CN114479831B - Preparation method of perovskite quantum dot powder - Google Patents
Preparation method of perovskite quantum dot powder Download PDFInfo
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- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
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- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
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- 229910052793 cadmium Inorganic materials 0.000 description 3
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- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 2
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- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
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- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
The invention provides a preparation method of perovskite quantum dot powder, which comprises the following steps: 1) Mixing and grinding aluminum hydroxide powder, a hole sealing agent, a pore expanding agent and a perovskite precursor to obtain a mixture; 2) Calcining the mixture obtained in the step 1) at a high temperature; 3) Naturally cooling the calcined product to room temperature, adding distilled water, stirring, centrifuging, and then putting into a vacuum oven for drying to obtain perovskite quantum dot powder. The perovskite quantum dot powder prepared by the preparation method disclosed by the invention has the advantages of stable luminescence wavelength, stable half-width, good high-temperature resistance, blue light resistance and water resistance, so that the LED lamp prepared by using the perovskite quantum dot powder has a good effect and can be used for a long time to keep good luminescence efficiency.
Description
Technical Field
The invention belongs to the field of quantum dots, and particularly relates to a preparation method of perovskite quantum dot powder.
Background
The quantum dots have the advantages of high fluorescence quantum efficiency, adjustable luminescence color and the like, so that the research on semiconductor quantum dots is very long in the last thirty years. Despite such rapid development of quantum dots, its dominant material is still limited to cadmium-based quantum dots of wurtzite or sphalerite structure. The preparation method generally prepares the high-quality cadmium-based quantum dot material, generally adopts a thick core-shell structure technology, has long preparation period (2-50 h), high reaction temperature (200 ℃), complex process and great challenges in cost and price in the future commercialization process. The development of novel quantum dots with high quality, no cadmium and independent property rights has become a problem to be solved urgently. Accordingly, research on cadmium-free perovskite quantum dots is receiving attention.
Perovskite quantum dots are mainly composed of three ions, and the general structural formula ABX 3 (x=cl, br, I), a consists essentially of CH 3 NH 3 + 、HC(NH 2 ) 2+ Cs plasma, B is mainly Pb. Perovskite quantum dots as a novel luminescent material develop rapidly and have ultrahigh photoluminescence quantum efficiency>90%) and narrow linewidth (12-40 nm), the external quantum efficiency of perovskite quantum dot Light Emitting Diodes (LEDs) has been ramped from 0.12% for initial initiation to 6.27% for only two years. Compared with the traditional II-VI semiconductor quantum dot, the perovskite quantum dot can show high-efficiency luminescence performance without a core/shell structure, the luminescence wavelength is easier to regulate and control, and even under the condition of room temperature, the perovskite quantum dot can be randomly regulated in the whole visible region range, so that the perovskite quantum dot has important application prospect in the fields of solid state illumination, display and the like. The current wide-color-gamut white light emitting diode based on perovskite quantum dots has a color gamut reaching 130% NTSC standard, which shows great application potential of the perovskite quantum dots in the display field.
Typically, the perovskite quantum dot synthesis is typically performed by thermal implantation. Cesium carbonate, oleylamine and octadecene are placed in a three-necked flask, and heated under a nitrogen atmosphere to completely dissolve cesium carbonate, thereby obtaining a precursor solution of cesium. And (3) placing oleylamine, oleic acid and lead halide in a three-necked flask, heating under nitrogen atmosphere to enable the lead halide to be completely dissolved in the solution, rapidly heating, rapidly injecting the prepared cesium precursor solution, reacting for a few seconds, carrying out ice bath in an ice-water mixture, centrifuging to obtain precipitate, and dissolving the precipitate in an organic solvent to prepare the quantum dot.
However, perovskite materials prepared by the thermal injection method have many surface defects due to unbalanced surface ion numbers and many dangling bonds, and are limited in application to the field of luminescence. The perovskite quantum dots have poor stability in the environments of air, high temperature, illumination, water and the like, so that the perovskite quantum dots become a main obstacle for application.
The perovskite quantum dots with different luminous wavelengths are combined together, and the white light diode can be prepared through current excitation. The white light diode with high color rendering index can be prepared by adjusting the proportion of quantum dots with different wavelengths. At present, perovskite quantum dots with different luminescence wavelengths are prepared by controlling the size and the morphology of the quantum dots. The size and morphology of the perovskite quantum dots are controlled to realize different light-emitting wavelengths, experimental conditions are required to be changed to prepare the quantum dots with different light-emitting characteristics, however, strict experimental variables are required in the process, otherwise, the defects of wavelength shift, half-peak width widening and the like caused by non-uniform size and morphology of the quantum dots are caused. The preparation of single-system white light LEDs by different luminescent quantum dots through controlling the size and the morphology of the quantum dots still has some defects.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of perovskite quantum dot powder, the perovskite quantum dot powder prepared by the preparation method has stable luminous wavelength, stable half-width, good high temperature resistance, blue light resistance and water resistance, so that an LED lamp prepared by using the perovskite quantum dot powder has good effect and can be used for a long time to maintain good luminous efficiency.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the perovskite quantum dot powder comprises the following steps:
1) Mixing and grinding aluminum hydroxide powder, a hole sealing agent, a pore expanding agent and a perovskite precursor to obtain a mixture;
2) Calcining the mixture obtained in the step 1) at a high temperature;
3) Naturally cooling the calcined product to room temperature, adding distilled water, stirring, centrifuging, and then putting into a vacuum oven for drying to obtain perovskite quantum dot powder.
The basic principle of the invention is as follows: the aluminum hydroxide is sintered at high temperature to form porous active alumina, the pore diameter of the active alumina is generally about 5-15nm, perovskite precursors volatilize in the high-temperature process, vapor meets in pores to form perovskite quantum dots which are embedded in the pores, and meanwhile, the pores are sealed after the low-melting-point hole sealing agent is melted, so that the perovskite quantum dots in the pores are prevented from being corroded by water and oxygen, the problem of poor perovskite stability is solved, meanwhile, the sealed pores isolate the perovskite quantum dots, agglomeration among the quantum dots is avoided, and the stability of perovskite quantum dot powder is improved. The pore-expanding agent aims to adjust the size of the pore diameter, and then adjust the emission wavelength of the perovskite quantum dot.
Further, in the step 1), aluminum hydroxide powder, a hole sealing agent, a pore expanding agent and a perovskite precursor are respectively as follows in percentage by weight: 50-80% of aluminum hydroxide powder, 1-10% of hole sealing agent, 1-10% of hole expanding agent and 10-40% of calcium-titanium precursor.
Further, in the step 1), aluminum hydroxide powder, a hole sealing agent, a pore expanding agent and a perovskite precursor are respectively as follows in percentage by weight: 60-80% of aluminum hydroxide powder, 5-10% of hole sealing agent, 5-10% of hole expanding agent and 10-30% of calcium-titanium precursor.
Further, the pore-expanding agent is NH 4 HCO 3 、NH 4 H 2 PO 4 Ammonium oxalate, PVA, polyethylene glycol, starch and derivatives thereof, cellulose, wood dust, activated carbon or carbon powder.
Further, the hole sealing agent is phosphate, phosphite, boric acid, borate or oxide of phosphorus and boron.
Further, the perovskite precursor is a mixture of CsY and PbXWherein Y is CO 3 2- 、Br - 、Cl - Or I - X is Br - 、Cl - Or I - 。
Further, in the step 2), the calcination is performed at a speed of 1-10 ℃/min to 400-800 ℃.
Further, the calcination is carried out at a speed of 1-10 ℃/min to 500-700 ℃.
Further, the calcination time is 10min-3h.
Further, the calcination is performed in air.
The invention has the advantages and positive effects that:
1. the preparation method disclosed by the invention is simple to operate, adopts a calcination mode to prepare, does not generate a large amount of waste liquid in the preparation process, and is convenient for mass production and use.
2. The perovskite quantum dot prepared by the preparation method disclosed by the invention is high-temperature resistant and is more suitable for a high-temperature processing technology.
3. The perovskite quantum dot synthesized by the method has a rigid and compact crystal structure, is sealed in a porous carrier, avoids water oxygen erosion, has good blue light irradiation resistance and water resistance, and can meet the application requirement of high stability.
Drawings
FIG. 1 is a graph showing the luminous efficiency obtained in test example 1 of the present invention;
FIG. 2 is a graph showing the luminous efficiency obtained in test example 2 of the present invention;
FIG. 3 is a graph showing the luminous efficiency obtained in test example 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1:
the preparation method of the perovskite quantum dot powder comprises the following steps:
1) Weighing Cs 2 CO 3 Powder 0.6g, pbBr 2 1.37g of powder is poured into a mortar, ground into brown yellow powder, then 5g of aluminum hydroxide powder, 0.5g of carbon powder and 0.5g of boric acid powder are addedGrinding is continued for 10min to form pale yellow powder, and a mixture is obtained.
2) Pouring the ground powder into a crucible, and placing the crucible into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 1 ℃/min, and the muffle furnace is heated to 600 ℃ and then is kept at the temperature for calcination for 30min.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
The perovskite quantum dot powder obtained in this example was tested, wherein the test wavelength was 511nm and the half-width was 24nm.
Example 2:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the content of the components, specifically as follows:
in step 1), cs is weighed 2 CO 3 2g of powder, pbBr 2 2g of powder is poured into a mortar and ground into brown yellow powder, then 5g of aluminum hydroxide powder, 0.5g of carbon powder and 0.5g of boric acid powder are added, and grinding is continued for 10min to form light yellow powder, so as to obtain a mixture.
Example 3:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the content of the components, specifically as follows:
in step 1), cs is weighed 2 CO 3 Powder 0.5g, pbBr 2 0.5g of powder is poured into a mortar and ground into a brown yellow powder, then 8g of aluminum hydroxide powder, 0.5g of carbon powder and 0.5g of boric acid powder are added, and grinding is continued for 10min to form a light yellow powder, so as to obtain a mixture.
Example 4:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the content of the components, specifically as follows:
in step 1), cs is weighed 2 CO 3 1g of powder, pbBr 2 2g of powder is poured into a mortar and ground into brown yellow powder, then 6.8g of aluminum hydroxide powder, 0.1g of carbon powder and 0.1g of boric acid powder are added for continuous grindingGrinding for 10min to form pale yellow powder to obtain mixture.
Example 5:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the content of the components, specifically as follows:
in step 1), cs is weighed 2 CO 3 Powder 0.5g, pbBr 2 1.5g of the powder is poured into a mortar and ground into a brown yellow powder, then 6g of aluminum hydroxide powder, 1g of carbon powder and 1g of boric acid powder are added, and grinding is continued for 10min to form a light yellow powder, so as to obtain a mixture.
Example 6:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the content of the components, specifically as follows:
in step 1), cs is weighed 2 CO 3 Powder 0.5g, pbBr 2 1g of powder is poured into a mortar and ground into brown yellow powder, then 7g of aluminum hydroxide powder, 0.75g of carbon powder and 0.75g of boric acid powder are added, and grinding is continued for 10min to form light yellow powder, so as to obtain a mixture.
Example 7:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the content of the components, specifically as follows:
in step 1), cs is weighed 2 CO 3 1g of powder, pbBr 2 1g of powder is poured into a mortar and ground into brown yellow powder, then 7g of aluminum hydroxide powder, 0.5g of carbon powder and 0.5g of boric acid powder are added, and grinding is continued for 10min to form light yellow powder, so as to obtain a mixture.
Comparative example 1:
the comparative example was prepared as in example 1, with the following differences from example 1 in terms of the components and contents:
in step 1), cs is weighed 2 CO 3 Powder 0.6g, pbBr 2 1.37g of the powder was poured into a mortar, ground into a brown yellow powder, then 5g of aluminum hydroxide powder and 0.5g of boric acid powder were added, and grinding was continued for 10 minutes to form a pale yellow powder, to obtain a mixture.
Comparative example 2:
the comparative example was prepared as in example 1, with the following differences from example 1 in terms of the components and contents:
in step 1), cs is weighed 2 CO 3 Powder 0.6g, pbBr 2 1.37g of the powder is poured into a mortar, ground into a brown yellow powder, then 5g of aluminum hydroxide powder is added, and grinding is continued for 10min to obtain a light yellow powder, so as to obtain a mixture.
Comparative example 3:
the comparative example was prepared as in example 1, with the following differences from example 1 in terms of the components and contents:
in step 1), cs is weighed 2 CO 3 Powder 0.6g, pbBr 2 1.37g of powder is poured into a mortar, ground into a brown yellow powder, then 5g of aluminum hydroxide powder and 0.5g of carbon powder are added, and grinding is continued for 10min to form a light yellow powder, so as to obtain a mixture.
Comparative example 4:
the perovskite quantum dot powder is prepared by adopting a preparation method in the prior art, and the specific preparation method is as follows:
weighing 0.36g cesium carbonate, 1.5ml oleic acid, 20ml octadecene, placing cesium carbonate, oleic acid, octadecene in 100ml three-necked flask, heating, vacuumizing at 120deg.C for 1 hr, and introducing N 2 Heating to 150 ℃ and preserving heat for 2 hours continuously until the solid powder is completely dissolved, and obtaining transparent cesium oleate precursor solution. Respectively weighing octadecene (20 ml), oleic acid (5 ml), oleylamine (5 ml) and lead bromide (0.75 g), placing into a 100ml three-neck flask, heating to 120deg.C, vacuumizing for 1h, and N 2 Heating to 150 deg.c in the atmosphere, and maintaining until the lead bromide is dissolved completely. Again, the temperature was raised to 180 ℃, 1ml of cesium oleate precursor liquid was injected, and after 10s of reaction, the mixture was cooled rapidly with an ice-water bath. Placing the reaction product into a centrifuge tube, centrifuging (10000 rpm,10 min), and dissolving the centrifuged perovskite quantum dots into normal hexane solution to obtain CsPbBr 3 Perovskite quantum dot n-hexane solution.
Perovskite quantum dot powders prepared in examples 1 to 7 and comparative examples 1 to 4 were tested, and the test data are shown in table 1:
table 1 table of test data for examples 1-7
| Sequence number | Test wavelength (nm) | Half-width (nm) | Quantum yield |
| Example 1 | 518nm | 23nm | 95％ |
| Example 2 | 521nm | 22nm | 96％ |
| Example 3 | 512nm | 24nm | 93％ |
| Example 4 | 504nm | 24nm | 91％ |
| Example 5 | 524nm | 22nn | 94％ |
| Example 6 | 514nm | 23nm | 93％ |
| Example 7 | 527nm | 24nm | 90％ |
| Comparative example 1 | 515nm | 23nm | 85％ |
| Comparative example 2 | 499nm | 28nm | 80％ |
| Comparative example 3 | 508nm | 26nm | 82％ |
| Comparative example 4 | 519nm | 21nm | 98％ |
From the above data, it can be seen that the perovskite quantum dot powder prepared by the preparation method of the present invention is clean and simple in production process, and the half-peak width is stable, compared with the perovskite quantum dot powder prepared by the preparation method of the prior art of comparative example 4, in which the wavelength of the quantum dot light can be adjusted within a certain range. The biggest advantage is that the high temperature resistance is excellent, the resistance to water and oxygen erosion is strong, and the light stability is high.
In the preparation method, in each component of the perovskite quantum dot, the pore-expanding agent is used for expanding the pore size of the active alumina carrier to accommodate the formation and growth of the perovskite quantum dot, and the pore-expanding agent is used for sealing the pore to protect the perovskite quantum dot. Because the active alumina formed by high-temperature sintering of aluminum hydroxide is of a porous structure, the pore diameter of the active alumina carrier can be increased due to the increase of a pore-enlarging agent, the particle size of the prepared perovskite quantum dot is increased, and the corresponding luminescence wavelength is red shifted. If too little hole sealing agent can expose the perovskite quantum dot formed in the air, directly influenced by moisture and oxygen, the quantum dot is subjected to fluorescence quenching, so that the hole sealing agent is selected to occupy 1% -10% to fully cover the perovskite quantum dot, thereby avoiding the phenomenon of fluorescence quenching caused by the factors of moisture, oxygen and the like, and ensuring the long-time stable luminescence performance.
Because the perovskite quantum dots prepared by high-temperature sintering are freely dispersed and are easy to agglomerate, the quantum dots can be agglomerated and regrown into nano crystals with large particle size under the high-temperature condition by increasing the consumption of the perovskite precursor, and the corresponding luminescence wavelength is red shifted.
Test example 1:
the test example is used for detecting the high temperature resistance of the perovskite quantum dot:
the perovskite quantum dots prepared in example 1 and comparative examples 2 to 4 were subjected to a high temperature resistance experiment, and the specific detection method was as follows: taking 1g of perovskite quantum dot powder of example 1 and 1g of perovskite quantum dot powder of comparative examples 2-4 respectively, placing at 85 ℃, taking out at different times, and testing the 450nm blue light excitation efficiency of the quantum dots of different examples by using an integrating sphere; a graph of luminous efficiency as shown in fig. 1 was prepared with time on the abscissa and relative efficiency on the ordinate.
As can be seen from fig. 1, the perovskite quantum dot powder of example 1 was relatively indistinguishable from the initial light-emitting efficiency after being continuously baked at 85 ℃ for 30 days, whereas the perovskite quantum dots of comparative examples 2 and 3 and comparative example 4 were gradually lowered in light-emitting efficiency with the long-time baking, and hardly emitted any more at less than 15 days. The perovskite quantum dot of comparative example 4 has the advantages that the luminous efficiency is greatly reduced immediately after the perovskite quantum dot is baked at a high temperature, and the high temperature resistance is extremely poor. Therefore, the perovskite quantum dot prepared by the preparation method has good high-temperature resistance, and can keep good luminous efficiency at high temperature and stable performance.
In addition, the above-described tests were also performed on perovskite quantum dot powders prepared in example 2 and example 3 of the present invention, and the results obtained were similar to example 1.
Test example 2:
the test example is used for detecting the water resistance of the perovskite quantum dot:
the perovskite quantum dots prepared in example 1 and comparative examples 2 to 4 were subjected to a water resistance test by the following specific methods: taking 1g of perovskite quantum dot powder of example 1 and 1g of perovskite quantum dot powder of comparative examples 2-4 respectively, placing the perovskite quantum dot powder in distilled water respectively, placing the perovskite quantum dot powder in a dark place at normal temperature, taking out part of quantum dot powder at different times, drying the quantum dot powder at normal temperature, and placing the quantum dot powder into an integrating sphere to test the 450nm excitation efficiency of the quantum dots of different examples; the luminous efficiency map shown in fig. 2 is prepared by taking time as an abscissa and the relative efficiency as an ordinate.
As can be seen from fig. 1, the perovskite quantum dot powder of example 1 had a decrease in light reflection efficiency with an increase in soaking time, but remained substantially above 75% after 30 days of soaking, whereas the perovskite quantum dots of comparative examples 2, 3 and 4 had a rapid decrease in soaking time, and had a decrease in light emission efficiency below 10% after less than 15 days, and hardly emitted light. Therefore, the perovskite quantum dot prepared by the preparation method has good water resistance, and can keep good luminous efficiency and stable performance under the condition of soaking water.
In addition, the above-described tests were also performed on perovskite quantum dot powders prepared in example 2 and example 3 of the present invention, and the results obtained were similar to example 1.
Test example 3:
the experimental example is used for detecting the blue light irradiation resistance of the perovskite quantum dot:
the perovskite quantum dots prepared in example 1 and comparative examples 2 to 4 were subjected to a blue light irradiation resistance test, and the test method was as follows: respectively taking 1g of perovskite quantum dot powder from example 1 and comparative examples 2-4, placing the perovskite quantum dot powder under blue light of 38W/m < 2 >, irradiating, taking a small part of quantum dot powder at different times, and using an integrating sphere to test the quantum dot efficiency; a graph of luminous efficiency as shown in fig. 3 was prepared with time on the abscissa and relative efficiency on the ordinate.
As can be seen from fig. 1, the perovskite quantum dot powder of example 1 has a reduced luminous efficiency with the increase of irradiation time under irradiation of ultraviolet rays, but the luminous efficiency is maintained at 90% or more even after 30 days of ultraviolet irradiation, so that the perovskite quantum dot powder has good light resistance; the perovskite quantum dots of comparative example 2, comparative example 3 and comparative example 4 were gradually stabilized after the rapid decrease in luminous efficiency with the long-time irradiation of ultraviolet rays, and finally remained between 25% and 35%. Therefore, the perovskite quantum dot prepared by the preparation method has good light resistance, can keep good luminous efficiency under the irradiation of ultraviolet rays, and has stable performance.
In addition, the above-described tests were also performed on perovskite quantum dot powders prepared in example 2 and example 3 of the present invention, and the results obtained were similar to example 1.
Example 8:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the components, the content of which is the same, and the specific differences are as follows:
in step 1), cs is weighed 2 CO 3 Powder 0.6g, pbCl 2 1.37g of the powder was poured into a mortar, ground into a brown yellow powder, and then 5g of aluminum hydroxide powder, 0.5. 0.5gNH, was added 4 H 2 PO 4 0.5g boric acid powder, grinding for 10min, and forming yellowish powder to obtain mixture.
Example 9:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the components, the content of which is the same, and the specific differences are as follows:
in step 1), csBr is weighed 2 Powder 0.6g, pbBr 2 1.37g of the powder is poured into a mortar, ground into a brown yellow powder, and then 5g of aluminum hydroxide powder and 0.5g of NH are added 4 H 2 PO 4 0.5g of borax powder was continuously ground for 10min to form pale yellow powder, and a mixture was obtained.
Example 10:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the components, the content of which is the same, and the specific differences are as follows:
in step 1), cs is weighed 2 CO 3 Powder 0.6g, pbI 2 1.37g of the powder was poured into a mortar, ground into a brown yellow powder, then 5g of aluminum hydroxide powder, 0.5g of PVA,0.5g of calcium phosphate were added, and grinding was continued for 10 minutes to form a pale yellow powder, to obtain a mixture.
Example 11:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the components, the content of which is the same, and the specific differences are as follows:
in step 1), csBr is weighed 2 Powder 0.6g, pbBr 2 1.37g of powder is poured into a mortar and ground into a brown yellow powder, then 5g of aluminum hydroxide powder, 0.5g of polyethylene glycol and 0.5g of boric acid powder are added, and grinding is continued for 10min to form a light yellow powder, so as to obtain a mixture.
Example 12:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the components, the content of which is the same, and the specific differences are as follows:
in step 1), csI is weighed 2 Powder 0.6g, pbBr 2 1.37g of the powder was poured into a mortar, ground into a brown yellow powder, then 5g of aluminum hydroxide powder, 0.5g of PVA and 0.5g of boric acid powder were added, and grinding was continued for 10 minutes to form a pale yellow powder, to obtain a mixture.
Example 13:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the components, the content of which is the same, and the specific differences are as follows:
in step 1), csBr is weighed 2 Powder 0.6g, pbBr 2 1.37g of powder is poured into a mortar and ground into a brown yellow powder, then 5g of aluminum hydroxide powder, 0.5g of carbon powder and 0.5g of boric acid powder are added, and grinding is continued for 10min to form a light yellow powder, so as to obtain a mixture.
The perovskite quantum dot powders prepared in examples 8 to 13 were tested, and the test data are shown in Table 2:
TABLE 2 detection data for examples 8-13
| Sequence number | Test wavelength (nm) | Half-width (nm) | Quantum dot yield |
| Example 8 | 520nm | 23nm | 94％ |
| Example 9 | 518nm | 24nm | 96％ |
| Example 10 | 521nm | 23nm | 95％ |
| Example 11 | 520nm | 24nm | 94％ |
| Example 12 | 522nm | 21nm | 96％ |
| Example 13 | 518nm | 24nm | 92％ |
From the experimental data in Table 2, it can be seen that when the perovskite precursor is a mixture of CsY and PbX, where Y is CO 3 2- 、Br - 、Cl - Or I - X is Br - 、Cl - Or I - The method comprises the steps of carrying out a first treatment on the surface of the When the perovskite precursors are selected to be combined, the luminous wavelength and half-peak width of the prepared perovskite quantum dots are relatively stable; meanwhile, different substances can be selected for reaction by the pore expanding agent and the pore sealing agent.
In addition, the perovskite quantum dot powders prepared in examples 8 to 13 of the present invention were also subjected to a high temperature resistance test, a water resistance test and a light irradiation test with milk blue, and the results obtained were similar to those of example 1.
Example 14:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 2 ℃/min, and the muffle furnace is heated to 600 ℃ and then calcined for 10min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 15:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 5 ℃/min, and the muffle furnace is heated to 600 ℃ and then calcined for 30min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 16:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 10 ℃/min, and the muffle furnace is heated to 600 ℃ and then calcined for 30min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 17:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 1 ℃/min, and the muffle furnace is heated to 600 ℃ and then calcined for 180min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 18:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 5 ℃/min, and the muffle furnace is heated to 400 ℃ and then calcined for 180min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 19:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 5 ℃/min, and the muffle furnace is heated to 400 ℃ and then calcined for 10min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 20:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 10 ℃/min, and the muffle furnace is heated to 800 ℃ and then calcined for 30min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Example 21:
the preparation method of this example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 10 ℃/min, and the muffle furnace is heated to 800 ℃ and then calcined for 10min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Comparative example 5:
the preparation method of this comparative example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to 15 ℃/min, and the muffle furnace is heated to 600 ℃ and then calcined for 30min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Comparative example 6:
the preparation method of this comparative example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 10 ℃/min, and the muffle furnace is heated to 900 ℃ and then calcined for 30min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Comparative example 7:
the preparation method of this comparative example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 10 ℃/min, and the muffle furnace is heated to 300 ℃ and then calcined for 30min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
Comparative example 8:
the preparation method of this comparative example is the same as that of example 1, and differs from example 1 in the process parameters in the preparation process, and the specific differences are as follows:
in the step 2), the ground powder is poured into a crucible and put into a muffle furnace for calcination, wherein the temperature rising speed of the muffle furnace is set to be 1 ℃/min, and the muffle furnace is heated to 300 ℃ and then calcined for 180min at the temperature.
3) And after calcining, taking out the crucible, naturally cooling to room temperature, adding distilled water, stirring for 1min, centrifuging, and then putting into a vacuum drying box to be dried at 60 ℃ to obtain perovskite quantum dot powder.
The perovskite quantum dot powders prepared in examples 14 to 21 and comparative examples 5 to 8 were tested, and the test results are shown in Table 3:
TABLE 3 detection results for examples 14-21
| Sequence number | Test wavelength (nm) | Half-width (nm) | Quantum dot yield |
| Example 14 | 516nm | 24nm | 92％ |
| Example 15 | 518nm | 22nm | 91％ |
| Example 16 | 517nm | 21nm | 95％ |
| Example 17 | 520nm | 23nm | 96％ |
| Example 18 | 514nm | 21nm | 92％ |
| Example 19 | 512nm | 24nm | 94％ |
| Example 20 | 515nm | 22nm | 93％ |
| Example 21 | 514nm | 24nm | 94％ |
| Comparative example 5 | 516nm | 33nm | 80％ |
| Comparative example 6 | 509nm | 31nm | 79％ |
| Comparative example 7 | 485nm | 28nm | 82％ |
| Comparative example 8 | 492nm | 29nm | 84％ |
From the experimental data, the growth of the perovskite quantum dots is influenced by the temperature rising rate, the calcination temperature and the heat preservation time; the slow heating rate can prolong the growth time of the quantum dots, increase the crystal size and red shift the luminescence wavelength; the temperature rising speed is too fast, so that the quantum dots grow unevenly, the size distribution range is wide, and the half-peak width is increased. In addition, the calcination temperature is also an important factor affecting the quantum dots; the perovskite component is difficult to form vapor to be embedded in the holes at too low temperature, so that the stability is poor, and fluorescence quenching is easy to occur; the temperature is low, the quantum dot crystal is difficult to grow, the grain diameter of the crystal is small, and the corresponding luminescence wavelength is short; the temperature is too high, the aperture of the alumina carrier is reduced, the growth size of perovskite quantum dots in holes is limited, the particle size is uneven, the size distribution range is wide, the corresponding luminescence wavelength is blue-shifted, and the half-peak width is increased. The influence of the heat preservation time on the quantum dots is shown in the invention, the short time can make the quantum dot crystals difficult to uniformly grow, and the particle size is small; the long time can lead the crystal particle size of the quantum dot to be large and easy to agglomerate, so that the fluorescence efficiency is reduced.
Therefore, proper heating rate, calcination temperature and heat preservation time play an important role in the preparation of the quantum dots, and the perovskite quantum dot powder with stable performance can be prepared by the process parameters defined in the invention.
The foregoing describes the embodiments of the present invention in detail, but the description is merely a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (6)
1. The preparation method of the perovskite quantum dot powder is characterized by comprising the following steps of:
1) Mixing and grinding aluminum hydroxide powder, a hole sealing agent, a pore expanding agent and a perovskite precursor to obtain a mixture;
2) Calcining the mixture obtained in the step 1) at a high temperature;
3) Naturally cooling the calcined product to room temperature, adding distilled water, stirring, centrifuging, and then putting into a vacuum oven for drying to obtain perovskite quantum dot powder;
in the step 1), aluminum hydroxide powder, hole sealing agent, pore expanding agent and perovskite precursor are respectively as follows by weight percent: 50-80% of aluminum hydroxide powder, 1-10% of hole sealing agent, 1-10% of hole expanding agent and 10-40% of perovskite precursor;
the pore-expanding agent is NH 4 HCO 3 、NH 4 H 2 PO 4 One or more of ammonium oxalate, PVA, polyethylene glycol, starch and derivatives thereof, cellulose, wood dust, activated carbon or carbon powder;
the hole sealing agent is phosphate, phosphite, boric acid, borate or oxide of phosphorus and boron;
the perovskite precursor is a mixture of CsY and PbX, wherein Y is CO 3 2- 、Br - 、Cl - Or I - X is Br - 、Cl - Or I - 。
2. The method for preparing perovskite quantum dot powder according to claim 1, wherein in step 1), aluminum hydroxide powder, hole sealing agent, hole expanding agent and perovskite precursor are respectively as follows in weight percent: 60-80% of aluminum hydroxide powder, 5-10% of hole sealing agent, 5-10% of hole expanding agent and 10-30% of calcium-titanium precursor.
3. The method of preparing perovskite quantum dot powder according to claim 1 or 2, wherein in step 2), the calcination is performed at a rate of 1-10 ℃/min up to 400-800 ℃.
4. A method of preparing perovskite quantum dot powder according to claim 3, wherein: the calcination is carried out at a speed of 1-10 ℃/min to 500-700 ℃.
5. The method for preparing perovskite quantum dot powder according to claim 4, wherein: the calcination time is 10min-3h, and the calcination is carried out in air.
6. The method for preparing perovskite quantum dot powder according to claim 5, wherein: the drying temperature in the vacuum drying box is 60 ℃.
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