CN113322062B - Preparation method and application of white-light, blue-green-yellow-light and non-lead perovskite nanocrystalline fluorescent powder - Google Patents

Preparation method and application of white-light, blue-green-yellow-light and non-lead perovskite nanocrystalline fluorescent powder Download PDF

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CN113322062B
CN113322062B CN202110614671.7A CN202110614671A CN113322062B CN 113322062 B CN113322062 B CN 113322062B CN 202110614671 A CN202110614671 A CN 202110614671A CN 113322062 B CN113322062 B CN 113322062B
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徐强
王冰
欧阳晓平
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Nanjing University of Aeronautics and Astronautics
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Abstract

The invention discloses a preparation method and application of white light and blue-green yellow light non-lead perovskite nanocrystalline fluorescent powder 2 X 3 Or Cs 3 Cu 2 X 5 And (3) fluorescent powder. The submicron fluorescent powder emitting white light under ultraviolet light is obtained by simply regulating the molar ratio of CsI to CuI for the first time and utilizing ethanol. The method selects ethanol as an extracting agent, has no pollution to the environment, high yield, stable performance, simple process and low cost, is convenient for large-scale industrial production, and the prepared perovskite nano-crystal fluorescent powder particles have uniform particle size, lower dispersion, higher crystallinity and fewer defects, and has higher light yield for electroluminescence/photoluminescence and high-energy rays. Paves the way for the large-scale application of perovskite nano-crystalline fluorescent powder in future photoelectric fields, such as medical radiation imaging, nondestructive testing, color display screens, LEDs and other occasions.

Description

Preparation method and application of white-light, blue-green-yellow-light and non-lead perovskite nanocrystalline fluorescent powder
Technical Field
The invention belongs to the technical field of all-inorganic metal halide nano material application, and particularly relates to a preparation method and application of white light and blue-green-yellow light non-lead perovskite nano crystal fluorescent powder.
Technical Field
The application of novel solid state lighting offers great potential for various applications such as white Light Emitting Diodes (LEDs), photodetectors, and the like. A typical white light LED is prepared by coating a yellow fluorescent powder on a blue InGaN chip, and most of general fluorescent powder contains rare earth ions Eu 2+ ，Ce 3+ Or other toxic elements, eventuallyThe problems of white light LED environmental resource and cost economy are difficult to solve. Therefore, active exploration of a green and environment-friendly preparation method of the high-performance white light LED fluorescent powder becomes an important research topic at present.
In recent years, halogenated perovskite nanocrystals have been widely studied in the fields of Solar Cells (SC), Light Emitting Diodes (LED), scintillators and optoelectronic devices due to their high luminous efficiency (PLQY), simple tunability of luminescence over the entire visible range, large absorption cross-sections for high-energy radiation, and high tolerance factors. Due to the quantum confinement effect and the increased overlap of the electron and hole wave functions, the spatial distribution of the luminescent center and the generated excitons can be confined within the bohr radius of the nanocrystals, and the low-dimensional perovskite exhibits a high-emission triplet excited state or self-trapped exciton luminescence, so that the perovskite nanocrystal material is more widely researched.
The antisolvent extraction method is one of the most widely used methods to obtain high quality perovskite nanocrystals at present, due to its advantages of low cost and easy operation. The commonly used antisolvents at present are mainly Dichloromethane (DCM), toluene, Chlorobenzene (CB), etc., which are recognized to cause strong pollution to drinking water, showing high toxicity. Thereby severely limiting the wider future applications of perovskite materials. Therefore, the development of an environment-friendly and green harmless method for preparing the high-performance perovskite material is hopeful. Ethanol (ET) is used as a green solvent, has low toxicity, is generally used as beverages, fuels, essences and the like, and is also commonly used as a disinfectant in the medical field by 70 to 75 percent. Furthermore, ethanol is biodegradable and therefore does not cause accumulation in the ecological environment and biology. Therefore, ethanol is a green pollution-free processing solvent, and is a potential green solvent for preparing high-performance and stable perovskite materials instead of dichloromethane, toluene, chlorobenzene and the like.
Disclosure of Invention
Aiming at the defects of large use of toxic reagents and the characteristic of green and environment-friendly ethanol in the prior art, the invention provides a preparation method and application of white light and blue-green-yellow light non-lead perovskite nanocrystalline fluorescent powder,ethanol is used as an extracting agent, and a series of CsCu with different luminescent colors and white light emission are prepared in an ambient atmosphere 2 X 3 And Cs 3 Cu 2 X 5 Perovskite nanocrystalline phosphor. The method has the advantages of simple process, green and pollution-free used reagents, suitability for large-scale preparation, high luminous efficiency of products, high yield and excellent and stable performance. The method is suitable for the fields of white light LED illumination, color LEDs, scintillators, photoelectric devices and the like.
The invention adopts the following technical scheme:
the preparation method of the white light and blue-green-yellow light non-lead perovskite nanocrystalline fluorescent powder comprises the following steps:
(1) CsX and CuX powder are added into a round-neck flask filled with solvent;
(2) violently stirring for 10-120 min at 30-100 ℃ in a water bath kettle to fully dissolve CsX and CuX to form CsCu 2 X 3 Or Cs 3 Cu 2 X 5 The precursor solution of (1);
(3) cooling and filtering the precursor solution obtained in the step (2) to obtain a clear precursor solution;
(4) under the condition of intense stirring, injecting the clear precursor solution obtained in the step (3) into absolute ethyl alcohol, and changing the solution into milky white suspension;
(5) and (4) centrifuging the milky white suspension obtained in the step (4), discarding supernatant, and drying powder precipitated at the bottom to obtain the perovskite nano-crystal fluorescent powder.
Further, in the CsX and CuX in the step (1), X is one or more of Cl, Br and I.
Further, the molar ratio of the CsX added in the step (1) to the CuX is 0.25-4: 1.
further, the solvent in the step (1) is DMF, DMSO or a mixed solvent of the DMF and the DMSO in any proportion.
Further, the concentration range of the precursor solution in the step (2) is 0.01 mm/L-2.5 m/L.
Further, the filtration in the step (3) comprises injection filtration and negative pressure suction filtration;
further, the specification of the suction filter funnel in the step (3) comprises 0.22 μm and 0.40 μm;
further, the purity range of the absolute ethyl alcohol used in the step (4) is 45-99.5%;
further, the volume ratio of the injected clear precursor solution to the absolute ethyl alcohol in the step (4) is 1: 8 to 50.
Further, the rotating speed of the centrifugation in the step (5) is 500-8000 rpm/min, and the centrifugation time is 3-20 min.
Further, in the step (5), the drying temperature is 30-100 ℃, and the drying time is 5-120 min.
According to the application of the perovskite nanocrystalline fluorescent powder prepared by the method in the field of LED illumination, white light and blue-green yellow light LEDs are prepared by coating the fluorescent powder on the surface of an ultraviolet lamp chip, and the wavelength range of the selected ultraviolet lamp is 255-310 nm.
Advantageous effects
1. The experimental operation is simple, the preparation process has low requirements on experimental conditions, strict vacuum and high-temperature environments are not needed, and the cost of required equipment and raw materials is low.
2. The used extractant ethanol is a green solvent, has low toxicity and no pollution to the environment;
3. the used extractant is ethanol, and perovskite nanocrystalline fluorescent powder with good performance can be extracted even by the ethanol with low purity;
4. prepared CsCu 2 X 3 Or Cs 3 Cu 2 X 5 The nano-crystal fluorescent powder has uniform granularity, excellent optical performance, high luminous efficiency, good stability, corresponding sensitivity to X-rays and high radiation luminous efficiency.
5. The mixed fluorescent powder of the CsI and the CuI is obtained by direct extraction through the regulation and control of the molar ratio of the CsI to the CuI, and can present white light with chromaticity coordinates of (0.35 ) under the excitation of ultraviolet.
Drawings
FIG. 1 shows Cs 3 Cu 2 I 5 XRD of nanocrystalline fluorescent powder;
FIG. 2 shows Cs 3 Cu 2 I 5 Purple of nano crystal fluorescent powder at 310nmPhotographs of the exterior;
FIG. 3 shows Cs 3 Cu 2 I 5 PL spectrum of nano-crystal fluorescent powder under 310nm ultraviolet;
FIG. 4 shows Cs 3 Cu 2 I 5 PL spectrum of nanocrystalline fluorescent powder under different excitation power intensity of 310nm ultraviolet;
FIG. 5 is a photograph of fluorescent powders prepared under a fluorescent lamp and a 310nm ultraviolet lamp, respectively, with CsI and CuI in a series of different molar ratios;
FIG. 6 shows the results of scanning electron microscopy on Cs 3 Cu 2 I 5 And CsCu 2 I 3 The microscopic morphology of (a);
FIG. 7 is a white LED prepared by coating the prepared phosphor on the surface of a 310nm ultraviolet lamp chip.
Detailed Description
For the purpose of making the objects, technical lines and advantages of the present invention more apparent, the following further describes the patent details of the present invention with reference to the accompanying drawings and examples, it being understood that the specific examples described herein are for the purpose of illustration only and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the research process of Cu-based perovskite quantum dots, aiming at the defects of large use of toxic reagents and the characteristic of environmental friendliness of ethanol in the prior art, the invention provides a method for preparing CsCu in an environmental atmosphere by using ethanol as an extracting agent 2 X 3 And Cs 3 Cu 2 X 5 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: CsX and CuX are fully dissolved in DMF or DMSO solution according to a certain molar ratio, clear precursor solution is obtained by filtration, the clear precursor solution is injected into an ethanol reagent, and the supernatant is removed by centrifugation, so that the perovskite nano-crystal fluorescent powder can be obtained. The method has the advantages of simple process, green and pollution-free used reagents, suitability for large-scale preparation, high luminous efficiency of products, good stability, high yield and excellent and stable performance. Suitable for medical imaging, LED. Scintillators, photoelectric devices and the like.
Example 1
The invention provides a method for preparing Cs in an environmental atmosphere by using ethanol as an extracting agent 3 Cu 2 I 5 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: fully dissolving CsI and CuI in a DMSO solution according to a molar ratio of 3:2, performing suction filtration to obtain a clear precursor solution, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove a supernatant to obtain the Cs 3 Cu 2 I 5 Nanocrystalline fluorescent powder.
The method specifically comprises the following steps:
1. CsI (0.3mmol), CuI (0.2mmol), DMSO (10mL) were mixed in a glass vial.
2. Heating the small glass bottle in the step (1) to 60 ℃ in a water bath kettle, and vigorously stirring by utilizing magnetons for 30min to fully dissolve CsI and CuI to form Cs 3 Cu 2 I 5 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, and plugging the conical flask by using a rubber plug, wherein the conical flask is connected with a vacuum pump for suction filtration;
4. clear Cs prepared in the step (3) 3 Cu 2 I 5 The precursor solution is injected into a glass bottle filled with 50ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into milky white suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, centrifuging for 5min at 1000rpm/min,
6. discarding supernatant of the solution centrifuged in the step (5), taking out powder precipitated at the bottom, and putting the powder into a vacuum drying oven to be dried in vacuum at 60 ℃ for 60min to obtain the Cs 3 Cu 2 I 5 Nanocrystalline fluorescent powder.
The obtained Cs 3 Cu 2 I 5 The performance characterization of the optical properties of the nanocrystals is as follows:
as shown in FIG. 1, the powder prepared by XRD results analysis was Cs 3 Cu 2 I 5 。
Cs as shown in FIG. 2 3 Cu 2 I 5 The nanocrystalline fluorescent powder shows bright purple luminescence under the ultraviolet of 310nm, and the luminous efficiency reaches 81.6%.
As shown in FIG. 3, the fluorescence emission spectrum was measured on a fluorescence spectrometer with 310nm UV excitation, and it can be seen from FIG. 4 that the Cs 3 Cu 2 I 5 The photoluminescence PL peak of the nanocrystalline fluorescent powder is at 444 nm.
As shown in FIG. 4, Cs is added 3 Cu 2 I 5 The photoluminescence spectra obtained from the nanocrystalline fluorescent powder under different intensity of ultraviolet excitation are shown in the figure, and it can be seen that at room temperature, the PL intensity linearly increases with the increase of excitation intensity, and there is no sign of PL saturation. This indicates that the mechanism of luminescence is not due to permanent defects, but rather Cs 3 Cu 2 I 5 The inherent energy-emitting property of the nano-crystal fluorescent powder material.
Example 2
The invention provides a method for preparing Cs in an environmental atmosphere by using ethanol as an extracting agent 3 Cu 2 Br 5 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: fully dissolving CsBr and CuBr in a DMSO solution according to a molar ratio of 3:2, performing suction filtration to obtain a clear precursor solution, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove a supernatant to obtain the Cs 3 Cu 2 Br 5 Nanocrystalline fluorescent powder.
The method specifically comprises the following steps:
1. CsBr (0.15mmol), CuBr (0.1mmol), DMSO (10mL) were mixed in a glass vial.
2. Heating the small glass bottle in a water bath to 60 deg.C, and vigorously stirring with magnetons for 30min to dissolve CsBr and CuBr to form Cs 3 Cu 2 Br 5 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, plugging the conical flask by using a rubber plug, and connecting the conical flask with a vacuum pump for suction filtration;
4. the above-mentioned steps (A) and (B)3) The obtained clear Cs 3 Cu 2 Br 5 The precursor solution is 500 mul, and is injected into a glass bottle filled with 10ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into milky white suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, centrifuging for 5min at the rotating speed of 1000rpm/min,
6. discarding supernatant of the solution centrifuged in the step (5), taking out powder precipitated at the bottom, and putting the powder into a vacuum drying oven to be dried in vacuum at 60 ℃ for 60min to obtain the Cs 3 Cu 2 Br 5 Nanocrystalline fluorescent powder.
Example 3
The invention provides a method for preparing Cs in an environmental atmosphere by using ethanol as an extracting agent 3 Cu 2 Cl 5 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: CsCl and CuCl were dissolved well in DMF at a molar ratio of 3:2: the volume ratio of DMSO is 3: 7, obtaining a clear precursor solution by suction filtration, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove supernatant fluid to obtain the Cs 3 Cu 2 Cl 5 Nanocrystalline fluorescent powder.
The method specifically comprises the following steps:
1. CsCl (0.15mmol), CuCl (0.1mmol), DMSO (10mL) were mixed in a glass vial.
2. Heating the small glass bottle in a water bath to 60 deg.C, and vigorously stirring with magnetons for 30min to dissolve CsCl and CuCl to form Cs 3 Cu 2 Cl 5 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, and plugging the conical flask by using a rubber plug, wherein the conical flask is connected with a vacuum pump for suction filtration;
4. taking the clear Cs prepared in the step (3) 3 Cu 2 Cl 5 The precursor solution is 500 mul, and is injected into a glass bottle filled with 10ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into milky white suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, centrifuging for 5min at the rotating speed of 1000rpm/min,
6. discarding supernatant of the solution centrifuged in the step (5), taking out powder precipitated at the bottom, and putting the powder into a vacuum drying oven to be dried in vacuum at 60 ℃ for 60min to obtain the Cs 3 Cu 2 Cl 5 Nanocrystalline fluorescent powder.
Example 4
The invention provides a method for preparing Cs in an environmental atmosphere by using ethanol as an extracting agent 3 Cu 2 I 2.5 Br 2.5 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: fully dissolving CsI, CsBr, CuI and CuBr in a DMF solution according to the molar ratio of 3:3:2:2, carrying out suction filtration to obtain a clear precursor solution, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove supernatant, thus obtaining the Cs 3 Cu 2 I 2.5 Br 2.5 Nanocrystalline fluorescent powder.
The method specifically comprises the following steps:
1. CsI (0.075mmol), CsBr (0.075mmol), CuI (0.05mmol), CuBr (0.05mmol) were added to a glass vial with DMSO (10mL) and mixed.
2. Heating the small glass bottle in a water bath to 50 deg.C, and vigorously stirring with magnetons for 60min to dissolve CsI, CsBr, CuI and CuBr to form Cs 3 Cu 2 I 2.5 Br 2.5 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, and plugging the conical flask by using a rubber plug, wherein the conical flask is connected with a vacuum pump for suction filtration;
4. taking the clear Cs prepared in the step (3) 3 Cu 2 I 2.5 Br 2.5 The precursor solution is 250 mul, and is injected into a glass bottle filled with 10ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into milky white suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, centrifuging for 8min at the rotating speed of 5000rpm/min,
6. centrifuging the solution obtained in the step (5)Removing supernatant, taking out bottom precipitate powder, and vacuum drying in vacuum drying oven at 60 deg.C for 10min to obtain Cs 3 Cu 2 I 2.5 Br 2.5 Nanocrystalline fluorescent powder.
Example 5
The invention provides a method for preparing Cs in an environmental atmosphere by using ethanol as an extracting agent 3 Cu 2 Cl 2.5 Br 2.5 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: fully dissolving CsCl, CsBr, CuCl and CuBr in a DMF solution according to the molar ratio of 3:3:2:2, carrying out suction filtration to obtain a clear precursor solution, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove supernatant, thus obtaining the Cs 3 Cu 2 Cl 2.5 Br 2.5 Nanocrystalline fluorescent powder.
The method specifically comprises the following steps:
1. CsCl (0.075mmol), CsBr (0.075mmol), CuCl (0.05mmol), and CuBr (0.05mmol) were added to and mixed with a glass vial containing DMSO (10 mL).
2. Heating the small glass bottle in a water bath to 50 deg.C, and vigorously stirring with magnetons for 60min to dissolve CsCl, CsBr, CuCl and CuBr to form Cs 3 Cu 2 Cl 2.5 Br 2.5 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, and plugging the conical flask by using a rubber plug, wherein the conical flask is connected with a vacuum pump for suction filtration;
4. taking the clear Cs prepared in the step (3) 3 Cu 2 Cl 2.5 Br 2.5 The precursor solution is 250 mul, and is injected into a glass bottle filled with 10ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into milky white suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, centrifuging for 8min at the rotating speed of 5000rpm/min,
6. centrifuging the solution obtained in step (5), removing supernatant, taking out the powder precipitated at the bottom, and vacuum drying in a vacuum drying oven at 60 deg.C for 10min to obtain the final productTo the Cs 3 Cu 2 Cl 2.5 Br 2.5 Nanocrystalline fluorescent powder.
Example 6
The invention provides a method for preparing CsCu in an environmental atmosphere by using ethanol as an extracting agent 2 I 3 A method for preparing perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: fully dissolving CsI and CuI in a DMSO solution according to a molar ratio of 1:2, performing suction filtration to obtain a clear precursor solution, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove a supernatant, thus obtaining the CsCu 2 I 3 Nanocrystalline fluorescent powder.
The method specifically comprises the following steps:
1. CsI (0.1mmol), CuI (0.2mmol), DMSO (10mL) were mixed in a glass vial.
2. Heating the glass bottle in the step (1) to 60 ℃ in a water bath kettle, and vigorously stirring by utilizing magnetons for 30min to fully dissolve CsI and CuI to form CsCu 2 I 3 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, and plugging the conical flask by using a rubber plug, wherein the conical flask is connected with a vacuum pump for suction filtration;
4. the clear CsCu prepared in the step (3) is added 2 I 3 The precursor solution is injected into a glass bottle filled with 10ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into milky white suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, centrifuging for 5min at 1000rpm/min,
6. and (4) removing supernatant of the solution obtained after the centrifugation in the step (5), taking out powder precipitated at the bottom, and putting the powder into a vacuum drying oven to be dried in vacuum for 60min at the temperature of 60 ℃, thus obtaining the CsCu 2 I 3 Nanocrystalline fluorescent powder.
Example 7
The invention provides a method for preparing Cs in an environmental atmosphere by using ethanol as an extracting agent 3 Cu 2 I 5 And CsCu 2 I 3 Mixed phase method of perovskite nanocrystalline fluorescent powder. The method specifically comprises the following steps: fully dissolving CsI and CuI in a DMSO solution according to a molar ratio of 3:5, performing suction filtration to obtain a clear precursor solution, injecting the clear precursor solution into an absolute ethyl alcohol reagent, and centrifuging to remove a supernatant to obtain the Cs 3 Cu 2 I 5 And CsCu 2 I 3 Perovskite nanocrystalline phosphor.
The method specifically comprises the following steps:
1. CsI (0.3mmol), CuI (0.5mmol), DMSO (10mL) were mixed in a glass vial.
2. Heating the small glass bottle in the step (1) to 60 ℃ in a water bath kettle, and vigorously stirring by utilizing magnetons for 30min to fully dissolve CsI and CuI to form Cs 3 Cu 2 I 5 And CsCu 2 I 3 The precursor solution of (1).
3. Placing the solution prepared in the step (2) on a conical flask by using a sand core funnel with the aperture of 2 mu m, and plugging the conical flask by using a rubber plug, wherein the conical flask is connected with a vacuum pump for suction filtration;
4. clarifying Cs prepared in the step (3) 3 Cu 2 I 5 /CsCu 2 I 3 The precursor solution of (a) is injected into a glass bottle filled with 50ml of absolute ethyl alcohol, and the absolute ethyl alcohol immediately turns into a light yellow suspension.
5. Transferring the milky white suspension prepared in the step (4) into a centrifuge tube, and centrifuging for 5min at 1000 rpm/min;
6. discarding supernatant of the solution centrifuged in the step (5), taking out powder precipitated at the bottom, and putting the powder into a vacuum drying oven to be dried in vacuum at 60 ℃ for 60min to obtain the Cs 3 Cu 2 I 5 And CsCu 2 I 3 And (3) uniformly mixing the fluorescent powder.
The obtained Cs 3 Cu 2 I 5 /CsCu 2 I 3 The performance characterization of the optical properties of the nanocrystals is as follows:
as shown in FIG. 5, photographs of phosphors prepared by CsI and CuI according to a series of different molar ratios under a fluorescent lamp and a 310nm ultraviolet lamp respectively show that the phosphors prepared under different molar ratios are all white powders under the fluorescent lamp, and blue, white and yellow luminescence is realized under the 310nm ultraviolet lamp.
As shown in FIG. 6, the scanning electron microscope results showed Cs 3 Cu 2 I 5 And CsCu 2 I 3 The two crystal grains coexist, and the crystal grains coexist from the beginning stage of crystallization, so that the mixture is very uniform and the crystallinity is better.
As shown in fig. 7, the white LED prepared by coating the phosphor prepared in example 7 on the surface of a 310nm ultraviolet lamp chip has color coordinates of (0.35 ), and realizes a good illumination effect.
The perovskite nanocrystalline fluorescent powder prepared in examples 2 to 6 was used in sequence for the same performance characterization as in example 1, with only the change of the position of the luminescence peak, so that the description thereof will be omitted.
While the invention has been described with reference to a number of illustrative embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

Claims (8)

1. A preparation method of white light and blue-green yellow light non-lead perovskite nanocrystalline fluorescent powder is characterized by comprising the following steps:
(1) CsX and CuX powder are added into a round-neck flask filled with solvent; x in the CsX and CuX is one or more of Cl, Br and I;
(2) violently stirring for 10-120 min at 30-100 ℃ in a water bath kettle to fully dissolve CsX and CuX to form CsCu 2 X 3 Or Cs 3 Cu 2 X 5 The precursor solution of (1);
(3) cooling and filtering the precursor solution obtained in the step (2) to obtain a clear precursor solution;
(4) under the condition of vigorous stirring, injecting the clear precursor solution obtained in the step (3) into ethanol, and changing the solution into emulsion;
(5) centrifuging the emulsion obtained in step (4), discarding the supernatant and drying the bottom precipitate powder to obtain Cs 3 Cu 2 I 5 、Cs 3 Cu 2 I 2.5 Br 2.5 、Cs 3 Cu 2 Br 5 、Cs 3 Cu 2 Cl 2.5 Br 2.5 And Cs 3 Cu 2 Cl 5 The perovskite nanocrystalline fluorescent powder.
2. The method for preparing non-lead perovskite nanocrystalline phosphor with white light and blue-green-yellow light according to claim 1, wherein the molar ratio of CsX and CuX added in the step (1) is 0.25-4: 1.
3. the method for preparing non-lead perovskite nano-crystalline phosphor of white light and blue-green-yellow light according to claim 1, wherein the solvent in step (1) is DMF, DMSO or a mixed solvent of DMF and DMSO in any proportion.
4. The method for preparing non-lead perovskite nano-crystalline phosphor of white light and blue-green yellow light according to claim 1, wherein the concentration range of the precursor solution in the step (2) is 0.01 mm/L-2.5 m/L.
5. The method for preparing non-lead perovskite nanocrystalline phosphor of white light and blue-green yellow light according to claim 1, wherein the volume ratio of the injected clear precursor solution and absolute ethyl alcohol in the step (4) is 1: 8 to 50.
6. The method for preparing the white-light, blue-green-yellow-light, non-lead perovskite nanocrystalline phosphor according to claim 1, wherein the rotation speed of the centrifugation in the step (5) is 500-8000 rpm/min, and the centrifugation time is 3-20 min.
7. The method for preparing non-lead perovskite nano-crystalline phosphor of white light and blue-green yellow light according to claim 1, wherein the drying temperature in the step (5) is 30-100 ℃ and the drying time is 5-120 min.
8. The application of the perovskite nanocrystalline phosphor prepared by the method according to any one of claims 1 to 7 in the field of LED lighting, characterized in that white light and blue-green-yellow light LEDs are prepared by coating the phosphor on the surface of an ultraviolet lamp chip, and the wavelength range of the selected ultraviolet lamp is 255 to 310 nm.
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Rapid synthesis and mechanochemical reactions of cesium copper halides for convenient chromaticity tuning and efficient white light emission;Fang Shaofan;《Journal of Materials Chemistry C》;20200306;第8卷(第14期);第4896页左栏倒数第1段-右栏第1段,图3 *

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