is a photograph of example 3 stored in aqueous solution for various times under irradiation with ultraviolet light. Wherein, (a) is stored for 0 day, (b) is stored for 5 days, and (c) is stored for 10 days.
Fig. 10 is a photoluminescence spectrum of example 3 stored in an aqueous solution for ten days.
Fig. 11 is a photograph of an assembled LED device of example 4. Wherein, (a) is a photograph of the LED device under the unpowered condition, and (b) is a photograph of the LED device under the powered condition.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The high water stability Cs of the invention 2 NaBiCl 6 :Mn 2+ @SiO 2 The preparation method of the core-shell microcrystal comprises the following steps:
first, cesium chloride (cesium carbonate) and hydrochloric acid solution (37% by mass concentration) were mixed in a 10 mL glass bottle in an amount of (1-2) mmol: (2-4) mL, to form a precursor solution A.
Then, in another 10 mL glass bottle, sodium chloride (or sodium acetate), bismuth chloride (or bismuth acetate), manganese chloride (or manganese acetate) and hydrochloric acid solution were mixed in an amount of (0.5-1) mmol: (0.5-1) mmol: (0.01-0.3) mmol: (3-6) mL, to form a precursor solution B. Then, adding 2-4 mL of precursor solution A into the mixed solution B under the condition of intense stirring (stirring speed is 500 r/min), and reacting 5-10s to obtain Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals.
Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ The microcrystals are dispersed in 10-20mL absolute ethanol to obtain solution C, and 0.5-2mL tetraethyl silicate and 10-50 mu L of ultrapure water are added into the solution C under the condition of intense stirring at room temperature (the stirring speed is 500 r/min), and stirring is continued for 30-60 min at room temperature to ensure that the tetraethyl silicate is completely hydrolyzed.
Finally, after the hydrolysis is finished, the solution system is subjected to centrifugal separation (the centrifugal rate is 5000-7000 r/min), washing by absolute ethyl alcohol and drying for 30-60 min at 50-70 ℃ to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core-shell microcrystal with high-permeability and water-stable SiO on surface 2 The shell layer can effectively isolate the immersion of external aqueous solution.
The choice of the species in the present invention has little effect on the final properties, they only provide the constitution Cs 2 NaBiCl 6 :Mn 2+ Microcrystalline elements.
The dosage of the substances (namely the proportion of the reactants) in the invention has larger influence on the final performance, and if the proportion deviation of the reactants is too large, cs can not be obtained 2 NaBiCl 6 :Mn 2+ And (3) microcrystals.
The Cs with high water stability of the invention 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystals emit bright orange-red light that is suitable in water for use in lighting and display devices in high humidity environments.
The invention is further illustrated below with reference to specific examples.
Example 1
First, 1 mmol of cesium chloride was mixed with 2mL hydrochloric acid solution in a 10 mL glass bottle to form a precursor solution a. Then, 1 mmol of sodium chloride, 1 mmol of bismuth chloride, 0.1 mmol of manganese chloride and 3 mL hydrochloric acid solution were mixed in another 10 mL glass bottle to form a precursor solution B. Subsequently, the precursor solution A of 4 mL is added into the mixed solution B under the condition of intense stirring, and the mixture is reacted for 5 s to obtain Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals. Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ The microcrystals were dispersed in 10 mL absolute ethanol to give solution C, and 0.5 mL tetraethyl silicate and 10 μl of ultrapure water were added to the solution C with vigorous stirring at room temperature, and stirring was continued for 30 mins to allow the tetraethyl silicate to hydrolyze completely. Finally, after the hydrolysis is finished, separating the solution system, adopting absolute ethyl alcohol to carry out multiple times of cleaning, and then drying at 50 ℃ for 60 min to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals.
FIG. 1 is a Cs prepared according to example 1 2 NaBiCl 6 :Mn 2+ @SiO 2 The X-ray diffraction spectrum of the core-shell microcrystal shows that no impurity peak appears.
FIGS. 2 and 3 show Cs prepared according to example 1 2 NaBiCl 6 :Mn 2+ @SiO 2 SEM morphology pictures of core shell crystallites, it can be seen that Cs 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystal is in an octahedral particle shape, and the average grain diameter of the obtained microcrystal is about 10 microns.
FIGS. 4 (a) - (h) are Cs prepared according to example 1 2 NaBiCl 6 :Mn 2+ @SiO 2 Element mapping pictures of core-shell microcrystals, it can be seen that Cs 2 NaBiCl 6 :Mn 2+ The surface of the micron crystal is uniformly distributed with SiO 2 A layer.
FIG. 5 is a Cs prepared according to example 1 2 NaBiCl 6 :Mn 2+ @SiO 2 High resolution TEM image of core shell crystallites, it can be seen that Cs 2 NaBiCl 6 :Mn 2+ SiO with uniform surface of micron crystal 2 The layer thickness was about 10 a nm a.
Example 2
First, 2 mmol of cesium chloride was mixed with 4 mL hydrochloric acid solution in a 10 mL glass bottle to form a precursor solution a. Then, 1 mmol of sodium chloride, 1 mmol of bismuth chloride, 0.2 mmol of manganese chloride and 5 mL hydrochloric acid solution were mixed in another 10 mL glass bottle to form a precursor solution B. Subsequently, the precursor solution A of 4 mL is added into the mixed solution B under the condition of intense stirring, and the reaction is carried out for 8 s, thus obtaining Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals. Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ The microcrystals were dispersed in 15 mL absolute ethanol to give solution C, and 1 mL tetraethyl silicate and 50 μl of ultrapure water were added to the solution C with vigorous stirring at room temperature, and stirring was continued for 50 mins to allow the tetraethyl silicate to hydrolyze completely. Finally, after the hydrolysis is finished, separating the solution system, adopting absolute ethyl alcohol to carry out multiple times of cleaning, and then drying at 60 ℃ for 40 min to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals.
FIG. 7 is a Cs prepared according to example 2 2 NaBiCl 6 :Mn 2+ @SiO 2 Absorption spectrum of core-shell microcrystal, it can be seen that Cs 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell nanocrystals still exhibit strong absorption properties in the uv region.
FIG. 6 is a Cs prepared according to example 2 2 NaBiCl 6 :Mn 2+ @SiO 2 Photoluminescence spectra of core-shell nanocrystals, it can be seen that Cs under excitation by 365nm laser 2 NaBiCl 6 :Mn 2+ @SiO 2 The PL emission peak of the core-shell microcrystal is at 585 nm and appears as orange-red emission.
Example 3
First, 2 mmol of cesium chloride was mixed with 4 mL hydrochloric acid solution in a 10 mL glass bottle to form a precursor solution a. Then, 1 mmol of sodium chloride, 1 mmol of bismuth chloride, 0.3 mmol of manganese chloride and 6 mL hydrochloric acid solution were mixed in another 10 mL glass bottle to form a precursor solution B. Subsequently, the precursor solution A of 4 mL is added into the mixed solution B under the condition of intense stirring to react 10s to obtain Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals. Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ The microcrystals were dispersed in 10 mL absolute ethanol to obtain solution C, and 1 mL tetraethyl silicate and 30. Mu.L of ultrapure water were added to the solution C with vigorous stirring at room temperature, and stirring was continued for 60 minutes to allow the tetraethyl silicate to hydrolyze completely. Finally, after the hydrolysis is finished, separating the solution system, adopting absolute ethyl alcohol to wash for multiple times, and then drying at 50 ℃ for 40 min to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals.
FIG. 8 is a Cs prepared according to example 3 2 NaBiCl 6 :Mn 2+ @SiO 2 Core-shell microcrystals store XRD patterns for ten days in aqueous solution, and it can be seen that Cs 2 NaBiCl 6 :Mn 2+ @SiO 2 Core-shell microcrystals exhibit in aqueous solutionExcellent structural stability is obtained.
In FIG. 9, (a), (b) and (c) are Cs prepared according to example 3 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystals are stored in aqueous solution for 0, 5 and 10 days under UV irradiation, and it can be seen that Cs 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell crystallites retain good fluorescence emission.
FIG. 10 is a sample of Cs prepared according to example 3 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystals are stored in aqueous solution for ten days to give a photoluminescence spectrum. As can be seen, cs 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystal optical properties are unaffected.
From FIGS. 8, 9 (a), (b) and (c), FIG. 10 shows Cs prepared according to the present invention 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell micron crystal has good stability, and after ten days of storage in aqueous solution, the crystal structure and fluorescence characteristics are not affected, thus completely overcoming Cs in the prior art 2 NaBiCl 6 :Mn 2+ The problem of the microcrystals being unstable in a high humidity environment.
Example 4
First, 2 mmol of cesium chloride was mixed with 4 mL hydrochloric acid solution in a 10 mL glass bottle to form a precursor solution a. Then, 1 mmol of sodium chloride, 1 mmol of bismuth chloride, 0.1 mmol of manganese chloride and 6 mL hydrochloric acid solution were mixed in another 10 mL glass bottle to form a precursor solution B. Subsequently, the precursor solution A of 4 mL is added into the mixed solution B under the condition of intense stirring, and the reaction is carried out for 6 s, thus obtaining Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals. Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ The microcrystals were dispersed in absolute ethanol of 17 mL to obtain solution C, and tetraethyl silicate of 2mL and 30. Mu.L of ultra-pure water were added to the solution C with vigorous stirring at room temperature, and stirring was continued for 40 min to allow the tetraethyl silicate to hydrolyze completely. Finally, after the hydrolysis is finished, separating the solution system, adopting absolute ethyl alcohol to wash for a plurality of times, and thenDrying at 70deg.C for 30 min to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals.
FIGS. 11 (a) and (b) are Cs prepared according to example 4 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell microcrystal is coated on the surface of a 365nm GaN ultraviolet light chip to be assembled into an LED lighting device, and the LED device can be seen to emit bright orange red light.
Example 5
First, 1 mmol of cesium carbonate was mixed with 4 mL hydrochloric acid solution in a 10 mL glass bottle to form a precursor solution a. Then, in another 10 mL glass bottle, 0.5 mmol of sodium acetate, 1 mmol of bismuth acetate, 0.01 mmol of manganese acetate, and 6 mL hydrochloric acid solution were mixed to form a precursor solution B. Subsequently, 3 mL of the precursor solution A is added into the mixed solution B under the condition of intense stirring at 500 r/min, and the reaction is carried out for 5 s, thus obtaining Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals. Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ The microcrystals were dispersed in 10 mL absolute ethanol to obtain solution C, and 1 mL tetraethyl silicate and 10. Mu.L of ultra-pure water were added to the solution C under vigorous stirring at room temperature of 500 r/min, and stirring was continued for 30 min to allow the tetraethyl silicate to hydrolyze completely. Finally, after the hydrolysis is finished, separating the solution system, adopting absolute ethyl alcohol to carry out multiple times of cleaning, and then drying at 60 ℃ for 40 min to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals.
Example 6
First, 1 mmol of cesium chloride was mixed with 3 mL hydrochloric acid solution in a 10 mL glass bottle to form a precursor solution a. Then, 1 mmol of sodium chloride, 0.5 mmol of bismuth chloride, 0.3 mmol of manganese chloride and 3 mL hydrochloric acid solution were mixed in another 10 mL glass bottle to form a precursor solution B. Subsequently, the precursor solution A of 2mL is added into the mixed solution B under the condition of intense stirring to react for 10s, thus obtaining Cs 2 NaBiCl 6 :Mn 2+ And (3) microcrystals. Thereafter, cs is treated 2 NaBiCl 6 :Mn 2+ Anhydrous ethanol with microcrystals dispersed in 20mLIn the above, a solution C was obtained, and 0.5. 0.5 mL of tetraethyl silicate and 50. Mu.L of ultrapure water were added to the solution C with vigorous stirring at room temperature, and stirring was continued for 60 minutes to allow the tetraethyl silicate to be completely hydrolyzed. Finally, after the hydrolysis is finished, separating the solution system, adopting absolute ethyl alcohol to wash for multiple times, and then drying at 50 ℃ for 60 min to obtain Cs with high water stability 2 NaBiCl 6 :Mn 2+ @SiO 2 Core shell microcrystals.
The invention has short reaction time, does not adopt complex production equipment, and all operation steps are carried out at room temperature, thus being very simple and efficient and meeting the requirement of mass production. Cs obtained 2 NaBiCl 6 :Mn 2+ @SiO 2 The core-shell micron crystal has stable structure, strong orange-red fluorescence emission, especially long-time fluorescence emission stability in aqueous solution, long-time structure and optical stability, and can be widely applied to the fields of illumination display devices and fluorescence anti-counterfeiting.

Claims (10)

1. The preparation method of the core-shell microcrystal with high water stability is characterized by comprising the following steps of:
mixing cesium salt with hydrochloric acid solution, and stirring until the cesium salt and the hydrochloric acid solution are dissolved to obtain a precursor solution A;
mixing sodium salt, bismuth salt and manganese salt with hydrochloric acid solution, and stirring until the sodium salt, the bismuth salt and the manganese salt are dissolved to obtain a mixed solution B;
adding the precursor solution A into the mixed solution B for reaction to obtain Cs 2 NaBiCl 6 :Mn 2+ A microcrystal;
cs is processed by 2 NaBiCl 6 :Mn 2+ The micron crystals are dispersed in absolute ethyl alcohol to obtain solution C;
adding tetraethyl silicate and ultrapure water into the solution C, stirring to hydrolyze the tetraethyl silicate, separating and drying to obtain the core-shell micron crystal with high water stability.
2. The method for preparing a core-shell microcrystal with high water stability according to claim 1, wherein the cesium salt is cesium chloride or cesium carbonate.
3. The method for preparing the core-shell microcrystal with high water stability according to claim 1, wherein the dosage ratio of cesium chloride to hydrochloric acid solution is (1-2) mmol: (2-4) mL, the mass concentration of the hydrochloric acid solution is 37%.
4. The method for preparing the core-shell microcrystal with high water stability according to claim 1, wherein the sodium salt is sodium chloride or sodium acetate, the bismuth salt is bismuth chloride or bismuth acetate, and the manganese salt is manganese chloride or manganese acetate.
5. The method for preparing the core-shell microcrystal with high water stability according to claim 1, wherein the ratio of the amounts of substances of sodium salt, bismuth salt and manganese salt is (0.5-1): (0.5-1): (0.01-0.3).
6. The method for preparing the core-shell microcrystal with high water stability according to claim 1, wherein the volume ratio of the precursor solution A to the mixed solution B is 2-4:3-6.
7. The method for preparing a core-shell microcrystal with high water stability according to claim 1, wherein the reaction time is 5-10s.
8. The method for preparing the core-shell microcrystal with high water stability according to claim 1, wherein the dosage ratio of the tetraethyl silicate, the ultrapure water and the solution C is 0.5-2mL:10-50 μl:10-20mL.
9. A core-shell microcrystal with high water stability prepared by the method according to any one of claims 1 to 8, wherein the surface of the microcrystal is SiO 2 A shell layer.
10. Use of a core-shell microcrystal of high water stability according to claim 9 in the field of optoelectronic lighting.
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