CN114058367A - Perovskite quantum dot and mesoporous silica composite luminescent material and preparation thereof - Google Patents
Perovskite quantum dot and mesoporous silica composite luminescent material and preparation thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 55
- 239000002096 quantum dot Substances 0.000 title claims abstract description 55
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 32
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005642 Oleic acid Substances 0.000 claims abstract description 18
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000004820 halides Chemical class 0.000 claims abstract description 15
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940049964 oleate Drugs 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910001643 strontium iodide Inorganic materials 0.000 claims abstract description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910001427 strontium ion Inorganic materials 0.000 claims description 9
- 239000012045 crude solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 abstract 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 abstract 1
- 238000006862 quantum yield reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- -1 iodide ions Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a perovskite quantum dot and mesoporous silicon dioxide composite luminescent material and preparation thereof, wherein the composite luminescent material is CsPb (Br)xI1‑x)3:ySr2+@SiO2. Mixing, stirring and heating oleic acid, 1-octadecene and cesium carbonate to obtain a cesium oleate solution; heating and stirring mesoporous silica, 1-octadecene, oleylamine and oleic acid under the nitrogen atmosphere, vacuumizing and stirring, adding lead bromide, lead iodide and strontium iodide, heating and stirring to obtain a lead halide precursor solution; injecting the cesium oleate solution into the lead halide precursor solution, and performing ice-water bath to obtain coarse productAnd (3) centrifuging the solution, completely dissolving the precipitate by using n-hexane, standing, and drying the lower layer substance in vacuum to obtain the perovskite quantum dot and mesoporous silica composite luminescent material. According to the invention, the perovskite quantum dots are coated by silicon dioxide, so that the distance between adjacent perovskite quantum dots is increased, the direct contact and agglomeration of the adjacent perovskite quantum dots in a solid state are avoided, and the solid-state luminous efficiency of the perovskite quantum dots is improved.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and relates to a perovskite quantum dot and mesoporous silica-based composite luminescent material which can be excited by blue light and has high color purity and high luminescent efficiency, and a preparation method thereof.
Background
The white light LED has the advantages of energy conservation, environmental protection, long service life, high luminous efficiency and the like, and is widely applied to the fields of illumination and display. In order to obtain white light with high color rendering and a wide color gamut backlight device, green and red luminescent materials used in an LED backlight are required to have a narrow emission peak width in addition to high stability and quantum efficiency. Currently commercially available green and red narrow-band luminescent materials are beta-Sialon and KSF, respectively. The synthesis conditions of the beta-Sialon are harsh, and the emission peak is wide (the half-height width of the emission peak is 55 nm). A large amount of HF is needed in the KSF preparation process, the HF has strong volatility and strong corrosivity, is easy to damage the environment and harm the human health, and simultaneously has the problem of instability in a high-temperature and high-humidity environment, so that the service life of a device is seriously influenced. Therefore, the development of green and red luminescent materials with simple preparation process and high-efficiency narrow-band emission is particularly important for manufacturing white light LED devices with high color rendering and wide color gamut.
All-inorganic perovskite quantum dot material (CsPbX)3X ═ Br, I) has the characteristics of narrow emission peak width, high quantum yield and that the luminescence can be controlled by halogen components and quantum dot size, and is an ideal luminescent material for wide color gamut display, but due to the strong ionic property of perovskite quantum dots, the light, heat and water stability of the perovskite quantum dots are poor, and the serious problem of aggregated fluorescence quenching exists. Therefore, the key problem of perovskite quantum dot oriented wide color gamut display practical application is that the stability of perovskite quantum dot is improved and the problem that serious fluorescence quenching is generated due to agglomeration when the perovskite quantum dot is in a solid state is solved.
Disclosure of Invention
The invention aims to provide a perovskite quantum dot and mesoporous silica composite luminescent material with better stability.
The invention also aims to provide a preparation method of the composite luminescent material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a perovskite quantum dot and mesoporous silica composite luminescent material has a chemical formula of CsPb (Br)xI1-x)3:ySr2+@SiO2Wherein x is more than or equal to 0.4 and less than or equal to 1.0, and y is more than or equal to 20 and less than or equal to 50 percent (the percentage is the mol percentage of Sr relative to Pb); the perovskite quantum dot is formed by Cs (Pb, Sr) (Br, I)3The type of the mesoporous silica is SBA-15.
The other technical scheme adopted by the invention is as follows: a preparation method of the composite luminescent material specifically comprises the following steps:
step 1: preparation of cesium oleate precursor:
adding 0.102-0.407 g of cesium carbonate, 5-20 mL of 1-octadecene and 0.4-1.3 mL of oleic acid into a three-neck flask, stirring and heating to 120-150 ℃ in a nitrogen atmosphere, keeping the temperature for 1-2 hours, and completely dissolving the cesium carbonate to obtain a transparent cesium oleate solution;
step 2: preparing a lead halide precursor adsorbed into a silicon dioxide pore channel:
according to 0.1504-0.188 mmol of perovskite material (PbX)2) Respectively taking perovskite material, mesoporous silica and oleic acid according to the proportion of 0.0565 g-0.1468 g of mesoporous silica to 0.4-0.6 mL of oleic acid; then taking SrI2Oleylamine and 1-octadecene;
SrI2the molar mass ratio of Sr in the perovskite material to Pb in the perovskite material is 1: 4-5 (Sr: Pb);
the volume ratio of oleic acid to oleylamine to 1-octadecene is 1: 8-13;
perovskite material (PbX) in mol percent2) From 45 to 50% of PbBr2And 50-55% of PbI2The total amount of each component is 100 percent.
Adding mesoporous silicon dioxide, 1-octadecene, oleic acid and oleylamine into a three-neck flask, stirring and heating to 120 ℃ in a nitrogen atmosphere, vacuumizing and stirring for 20-30 min, and adding a perovskite material and SrI2Stirring the mixture in vacuum at 120 ℃ under the protection of nitrogen until the perovskite material and SrI are obtained2Completely dissolving, heating to 160-180 ℃, and keeping the temperature for 5-10 min to obtain a lead halide precursor solution;
the lead halide precursor solution is lead halide/strontium precursor solution dispersed in the mesoporous silicon dioxide pore channel.
And step 3: preparing the silicon dioxide coated perovskite quantum dot fluorescent powder:
under inert atmosphere, rapidly injecting 0.4-0.6 mL of 130-150 ℃ cesium oleate solution into 5.5-6.5 mL of 160-180 ℃ lead halide precursor, reacting for 5-10 s, immediately performing ice-water bath, and cooling to room temperature to obtain mesoporous silica coated Sr2+Doped CsPb (Br),I)3And centrifuging the crude solution of the quantum dots for 3-5 min (3000 rpm/min) to obtain a precipitate, completely dissolving the precipitate with n-hexane, standing at room temperature for 1-2 h, removing a supernatant, and vacuum-drying a lower layer substance to obtain the perovskite quantum dot and mesoporous silica composite luminescent material (the silica-coated strontium-doped perovskite quantum dot luminescent material).
The preparation method adopts an in-situ synthesis method to prepare the narrow-band-emission strontium-doped perovskite quantum dot and mesoporous silica composite luminescent material with better luminescent stability and solid luminescent performance, and the composite luminescent material has high luminescent efficiency (solid luminescence is more than 90 percent) and narrow half-height width (less than 35 nm).
The composite luminescent material is applied to lighting display, in particular to the fields of white light LEDs, lasers, photodetectors, visible light communication and the like.
The solid red CsPb (Br) prepared by the preparation method of the inventionxI1-x)3:ySr2+@SiO2In the composite sample, the quantum yield can reach 96 percent, and the composite sample is used as a comparative solid CsPb (Br)0.5I0.5)3The quantum yield of the quantum dots is only 16%, because the doping of strontium ions enables the surface defects of the quantum dots to be modified, the tolerance factors are improved, the quantum dots have a more stable structure, in addition, the existence of mesoporous silica disperses the quantum dots, the reabsorption during the light emitting of the quantum dots is avoided, and the comprehensive action enables the quantum yield of the quantum dots to be greatly improvedIt is good.
The composite luminescent material has the following advantages:
1. the strontium ions are used for partially replacing lead ions, so that the toxicity of the perovskite quantum dots is reduced, the surface defects of the quantum dots are passivated, the stability of the composite luminescent material is improved, and the luminous efficiency of the perovskite quantum dots is improved.
2. The composite luminescent material is based on mesoporous silica as a carrier of quantum dots, and has good environmental stability; the perovskite quantum dots are coated by the silicon dioxide, so that the direct contact of the adjacent perovskite quantum dots can be avoided, the distance between the adjacent perovskite quantum dots is increased, the agglomeration of the perovskite quantum dots in a solid state is avoided, and the luminous efficiency of the perovskite quantum dots in the solid state is improved.
3. The composite luminescent material fully exerts the luminescent property of the perovskite quantum dot, has high quantum efficiency, narrow emission peak and adjustable emission wavelength to about 630nm, does not contain rare earth materials, and has good application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of a composite luminescent material obtained in example 1.
FIG. 2 is a photoluminescence spectrum of the composite luminescent material prepared in examples 1 to 3 of the present invention.
FIG. 3 is a transmission electron microscope photograph of a composite luminescent material prepared in example 1.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1
0.102g of cesium carbonate, 5mL of 1-octadecene and 0.4mL of oleic acid were added to a 50mL three-necked flask, and the temperature was raised to 120 ℃ in a nitrogen atmosphere, and the mixture was kept for 1 hour to completely dissolve the cesium carbonate, thereby obtaining a transparent cesium oleate solution. Adding 0.1468g of mesoporous silica, 0.5mL of oleic acid, 0.5mL of oleylamine and 5mL of 1-octadecene into a three-neck flask, heating to 120 ℃ in nitrogen atmosphere, vacuumizing for 30min, and adding 0.031g of PbBr20.0477g of PbI2And 0.013g SrI2At this time, Sr and PbThe molar mass ratio of the raw materials is 1: 5, and the mixture is vacuumized and stirred at the temperature of 120 ℃ under the protection of nitrogen until PbBr is obtained2、PbI2And SrI2Completely dissolving, heating to 180 ℃, and keeping the temperature for 10min to obtain a lead halide precursor; quickly injecting 0.5mL of 130 ℃ cesium oleate solution into 6mL of 180 ℃ lead halide precursor, reacting for 10s, immediately cooling to room temperature in an ice-water bath to obtain a red mesoporous silica coated strontium-doped quantum dot crude solution, centrifuging at the rotating speed of 3000rpm/min for 3min to obtain a first precipitate, completely dissolving the precipitate with n-hexane, standing at room temperature for 1h, removing supernatant, and vacuum drying the subnatant to obtain the perovskite quantum dot and mesoporous silica composite luminescent material CsPb (Br)0.45I0.55)3:20%Sr2+@SiO2(denoted as sample 1).
Example 2
0.407g of cesium carbonate, 20mL of 1-octadecene and 1.3mL of oleic acid were put into a 50mL three-necked flask, and the temperature was raised to 150 ℃ in a nitrogen atmosphere, and the temperature was maintained for 1.5 hours, whereby the cesium carbonate was completely dissolved, and a transparent cesium oleate solution was obtained. Then 0.0565g of mesoporous silica, 0.5mL of oleic acid, 0.5mL of oleylamine and 16mL of 1-octadecene are added into a three-neck flask, the temperature is raised to 120 ℃ in the nitrogen atmosphere, the vacuum pumping is carried out for 20min, and 0.0248g of PbBr is added20.0381g of PbI2And 0.013g SrI2At the moment, the molar mass ratio of Pb to Sr is 4: 1, and the mixture is vacuumized and stirred under the protection of nitrogen until PbBr is reached2、PbI2And SrI2Completely dissolving, heating to 160 ℃, and keeping the temperature for 5min to obtain a lead halide precursor; quickly injecting 0.4mL of 140 ℃ cesium oleate solution into 5.5mL of 160 ℃ lead halide precursor, reacting for 5s, immediately performing ice-water bath, cooling to room temperature to obtain a red mesoporous silica coated strontium-doped quantum dot crude solution, centrifuging at the rotating speed of 3000rpm/min for 5min to obtain a first precipitate, completely dissolving the precipitate with n-hexane, standing at room temperature for 2h, removing supernatant, and vacuum drying the subnatant to obtain the perovskite quantum dot and silica composite luminescent material to obtain the composite material CsPb (Br) of the perovskite quantum dot and silica composite luminescent material0.45I0.55)3:25%Sr2+@SiO2(denoted as sample 2).
Example 3
0.102g of cesium carbonate, 5mL of 1-octadecene and 0.4mL of oleic acid were added to a 50mL three-necked flask, and the temperature was raised to 120 ℃ in a nitrogen atmosphere, and the mixture was kept for 1 hour to completely dissolve the cesium carbonate, thereby obtaining a transparent cesium oleate solution. 0.1468g of mesoporous silica, 0.5mL of oleic acid, 0.5mL of oleylamine and 5mL of 1-octadecene are added into a three-neck flask, the temperature is raised to 120 ℃ in a nitrogen atmosphere, vacuum pumping is carried out for 30min, and 0.0276g of PbBr is added20.0347g of PbI2And 0.013g SrI2At the moment, the molar mass ratio of Pb to Sr is Pb: Sr = 4: 1, and the mixture is stirred in a vacuum pumping way at the temperature of 120 ℃ under the protection of nitrogen until PbBr is reached2、PbI2And SrI2Dissolving completely, heating to 180 deg.C, and keeping the temperature for 10 min; quickly injecting 0.5mL of cesium oleate solution with the temperature of 150 ℃ into 6mL of lead halide precursor with the temperature of 180 ℃, reacting for 10s, immediately cooling in an ice-water bath, obtaining a crude solution of red mesoporous silica coated strontium-doped quantum dots when the temperature is reduced to room temperature, centrifuging at the rotating speed of 3000rpm/min for 3min to obtain a first precipitate, completely dissolving the precipitate with n-hexane, standing at room temperature for 1.5h, removing supernatant, and vacuum drying a lower layer to obtain the perovskite quantum dot and mesoporous silica composite luminescent material CsPb (Br)0.50I0.50)3:25%Sr2+@SiO2(denoted as sample 3).
Example 1 an X-ray diffraction pattern of a composite luminescent material was obtained as shown in fig. 1. With cubic phase CsPbBr3The comparison of the standard card (PDF # 54-0752) shows that the diffraction peaks of the samples are matched with those of the standard card, while the diffraction peak positions of the composite luminescent material prepared in example 1 are slightly shifted compared with those of the standard card as a whole, because of the small angle shift compared with pure CsPbBr3Compared with the prior art, the red emission is realized by replacing bromide with part of iodide ions, and the ionic radius of the iodide ions is obviously larger than that of the bromide, so that the small-angle deviation of an X-ray diffraction pattern is caused. The radius of the strontium ions is slightly smaller than that of the lead ions, but the strontium ions are very close to the lead ions, so that the influence on the diffraction peak position is small. In conclusion, the ion-doped composite material prepared by the invention does not change CsPbBr3The cubic phase structure of (a); at the same time as measuringThe X-ray diffraction comparison of the mesoporous silicon dioxide shows that amorphous SiO exists in the prepared composite material2。
The photoluminescence spectra of samples 1, 2 and 3 prepared in examples 1 to 3 are shown in FIG. 2. Sample 1 is a red composite emitting light at 655 nm; sample 2 is a red composite emitting light at 647 nm; sample 3 is a red composite emitting light at 632 nm. As can be seen from FIG. 2, the emission spectrum of the prepared composite material shifts correspondingly with the change of the halogen ion dosage ratio.
Fig. 3 a is a transmission electron microscope topographic image of the sample 1, and fig. 3 b is a partial enlarged view of fig. 3 a. It is obvious from the figure that the quantum dots are uniformly dispersed and grow in the pore channels of the mesoporous silica.
Examples 1-3 prepared samples 1-3 had emission peak positions and quantum efficiencies as shown in Table 1.
TABLE 1 emission peak position and Quantum efficiency of samples 1-3
As can be seen from Table 1, the composition ratio of sample 1 is PbX20.188mmol, PbBr245% of PbI, and2the molar mass of the compound is 55%, and Pb: Sr = 5: 1; PbX in sample 2 and sample 3 synthesis ratios2 0.1504mmol, Pb: Sr = 4: 1. Wherein, PbBr in sample 2245% of PbI, and255% by molar mass of (B), PbBr in sample 3250% of PbI, and PbI2The molar mass of (b) is 50%. The method for improving the quantum yield is proved to be stable and effective.
Claims (4)
1. The perovskite quantum dot and mesoporous silica composite luminescent material is characterized in that the chemical formula of the composite luminescent material is CsPb (B)rxI1-x)3:ySr2+@SiO2Wherein x is more than or equal to 0.4 and less than or equal to 1.0, and y is more than or equal to 20 and less than or equal to 50 percent.
2. The perovskite quantum dot and mesoporous silica composite luminescent material as claimed in claim 1, wherein the composition of the perovskite quantum dot is Cs (Pb, Sr) (Br, I)3The type of the mesoporous silica is SBA-15.
3. A preparation method of the perovskite quantum dot and mesoporous silica composite luminescent material as claimed in claim 1, which is characterized by comprising the following steps:
step 1: mixing and stirring 0.102-0.407 g of cesium carbonate, 5-20 mL of 1-octadecene and 0.4-1.3 mL of oleic acid in a nitrogen atmosphere, heating to 120-150 ℃, preserving heat, and completely dissolving the cesium carbonate to obtain a cesium oleate solution;
step 2: respectively taking a perovskite material, mesoporous silica and oleic acid according to the proportion of 0.1504-0.188 mmol of perovskite material needing 0.0565-0.1468 g of mesoporous silica and 0.4-0.6 mL of oleic acid; then taking SrI2Oleylamine and 1-octadecene;
SrI2the molar mass ratio of Sr in the perovskite material to Pb in the perovskite material is 1: 4-5;
the volume ratio of oleic acid to oleylamine to 1-octadecene is 1: 8-13;
the perovskite material comprises 45-50% of PbBr by mol percentage2And 50-55% of PbI2The total amount of each component is 100 percent;
adding mesoporous silicon dioxide, 1-octadecene, oleic acid and oleylamine into a three-neck flask, stirring and heating to 120 ℃ in a nitrogen atmosphere, vacuumizing and stirring, and then adding a perovskite material and SrI2Stirring the mixture in vacuum at 120 ℃ under the protection of nitrogen until the perovskite material and SrI are obtained2Completely dissolving, heating to 180 ℃, and keeping the temperature for 5-10 min to obtain a lead halide precursor;
and step 3: quickly injecting 0.4-0.6 mL of cesium oleate solution into 5.5-6.5 mL of lead halide precursor, reacting for 5-10 s, immediately performing ice-water bath, and waiting for the temperatureCooling to room temperature to obtain the mesoporous silica coated Sr2+Doped CsPb (Br),I)3And centrifuging the crude solution of the quantum dots to obtain a precipitate, completely dissolving the precipitate by n-hexane, standing at room temperature, removing a supernatant, and drying a lower layer in vacuum to obtain the perovskite quantum dot and mesoporous silica composite luminescent material.
4. The preparation method of the perovskite quantum dot and mesoporous silica composite luminescent material as claimed in claim 3, wherein in the step 3, the temperature of the cesium oleate solution is 130-150 ℃; the temperature of the lead halide precursor is 160-180 ℃.
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