CN115948164B - Perovskite quantum dot with coating shell, preparation method of perovskite quantum dot and quantum dot device - Google Patents
Perovskite quantum dot with coating shell, preparation method of perovskite quantum dot and quantum dot device Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 41
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- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000005253 cladding Methods 0.000 claims description 19
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
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- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 12
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- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 5
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 4
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 4
- 229940009827 aluminum acetate Drugs 0.000 claims description 4
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 4
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract 1
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 10
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
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- 239000012296 anti-solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
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- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention belongs to the technical field of perovskite quantum dots, and particularly relates to a perovskite quantum dot with a coating shell, a preparation method thereof and a quantum dot device. In the method, an aluminum source which is strongly combined with halogen is adopted as a ligand to be added into a synthesis step of perovskite quantum dots, and halogen sites on the surfaces of the quantum dots are used for anchoring aluminum-containing ligands; and then the reaction environment is used for changing the reaction environment into a compact alumina shell, and the passivation effect of the ligand and the stable lattice effect are enhanced by utilizing the strong interaction between aluminum and halogen. The aluminum ligand can form an aluminum oxide shell by using a post-treatment means, takes the halogen site on the surface of the quantum dot as an active site, is firmly anchored on the surface of the quantum dot, greatly enhances the interaction between the core and the shell, and plays a double role of stabilizing the crystal lattice of the quantum dot and isolating the external environment; meanwhile, the strong coordination effect of halogen and aluminum on the surface of the perovskite quantum dot can greatly improve the resistance of the perovskite quantum dot to polar environment in the coating process, and greatly reduce the influence on the performance of the quantum dot.
Description
Technical Field
The invention belongs to the technical field of perovskite quantum dots, and particularly relates to a perovskite quantum dot with a coating shell, a preparation method thereof and a quantum dot device.
Background
With the development of technology, quantum dot display technology has become one of the most important components of modern photoelectric products. The popularization and development of photoelectric products are increasingly demanding in various aspects such as material display performance, stability and environmental protection. Compared with the traditional semiconductor quantum dots, the lead-halogen perovskite quantum dots are gradually becoming a powerful competitor in the display field in recent years due to the characteristics of excellent optical properties, lower synthesis cost, environmental friendliness and the like.
However, the current lead halogen perovskite quantum dot material is difficult to maintain good stability under severe conditions such as humidity, oxygen environment, ultraviolet light, thermal atmosphere and the like, and the practical application in the display field is greatly influenced. In this regard, researchers have largely explored to improve the stability of quantum dots. The core-shell structure is considered as one of effective means for improving the stability of the quantum dot, and the quantum dot is isolated from the external environment through the coating layer, so that the weather resistance and the service life of the quantum dot can be greatly improved.
For example, in the prior art, the quantum dot material is coated by mesoporous silica, so that the quantum dot material can be isolated from being in direct contact with the external environment, the environmental tolerance is greatly improved, but a large gap exists between the core shells, the shell material only plays a role in shielding, and cannot play a role in stabilizing crystal lattices; the surface of the quantum dot is passivated through ligand engineering, so that the lattice stability of the quantum dot can be improved, but the ligand is easy to fall off under severe environments such as light, heat, water, oxygen and the like, and the stability is poor; and a post-treatment method is adopted, the crystal lattice is stabilized through the ligand, and then the hydrolysis coating of the shell is carried out, but the hydrolysis process needs to use a polar environment to cause certain irreversible influence on the quantum dot. Such methods, either stabilize the lattice by ligand action or act as a dense shell to isolate the environment, but it is always difficult to achieve uniform bonding of the two.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects in the prior art by a method for improving the stability of quantum dots by constructing a core-shell structure, so as to provide perovskite quantum dots with coating shells, a preparation method thereof and a quantum dot device.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of perovskite quantum dots with coating shells, which comprises the following steps:
s1, preparing perovskite quantum dots by adopting a solution method, and adding aluminum ligands in the preparation process to obtain perovskite quantum dots containing the aluminum ligands;
s2, mixing the obtained product with an aluminum source, carrying out hydrolytic cladding in the presence of hydrogen halide, and separating the product to obtain the perovskite quantum dot with the cladding shell.
Alternatively, the molar ratio of halogen to aluminum ligand in the reaction system of step S1 is M (halogen): m (Al) =1: 0.8 to 2.5, preferably 1:1.2 to 1.5.
Optionally, the aluminum ligand is selected from one or a combination of a plurality of aluminum isopropoxide, aluminum sec-butoxide, aluminum n-butoxide, aluminum tert-butoxide, aluminum triethoxide, trimethylaluminum, tributylaluminum and basic aluminum acetate.
Optionally, in step S2, firstly dispersing perovskite quantum dots containing aluminum ligands into an organic solvent to obtain a quantum dot dispersion liquid, and then mixing with an aluminum source;
the organic solvent used in the present invention is a good solvent for the perovskite quantum dots, and typically, but not limited to, toluene.
Optionally, in step S2, the volume ratio of hydrogen halide to quantum dot dispersion is 1:25 to 600, preferably 1:50;
alternatively, the mass concentration of hydrogen halide is 36-57%.
Optionally, in step S2, the molar ratio of the aluminum source to the hydrogen halide is 1:0.1 to 1, preferably 1:0.2 to 0.4.
Optionally, in step S2, the aluminum source is selected from one or a combination of several of aluminum isopropoxide, aluminum sec-butoxide, aluminum n-butoxide, aluminum tert-butoxide, aluminum triethoxide, trimethylaluminum, tributylaluminum, basic aluminum acetate, aluminum dihydrogen phosphate, and sodium metaaluminate, preferably aluminum isopropoxide.
Optionally, in step S2, the stirring rate of the hydrolytic coating is 60 to 300rpm, preferably 80 to 120rpm;
and/or the stirring time of the hydrolytic coating is 2 to 10 hours, preferably 5 to 7 hours.
Optionally, the composition of the perovskite quantum dots with aluminum ligands obtained in step S1 is: FA (FA) a MA b Cs 1-a- b Pb 1-c-d-e-f Zn c Cd d Cu e Mg f Cl m Br n I 3-m-n Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, a+b is more than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, e is more than or equal to 0 and less than or equal to 1, f is more than or equal to 0 and less than or equal to 1, c+d+e+f is more than or equal to 1, m is more than or equal to 0 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 3, and m+n is more than or equal to 3;
preferably, the composition is FAPbBr 3 、CsPbBr 3 Or CsPbBr 1.2 I 1.8 。
The invention also provides the perovskite quantum dot with the coating shell, which is prepared by the preparation method.
The invention also provides a quantum dot device, which comprises the perovskite quantum dot with the coating shell.
The preparation method of the perovskite quantum dot is a conventional method in the field, wherein the solution method comprises a hot injection method and a room temperature antisolvent method, and is preferably a hot injection method.
The technical scheme of the invention has the following advantages:
according to the preparation method of the perovskite quantum dot with the coating shell, disclosed by the invention, a traditional ligand coordination mode with weak coordination strength is abandoned, the damage of the quantum dot coating process is avoided, an aluminum source which is strongly combined with halogen is adopted as a ligand to be added into the synthesis step of the perovskite quantum dot, and the aluminum-containing ligand is anchored by utilizing halogen sites on the surface of the quantum dot; and then the reaction environment is used for changing the reaction mixture into a compact alumina shell. According to the invention, the aluminum ligand is added into a synthesis system for preparing perovskite quantum dots in advance in a pre-doping mode for the first time, then a hydrolysis environment is provided to enable the pre-input aluminum-containing ligand to gradually generate aluminum oxide, and meanwhile, an aluminum source is additionally input for hydrolysis to increase the shell compactness. And in the quantum dot synthesis stage, an aluminum precursor is put into a ligand form, and the passivation effect of the ligand and the lattice stabilizing effect are enhanced by utilizing the strong interaction between aluminum and halogen. In addition, the aluminum ligand can form an aluminum oxide shell by utilizing a post-treatment means, takes the halogen site on the surface of the quantum dot as an active site, is firmly anchored on the surface of the quantum dot, greatly enhances the interaction between the core and the shell, and plays a double role of stabilizing the crystal lattice of the quantum dot and isolating the external environment; meanwhile, the strong coordination effect of the halogen and the aluminum on the surface of the perovskite quantum dot can greatly improve the resistance to polar environment in the coating process and greatly reduce the influence on the performance of the quantum dot. The hydrogen halide is added in the hydrolysis coating process to provide a halogen-rich protective atmosphere to prevent the quantum dots from generating halogen loss in the hydrolysis process. The cladding shell obtained by the method has the effect of isolating the external environment, and the stability in the harsh environment is greatly improved by utilizing chemical bonding and space limitation through firmly pinning together the halogen-aluminum bonding and the quantum dot crystal lattice. In addition, the method is suitable for various perovskite quantum dot preparation approaches, and has good universality; different aluminum sources can be utilized to customize and regulate the coordination strength, and the coordination strength is good in adjustability; the method is simple and easy to amplify, and is beneficial to industrialized landing. .
The perovskite quantum dot with the coating shell, which is prepared by the method, is internally provided with a perovskite quantum dot core, the surface of the perovskite quantum dot is provided with an alumina shell, the core shells are firmly pinned together with the quantum dot lattice through halogen-aluminum bonding, the bonding strength is stronger than that of a conventional ligand, and the problem of lattice coarsening caused by ligand falling can be avoided, so that the double functions of passivation defects, lattice stabilization and environment isolation are exerted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a process for preparing perovskite quantum dots having a cladding shell according to one embodiment of the invention;
FIG. 2 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example one of the invention;
FIG. 3 is the results of aging and stability testing of perovskite quantum dots with a cladding shell in example two of the invention;
FIG. 4 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example three of the invention;
FIG. 5 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example four of the invention;
FIG. 6 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example five of the invention;
FIG. 7 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example six of the invention;
FIG. 8 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example seven of the invention;
FIG. 9 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example eight of the invention;
FIG. 10 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example nine of the invention;
FIG. 11 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example ten of the invention;
FIG. 12 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example eleven of the invention;
FIG. 13 is the results of aging and stability testing of perovskite quantum dots with cladding shells in example twelve of the invention;
FIG. 14 is the results of aging and stability testing of perovskite quantum dots in comparative example one of the invention;
FIG. 15 is the results of aging and stability testing of perovskite quantum dots in comparative example II of the invention;
fig. 16 is the results of aging and stability testing of perovskite quantum dots in comparative example three of the invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of perovskite quantum dots with coating shells, which comprises the following specific steps and parameters:
(1) 0.4g cesium carbonate was added to a mixture of 1.5ml oleic acid and 15ml octadecene, evacuated and heated to 120℃and stabilized for 60 min.
(2) Adding 0.138g of lead bromide, 0.1g of aluminum isopropoxide and 1.5ml of oleic acid into 10ml of octadecene, vacuumizing and heating to 120 ℃, stabilizing for 30min, and introducing N 2 And heated to 170 ℃.
(3) 1ml of the solution obtained in the step (1) was poured into the step (2), and after the reaction for 5 seconds, it was cooled to room temperature with an ice-water bath.
(4) After the reaction, the crude solution was centrifuged at 8000rpm for 5 minutes, the precipitate was dispersed with a mixture of 10ml of ethyl acetate and 5ml of toluene, centrifuged again at 3000rpm for 5 minutes, and the precipitate was dispersed with 5ml of toluene for use.
(5) To the toluene dispersion obtained in the step (4) were added 100. Mu.l hydrobromic acid (mass concentration: 48%, the same applies hereinafter) and 0.05g aluminum isopropoxide, stirred at 100rpm for 6 hours, centrifuged at 5000rpm for 3 minutes, and the precipitate was taken and redispersed in 5ml toluene.
Example two
The embodiment provides a preparation method of perovskite quantum dots with coating shells, which comprises the following specific steps and parameters:
(1) After 0.085g cesium bromide, 0.1468g lead bromide, 0.1g aluminum isopropoxide and 1.5ml oleic acid were dissolved in 10ml DMF solution and mixed uniformly, the mixture was added to 50ml toluene solution, and the precipitate was separated by centrifugation and re-dispersed with 5ml toluene.
(2) To the toluene dispersion obtained in (1) were added 100. Mu.l hydrobromic acid and 0.05g of aluminum isopropoxide, stirred at 100rpm for 6 hours, centrifuged at 5000rpm for 3 minutes, and the precipitate was taken and redispersed in 5ml toluene.
Example III
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in step (2) 0.138g of lead bromide was changed to 0.092g of lead bromide and 0.0624g of potassium iodide.
Example IV
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in step (2) 0.1g of aluminum isopropoxide was replaced with aluminum sec-butoxide.
Example five
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in step (5) 100. Mu.l hydrobromic acid was changed to 10. Mu.l hydrobromic acid.
Example six
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in step (5) 100. Mu.l hydrobromic acid was changed to 200. Mu.l hydrobromic acid.
Example seven
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in the step (5), 0.05g of aluminum isopropoxide is changed into 0.0175g of aluminum isopropoxide.
Example eight
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in the step (5), 0.05g of aluminum isopropoxide is changed into 0.1754g of aluminum isopropoxide.
Example nine
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in the step (5), stirring at 100rpm is changed to 60rpm for 6 hours.
Examples ten
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in the step (5), stirring at 100rpm is changed to 300rpm for 6 hours.
Example eleven
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in the step (5), stirring at 100rpm is carried out for 6 hours, and stirring at 100rpm is carried out for 2 hours.
Example twelve
This example provides a method for preparing perovskite quantum dots with coating shells, which differs from example 1 only in that: in the step (5), stirring at 100rpm is carried out for 6 hours, and stirring at 100rpm is carried out for 10 hours.
Comparative example one
This comparative example provides a method of preparing perovskite quantum dots with a coating shell, differing from example 1 only in that: in step (2) 0.1g of aluminum isopropoxide was replaced with 1.5ml of oleylamine.
Comparative example two
This comparative example provides a method of preparing perovskite quantum dots with a coating shell, differing from example 1 only in that: in step (5), only 100. Mu.l hydrobromic acid was added, and aluminum isopropoxide was not added.
Comparative example three
This comparative example provides a method of preparing perovskite quantum dots with a coating shell, differing from example 1 only in that: in step (5), 100. Mu.l hydrobromic acid was not added, and only aluminum isopropoxide was added.
Aging and stability test
The quantum dot dispersion liquid prepared in each example and comparative example and the film-forming glue are mixed according to the mass ratio of 1:10, and a water-oxygen barrier film (10 -2 ) After packaging, the film is solidified by ultraviolet light and cut into 50 multiplied by 50cm films to be measured.
Dry heat aging (HT): placing the sample membrane in an oven at 85 ℃ for aging;
blue light aging (BL): placing the sample membrane under a 705nits and 450nm LED light source for aging;
standing at room temperature (CW): aging the sample membrane at normal temperature and normal pressure;
after aging for different time, corresponding samples are taken, cooled to normal temperature and normal pressure, and the sample membrane is subjected to aging and stability test by a fluorescence tester, and the results are shown in figures 2-16, and can be seen from the figures:
the data results of examples 1-12 show that the prepared perovskite quantum dots with the coating shells have better stability, and the invention is effective on quantum dots prepared by a thermal injection method (example 1) and an antisolvent method (example 2), is effective on perovskite quantum dots with different components and is applicable to different aluminum ligands.
As can be seen from comparison of the data results of example 1 and comparative example 1, the surface ligand fails to fall off due to the strong interaction between halogen and aluminum when the aluminum source is added, and the luminescence and stability of the quantum dot are seriously affected, without adding the aluminum ligand in advance, only using the conventional amine ligand.
As can be seen from comparison of the data results of example 1 and comparative example 2, only coating is performed by the hydrolysis process of aluminum ligand, no additional aluminum source is added, and dense coating cannot be performed due to limited aluminum ligand content, and a large number of exposed surfaces of quantum dots still exist, so that stability is seriously affected.
As can be seen from comparison of the data results of example 1 and comparative example 3, the hydrolysis process was very slow if no hydrogen halide was added to provide an acidic environment, and even if an additional aluminum source was added, it was difficult to form a dense coating, and still the stability could not be improved.
Comparison of the data in examples 1 and 5 and 6 shows that hydrobromic acid is added too little, the hydrolysis process is incomplete, the coating shell is not compact enough, and the stability is affected to a certain extent; and too much water molecules in hydrobromic acid can corrode the crystal lattice, gradually weakening the luminescence property and affecting the stability.
Comparison of the data results of example 1 and examples 7 and 8 shows that the post-treatment hydrolysis coating process has too little aluminum source, the coating is not compact, and the stability is affected to a certain extent; and too much light is added, although the coating is denser and the stability is better, the thicker wall thickness can block light, and the light emission of the quantum dots is affected.
Comparison of the data results of examples 1 and 9 and 10 shows that the slower stirring rate of the post-treatment hydrolysis coating process may affect coating uniformity and affect quantum dot luminescence; and the stirring speed is too high, and the ligand on the surface of the quantum dot can be influenced before coating is completed, so that the stability is poor.
Comparison of the data results of example 1 and examples 11 and 12 shows that the post-treatment hydrolysis coating process has shorter reaction time, the coating is not compact, and the stability is affected to a certain extent; and the reaction is too long, although the coating is denser and the stability is better, the thicker wall thickness can block light, and the light emission of the quantum dots is affected.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the perovskite quantum dot with the coating shell is characterized by comprising the following steps of:
s1, preparing perovskite quantum dots by adopting a solution method, and adding aluminum ligands in the preparation process to obtain perovskite quantum dots containing the aluminum ligands;
s2, mixing the obtained product with an aluminum source, carrying out hydrolytic cladding in the presence of hydrogen halide, and separating the product to obtain perovskite quantum dots with cladding shells;
the aluminum ligand is selected from one or a combination of a plurality of aluminum isopropoxide, aluminum sec-butoxide, aluminum n-butoxide, aluminum tert-butoxide, aluminum triethoxide, trimethylaluminum, tributylaluminum and basic aluminum acetate;
the aluminum source is selected from one or more of aluminum isopropoxide, aluminum sec-butoxide, aluminum n-butoxide, aluminum tert-butoxide, aluminum triethoxide, trimethylaluminum, tributylaluminum, basic aluminum acetate, aluminum dihydrogen phosphate and sodium metaaluminate.
2. The method for preparing perovskite quantum dots with coating shells according to claim 1, wherein the composition of the perovskite quantum dots with aluminum ligands obtained in the step S1 is: FA (FA) a MA b Cs 1-a-b Pb 1-c-d-e- f Zn c Cd d Cu e Mg f Cl m Br n I 3-m-n Wherein 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.1, a+b.ltoreq.1, 0.ltoreq.c.ltoreq.1, 0.ltoreq.d.ltoreq.1, 0.ltoreq.e.ltoreq.1, 0.ltoreq.f.ltoreq.1, c+d+e+f.ltoreq.1, 0.ltoreq.m.ltoreq.3, 0.ltoreq.n.ltoreq.3, m+n.ltoreq.3, the molar ratio of halogen to aluminum ligand in the reaction system of step S1 is M (halogen): m (Al) =1: 0.8 to 2.5.
3. The method for preparing perovskite quantum dot with coating shell according to claim 2, wherein the molar ratio of halogen to aluminum ligand in the reaction system of step S1 is M (halogen): m (Al) =1: 1.2 to 1.5.
4. A method for preparing a perovskite quantum dot having a coating shell according to any one of claims 1 to 3, wherein in step S2, perovskite quantum dots containing aluminum ligands are dispersed in an organic solvent to obtain a quantum dot dispersion, and then mixed with an aluminum source.
5. The method of claim 4, wherein in step S2, the volume ratio of hydrogen halide to quantum dot dispersion is 1:25 to 600;
and/or the mass concentration of hydrogen halide is 36-57%;
and/or, in step S2, adding a molar ratio of the aluminum source to the hydrogen halide of 1:0.1 to 1.
6. The method of claim 5, wherein in step S2, the volume ratio of hydrogen halide to quantum dot dispersion is 1:50;
and/or adding an aluminum source and hydrogen halide in a molar ratio of 1:0.2-0.4;
and/or the aluminum source is aluminum isopropoxide.
7. The method for preparing perovskite quantum dots with coating shell according to any one of claims 1-3 or 5-6, wherein in step S2, the stirring rate of hydrolytic coating is 60-300 rpm;
and/or the stirring time of the hydrolytic coating is 2 to 10 hours, preferably 5 to 7 hours.
8. The method for preparing perovskite quantum dots with coating shell according to claim 7, wherein in step S2, the stirring rate of hydrolytic coating is 80-120 rpm;
and/or the composition of the perovskite quantum dot with the aluminum ligand obtained in the step S1 is FAPbBr 3 、CsPbBr 3 Or CsPbBr 1.2 I 1.8 。
9. A perovskite quantum dot with a coated shell prepared by the preparation method according to any one of claims 1 to 8.
10. A quantum dot device comprising the perovskite quantum dot with cladding shell of claim 9.
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