CN115725296B - Quantum dot powder with coating connected to surface of quantum dot, preparation method of quantum dot powder and optical element comprising quantum dot powder - Google Patents
Quantum dot powder with coating connected to surface of quantum dot, preparation method of quantum dot powder and optical element comprising quantum dot powder Download PDFInfo
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- CN115725296B CN115725296B CN202111020758.8A CN202111020758A CN115725296B CN 115725296 B CN115725296 B CN 115725296B CN 202111020758 A CN202111020758 A CN 202111020758A CN 115725296 B CN115725296 B CN 115725296B
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 213
- 239000000843 powder Substances 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 78
- 238000000576 coating method Methods 0.000 title claims abstract description 78
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 silane compound Chemical class 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
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- 229910000077 silane Inorganic materials 0.000 claims description 13
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- 125000005647 linker group Chemical group 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
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- HBFCKUCCFLNUHJ-UHFFFAOYSA-N 3-dimethoxysilylpropane-1-thiol Chemical compound CO[SiH](OC)CCCS HBFCKUCCFLNUHJ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
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- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 4
- 229940009827 aluminum acetate Drugs 0.000 claims description 4
- 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 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
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- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- ICPMTQOYWXXMIG-OPDGVEILSA-K aluminum;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Al+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O ICPMTQOYWXXMIG-OPDGVEILSA-K 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
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- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 19
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 19
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
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- 230000005540 biological transmission Effects 0.000 description 5
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical group S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 5
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application provides a quantum dot powder with a coating connected to the surface of a quantum dot, a preparation method thereof and an optical element comprising the quantum dot powder, wherein the quantum dot powder with the coating connected to the surface of the quantum dot comprises a quantum dot body, a connecting group and the coating, and the coating is connected with the quantum dot body through the connecting group; wherein the coating is coated on the surface of the quantum dot body, and the coating contains a silicon-oxygen-aluminum bond; the quantum dot powder disclosed by the application has the advantages of good stability, simple preparation method, strong environmental tolerance of an optical element prepared from the quantum dot powder and excellent optical performance.
Description
Technical Field
The application belongs to the field of nano materials, and particularly relates to quantum dot powder with a coating connected to the surface of a quantum dot, a preparation method of the quantum dot powder and an optical element comprising the quantum dot powder.
Background
The quantum dots (also called semiconductor nanocrystals) are novel semiconductor nanomaterials with the size of 1-10nm. They have unique Photoluminescence (PL) and Electroluminescent (EL) properties due to quantum size effects and dielectric confinement effects. Compared with the traditional organic fluorescent dye, the quantum dot has the excellent optical characteristics of high quantum efficiency, high photochemical stability, difficult photolysis, wide excitation, narrow emission, high color purity, adjustable luminescence color by controlling the size of the quantum dot and the like, and has wide application prospect in the technical field of display.
Currently, to maintain good optical properties of quantum dots, the quantum dots synthesized in the prior art are generally dispersed in a liquid phase, but this also limits the application of quantum dots; meanwhile, the quantum dots in the liquid phase have certain limitations in terms of preservation and transportation; in addition, after the quantum dots in the liquid phase lose the protection of the solvent in the actual use process, the quantum dots are easy to react with oxygen, water vapor and the like in the environment, and the problems of ligand falling, oxidization, easy agglomeration and the like are generated, so that the dispersibility and the stability of the quantum dots are reduced.
Therefore, developing solid quantum dot powder with high luminous efficiency and a preparation method thereof have important significance for expanding the application range of the quantum dot.
Disclosure of Invention
Aiming at the technical problems, the application provides quantum dot powder with a coating connected to the surface of a quantum dot, which comprises a quantum dot body, a connecting group and the coating, wherein the coating is connected with the quantum dot body through the connecting group;
Wherein the coating is coated on the surface of the quantum dot body, and the coating contains a silicon-oxygen-aluminum bond.
Further, the linking group comprises one of mercapto, amino, carboxyl and phosphino.
Further, the linking group is directly linked to the silicon atom in the coating by a chemical bond.
Further, the mass percentage of the coating in the quantum dot powder is 50-90%.
Further, the molar ratio of the silicon element to the aluminum element in the coating is 0.1-3.
The application also provides a preparation method of the quantum dot powder with the surface connected with the coating, which comprises the following steps:
s1, mixing initial quantum dots, an organic solvent and a silane compound containing a connecting group, and reacting to form a first system;
S2, adding an organic aluminum and/or aluminum salt solution into the first system, and reacting to form a second system;
s3, removing the solvent of the second system to form quantum dot powder with a coating connected to the surface, wherein the quantum dot comprises a quantum dot body and a coating connected with the quantum dot body through the connecting group, and the coating comprises a silicon-oxygen-aluminum bond.
Further, in the step S1, the molar ratio of the initial quantum dot to the silane compound including a linking group is 1 (1-10).
Further, in the step S1, the reaction temperature is 80-120 ℃; in the step S2, the reaction temperature is 100-150 ℃.
Further, the molar ratio of the silane compound containing a linking group to the organoaluminum and/or aluminum salt is 0.1 to 3.
The application also provides an optical element, which comprises the quantum dot powder with the surface connected with the coating, or comprises the quantum dot powder prepared by the preparation method.
The beneficial effects are that:
(1) The quantum dot powder with the surface connected with the coating comprises a quantum dot body and the coating connected to the quantum dot body through the connecting group, wherein the coating is coated on the surface of the quantum dot body, and the coating contains silicon-oxygen-aluminum bonds, so that silicon atoms on the coating are firmly connected with the quantum dot body through the connecting group, the coating is firmly connected to the surface of the quantum dot body, the coating effectively blocks the influence of water, oxygen and heat in the environment on the quantum dot body, and the stability of the quantum dot powder is obviously enhanced.
(2) According to the preparation method of the quantum dot powder, the silane compound containing the connecting group, the organic aluminum and/or the aluminum salt are sequentially added into the initial quantum dot to react to form the quantum dot powder with high stability, the process is simple, the preparation method is environment-friendly, and good economic benefit and social benefit are achieved.
Drawings
FIG. 1 is a diagram showing the morphology of a transmission electron microscope of the quantum dot powder of example 1 of the present application;
FIG. 2 is a diagram showing the analysis of cadmium element by a transmission electron microscope of the quantum dot powder of example 1 of the present application;
FIG. 3 is a diagram showing the elemental analysis of a transmission electron microscope for a quantum dot powder according to example 1 of the present application;
Fig. 4 is a transmission electron microscope aluminum element analysis chart of the quantum dot powder of example 1 of the present application.
Detailed Description
The technical solutions in the examples of the present application will be described in detail below in connection with the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the application, and not all embodiments. Unless otherwise defined, all terms (including technical and scientific terms) in the specification can be defined as commonly understood by one of ordinary skill in the art. Unless clearly defined otherwise, terms defined in a general dictionary may not be interpreted ideally or exaggeratedly. Furthermore, unless explicitly described to the contrary, the word "comprise" and variations such as "comprises" or "comprising" will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.
In the drawings, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. Like numbers refer to like elements throughout.
It will be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
Furthermore, the singular includes the plural unless otherwise mentioned. As used herein, at least one of "a," "an," "the," and "… …" do not denote a limitation of quantity, but rather are intended to include both singular and plural, unless the context clearly indicates otherwise. For example, unless the context clearly indicates otherwise, "an element (element)" has the same meaning as "at least one element (element)". The "at least one" is not to be construed as limiting the "one" or the "one". "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms "comprises" and/or "comprising," or variations thereof, when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
As described in the background art, in the current process of using the quantum dot in the liquid phase, after losing the protection of the solvent, the quantum dot is easily affected by oxygen, water vapor, high temperature and the like in the environment, and the problems of ligand falling, oxidization, easy agglomeration and the like are generated, so that the stability of the quantum dot is reduced.
Based on the above, the application provides a quantum dot powder with a coating connected to the surface of a quantum dot, which comprises a quantum dot body, a connecting group and the coating, wherein the coating is connected with the quantum dot body through the connecting group, the coating is coated on the surface of the quantum dot body, and the coating contains silicon-oxygen-aluminum bonds. The inventor finds that the quantum dot body is connected with the coating through the connecting group, the coating is coated on the surface of the quantum dot body, one end of the connecting group is stably coordinated and connected with the surface of the quantum dot body, and the other end of the connecting group is connected with silicon atoms in the coating, so that the coating containing silicon-oxygen-aluminum chemical bonds is not easy to fall off from the surface of the quantum dot body, the quantum dot body is effectively protected from the influence of external environment, and the stability of the quantum dot powder is obviously improved.
In one embodiment of the application, the linking group comprises one of mercapto, amino, carboxyl and phosphine groups, and can be stably connected to the surface of the quantum dot body, and the linking group is preferably mercapto, so that the connection with the surface of the quantum dot is more stable.
In the preferred embodiment, the connecting group is directly connected with silicon through a chemical bond, the silicon element is closer to the quantum dot body than the aluminum element, the bond energy of the silicon element is large, a network structure is formed between the silicon element, the oxygen element and the aluminum element, and the aluminum element is arranged on one side of the silicon away from the connecting group, so that water and oxygen can be effectively insulated, and the stability of the quantum dot powder is obviously improved.
In another specific embodiment of the application, the mass percentage of the coating in the quantum dot powder is 50-90%, so that the coating thickness of the coating formed on the surface of the quantum dot body is proper, and the stability of the quantum dot powder is further improved while the optical performance of the quantum dot powder is not influenced.
In still another specific embodiment of the application, the molar ratio of the silicon element to the aluminum element in the coating is 0.1-3, and the proper molar ratio of the two elements can make the structure of the coating more stable, thereby effectively blocking the influence of the external environment on the optical performance of the quantum dot powder.
The application also provides a preparation method of the quantum dot powder with the surface connected with the coating, which comprises the following steps:
s1, mixing initial quantum dots, an organic solvent and a silane compound containing a connecting group, and reacting to form a first system;
S2, adding an organic aluminum and/or aluminum salt solution into the first system, and reacting to form a second system;
S3, removing the solvent of the second system to form quantum dots with the surfaces connected with the coating, wherein the quantum dots comprise quantum dot bodies and the coating connected with the quantum dot bodies through connecting groups, and the coating comprises silicon-oxygen-aluminum bonds.
In the preparation method of the quantum dot powder, a silicon precursor containing a connecting group is added to react with an initial quantum dot, so that the surface of the initial quantum dot is connected with the connecting group and the silicon oxygen group to form a first system; then adding organic aluminum and/or aluminum salt into the first system to react, so that the organic aluminum group reacts with the silicon oxygen group to form connection, and a second system is formed; removing the organic solvent in the second system to form quantum dot powder with the initial quantum dot surface connected with the coating, namely adding silane compound containing a connecting group to be connected with the initial quantum dot first to improve the surface defect of the initial quantum dot, and then adding organic aluminum and/or aluminum salt to react with a silicon oxygen group to form the coating to coat the surface of the quantum dot body. The obtained quantum dot powder can effectively cope with various harsh use environments, and effectively avoids the influence of water vapor, oxygen, heat and the like in the environment, so that the quantum dot powder can be placed in the environment for a long time without the influence of the optical performance.
The initial quantum dots of the present application may be prepared by any known method or may be commercially available. The initial quantum dots include group II-VI compounds, group III-V compounds, group IV-VI compounds, group I-III-VI compounds, group I-II-IV-VI compounds, perovskite compounds, carbon quantum dots, or combinations thereof. The initial quantum dot may further be a core-shell structure, e.g., the initial quantum dot may include a core of a nanocrystal and a shell disposed on at least a portion of a surface of the nanocrystal and including a composition different from the core of the nanocrystal. An alloyed intermediate layer may or may not be present at the interface between the core and the shell. The alloyed layer may comprise a homogeneous alloy. In addition, the shell may include a multi-layered shell having at least two layers, wherein adjacent layers have compositions different from each other. In the multi-layer shell, each layer may have a single composition. In the multi-layer shell, the layers may have an alloy. In the multi-layer shell, each layer may have a concentration gradient that varies in a radial direction according to the composition of the nanocrystals. In addition, the particle size of the initial quantum dot may have a size of about 1nm to about 100 nm. For example, the initial quantum dots may have a particle size of about 1nm to about 50nm, e.g., from 2nm to 20 nm. The shape of the initial quantum dot is a shape generally used in the art, and is not particularly limited.
It is understood that the structure of the quantum dot body of the present application is derived from the original quantum dot, for example, the structure of the quantum dot body of the present application is a core structure or a core-shell structure of the original quantum dot. The organic solvent is selected from, but not limited to, n-heptane, n-hexane, cyclohexane, as long as the organic solvent capable of dispersing the initial quantum dot with the mercaptosilane compound, organoaluminum and/or aluminum salt falls within the scope of the present application.
The silane compound containing a linking group of the present application may be at least one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl dimethoxysilane, 3-mercaptopropyl diethoxysilane, 3-aminopropyl triethoxysilane, and 3-aminopropyl trimethoxysilane.
The organic aluminum alkoxides of the application comprise at least one of aluminum isopropoxide, aluminum sec-butoxide, tripropylaluminum, triethylaluminum, basic aluminum acetate, aluminum gluconate, aluminum tartrate and aluminum acetylacetonate, and the aluminum salt comprises at least one of aluminum chloride, aluminum sulfate and aluminum nitrate.
In step S3 of the present application, the method for removing the solvent of the second system includes, but is not limited to, at least one of sintering, vacuum drying, and drying. The initial state of the quantum dot powder obtained after drying is a solid block, and in order to facilitate the use and storage of the quantum dot powder, a grinding device and the like can be adopted to further crush the solid block so as to obtain the quantum dot powder with the size of micron level. In the drying process, the structure of the quantum dot powder is not damaged in the heat treatment process, and the quantum dot powder can maintain good optical performance.
In a specific preparation method of the application, in S1 of the preparation method of the quantum dot, the molar ratio of the initial quantum dot to the mercaptosilane compound is 1 (1-10), so that a proper amount of mercaptosilane groups are connected to the quantum dot, and the subsequent mercaptosilane groups can be better connected with the organic aluminum groups.
In another specific preparation method of the application, in the step S1, the reaction temperature is 80-120 ℃, in the step S2, the reaction temperature is 100-150 ℃, so that the reaction of the connection coating on the initial quantum dot is more sufficient, the mercapto silane compound can effectively participate in the reaction and is not decomposed, a network structure with higher stability is obtained by crosslinking on the quantum dot body, the added organic aluminum and siloxane groups are thermally cracked to release micromolecular alcohols, and the mercapto silane is connected with an aluminum oxide chemical bond, thereby forming quantum dot powder with the connection coating coated on the surface of the quantum dot, and further improving the luminescence stability of the quantum dot powder in a quantum dot film.
In a preferred embodiment, the reaction time of the step S1 is 60-180 min, so that the compactness of the network structure of the mercaptosilane compound connected to the quantum dot body is better; the reaction time of the step S2 is 120-360 min, so that the mercaptosilane organic aluminum and/or aluminum salt connected to the quantum dot body has better coating property and stronger compactness, the preparation efficiency of the quantum dot is effectively improved, and the reaction is ensured to be fully carried out.
In the further specific preparation method, the molar ratio of the mercaptosilane compound to the organic aluminum and/or the aluminum salt is 0.1-3, so that the mercaptosilane organic aluminum and/or the aluminum salt connected to the quantum dot body has better connectivity to the quantum dot, and meanwhile, the quantum dot powder has better compactness, and the quantum dot powder is effectively prevented from being affected by water and oxygen.
In yet another embodiment of the present application, in steps S1 and/or S2, the reaction is carried out in an aqueous and/or oxygen environment to promote the formation of silicon-oxygen-aluminum bonds in the coating; in the preferred embodiment, the environment is air atmosphere, so that the requirements of the preparation of the quantum dots on reaction conditions are effectively reduced, and the production cost is reduced.
The application also provides an optical element, which comprises the quantum dot powder with good stability or the quantum dot powder prepared by the method, and the quantum dot powder with high stability can ensure that the optical performance of the optical element is more excellent and the service life is longer. The optical element comprises but is not limited to at least one of a quantum dot light conversion film, a quantum dot electroluminescent device and a quantum dot display device, wherein the optical element is preferably the quantum dot light conversion film, a coextrusion technology is preferably adopted when the quantum dot light conversion film is prepared, an organic high polymer is selected as a matrix material, the organic high polymer is at least one of polystyrene, polymethyl methacrylate, polypropylene, polyethylene terephthalate, polycarbonate, polyimide and polyvinyl chloride, the coextrusion melting temperature is 180-240 ℃, and the stability of the quantum dot light conversion film prepared by the coextrusion technology is obviously improved.
Quantum dot compositions, display devices according to some exemplary embodiments of the application are described in more detail below; however, the exemplary embodiments of the present application are not limited thereto.
Example 1
200Mg of green CdSe quantum dots dispersed by heptane are taken, 1mmol of 3-mercaptopropyl (dimethoxy) monosilane is added into the green CdSe quantum dots, the mixture is stirred in the air for 3 hours at normal temperature, then the temperature is raised to 80 ℃, the heat is preserved for 3 hours, and a clear first system is formed after cooling; adding 10mmol of aluminum isopropoxide dispersed by toluene into the first system, and stirring for 1h at normal temperature to form a second system; drying the second system to obtain CdSe quantum dot powder with surface coated with silicon aluminum oxide, wherein the morphology of the quantum dot powder is as shown in figure 1, and the dark quantum dots are uniformly dispersed in the slightly light-colored coating; the distribution of cadmium elements in the silicon aluminum oxide is shown in figure 2, and the bright color is cadmium elements which are uniformly distributed; the silicon element distribution condition in the silicon aluminum oxide is shown in figure 3, and the silicon element is uniformly distributed at the bright color part; the distribution of aluminum element in the silicon aluminum oxide is shown in figure 4, and the bright color part is aluminum element, and the distribution is uniform; therefore, the transmission electron microscope image shows that the quantum dots are uniformly distributed in the coating, and the aluminum element and the silicon element in the coating are uniformly dispersed, so that a good coating connection effect is formed on the quantum dots.
Example 2
Taking 2g of green CdSe quantum dots dispersed by heptane, adding 20mmol of 3-mercaptopropyl (dimethoxy) monosilane into the quantum dots, and stirring the mixture for 3 hours at 90 ℃ in air; adding 100mmol of aluminum isopropoxide hydrolyzed sol (Al (OH) 3), heating and stirring at 100 ℃ for 3h to form a second system; and drying the second system to obtain the quantum dot powder with the CdSe surface coated and connected with the silicon aluminum oxide.
Example 3
Taking 2g of green CdSe quantum dots dispersed by heptane, adding 20mmol of 3-mercaptopropyl (diethoxy) disilane into the green CdSe quantum dots, and stirring the mixture for 3 hours at 100 ℃ in air; adding 120mmol of aluminum isopropoxide dispersed by toluene, heating and stirring for 3 hours at 120 ℃ to form a second system; and drying the second system to obtain the quantum dot powder with the CdSe surface coated and connected with the silicon aluminum oxide.
Example 4
Taking 2g of green CdSe quantum dots dispersed by heptane, adding 20mmol of 3-aminopropyl triethoxysilane into the quantum dots, and stirring the mixture for 2 hours at 100 ℃ in air; adding 150mmol of aluminum sec-butoxide dispersed by toluene, heating and stirring for 3 hours at 120 ℃ to form a second system; and drying the second system to obtain the quantum dot powder with the CdSe surface coated and connected with the silicon aluminum oxide.
Example 5
Taking 2g of red light CdSe quantum dots dispersed by heptane, adding 20mmol of 3-mercaptopropyl (dimethoxy) monosilane into the red light CdSe quantum dots, and stirring the mixture for 2 hours at 100 ℃ in air; adding 100mmol basic aluminum acetate, heating and stirring at 120 ℃ for 3h to form a second system; and drying the second system to obtain the quantum dot powder with the CdSe surface coated and connected with the silicon aluminum oxide.
Example 6
2G of green CsPbBr 3 quantum dots dispersed in heptane are taken, 20mmol of 3-mercaptopropyl (diethoxy) disilane is added into the quantum dots, and the mixture is stirred for 3 hours at 80 ℃ in air; adding 120mmol of aluminum isopropoxide dispersed by toluene, heating and stirring for 3 hours at 120 ℃ to form a second system; and drying the second system to obtain the quantum dot powder with the CsPbBr 3 surface coated and connected with the silicon aluminum oxide.
Comparative example 1
18Mg of green CdSe quantum dots and 350mg of silicon dioxide aerogel are taken and dispersed in 20mL of heptane, and ultrasonic treatment is carried out for 3min. Stirring the magneton at normal temperature until no solvent exists, washing and centrifuging for many times until no obvious green light exists on the upper layer, and drying to obtain dry quantum dot powder.
Comparative example 2
180Mg of green CdSe quantum dots and 1.6g of nano alumina are taken and dispersed in 50mL of heptane, and ultrasonic treatment is carried out for 3min. Stirring the magneton at normal temperature until no solvent exists, washing and centrifuging for many times until no obvious fluorescence exists on the upper layer, and obtaining the dry quantum dot powder.
Comparative example 3
300Mg of green CdSe quantum dots and 3mmol of tetramethyl orthosilicate are taken and stirred in air at 80 ℃ for 3 hours; adding 18mmol of aluminum isopropoxide dispersed by toluene, mixing, heating and stirring for 3 hours at 120 ℃ to form a second system; and drying the second system to obtain the quantum dot powder with the CdSe surface coated and connected with the silicon aluminum oxide.
Comparative example 4
200Mg of green CdSe quantum dot is taken and mixed with 2mmol of bis (sec-butanol) triethyl aluminum orthosilicate DBATES, and the mixture is stirred at normal temperature for overnight to obtain quantum dot powder.
Mixing original QDs (green CdSe quantum dots) and 800mg quantum dot powder in examples 1-6 and comparative examples 1-4 with 20g polymethyl methacrylate respectively, preparing a quantum dot film by coextrusion in an extruder in a stepwise temperature rising mode at 185-200 ℃, and testing ageing data of the quantum dot film under two ageing conditions respectively, wherein the first ageing condition is that blue light irradiation at 447nm of 880W/m 2 is adopted under an environment with the temperature of 60 ℃ and the humidity of 90%, and the test results are shown in table 1; the second aging condition was blue light irradiation of 447nm at 8500W/m 2 at 70℃and the test results are shown in Table 2, with respect to the color coordinates, green light mainly seen the y-coordinate change and red light mainly seen the x-coordinate change.
Table 1 data for quantum dot films under first aging conditions
Table 2 data for quantum dot films under second aging conditions
As can be seen from tables 1 to 2, compared with the quantum dot films prepared by the original quantum dots and comparative examples 1 to 4, the quantum dot films prepared by the examples 1 to 6 of the present application have the advantages of strong aging resistance, small color coordinate shift, and high brightness and EQE maintenance rate, which indicates that the quantum dot powder prepared by the technical scheme of the present application has good stability, so that the quantum dot film prepared by the present application has high stability, and is favorable for promoting the commercialized application of the optical element comprising the quantum dots.
While the present application has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit of the application and that the terms used herein are intended to be illustrative and understanding of the application and not to be construed as limiting the application.
Claims (10)
1. The quantum dot powder is characterized by comprising a quantum dot body, a connecting group and a coating, wherein the coating is connected with the quantum dot body through the connecting group;
Wherein the coating is coated on the surface of the quantum dot body, and the coating contains a silicon-oxygen-aluminum bond; the silane compound containing a connecting group is added to react with the initial quantum dot, so that the connecting group and the silicon oxide group are connected to the surface of the initial quantum dot to form a first system; then adding organic aluminum and/or aluminum salt into the first system to react, so that the organic aluminum group reacts with the silicon oxygen group to form connection, and a second system is formed; removing the organic solvent in the second system to form quantum dot powder with the initial quantum dot surface connected with the coating; the silane compound comprising a linking group comprises: at least one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl dimethoxy silane, 3-mercaptopropyl diethoxy disilane, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane; the organoaluminum comprises: at least one of aluminum isopropoxide, aluminum sec-butoxide, tripropylaluminum, triethylaluminum, basic aluminum acetate, aluminum gluconate, aluminum tartrate and aluminum acetylacetonate, wherein the aluminum salt comprises: at least one of aluminum chloride, aluminum sulfate and aluminum nitrate.
2. The quantum dot powder with a coating attached to the surface of the quantum dot according to claim 1, wherein the linking group comprises one of a thiol group, an amino group, a carboxyl group, and a phosphine group.
3. The quantum dot powder with a coating attached to a surface of the quantum dot according to claim 1, wherein the linking group is directly attached to a silicon atom in the coating by a chemical bond.
4. The quantum dot powder with the coating connected to the surface of the quantum dot according to claim 1, wherein the mass percentage of the coating in the quantum dot powder is 50-90%.
5. The quantum dot powder with the coating connected to the surface of the quantum dot according to claim 1, wherein the molar ratio of silicon element to aluminum element in the coating is 0.1-3.
6. The preparation method of the quantum dot powder with the coating connected to the surface of the quantum dot is characterized by comprising the following steps:
s1, mixing initial quantum dots, a solvent and a silane compound containing a connecting group, and reacting to form a first system; the silane compound comprising a linking group comprises: at least one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl dimethoxy silane, 3-mercaptopropyl diethoxy disilane, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane;
S2, adding an organic aluminum and/or aluminum salt solution into the first system, and reacting to form a second system; the organoaluminum comprises: at least one of aluminum isopropoxide, aluminum sec-butoxide, tripropylaluminum, triethylaluminum, basic aluminum acetate, aluminum gluconate, aluminum tartrate and aluminum acetylacetonate, wherein the aluminum salt comprises: at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate;
s3, removing the solvent of the second system to form quantum dot powder with a coating connected to the surface, wherein the quantum dot powder comprises a quantum dot body and the coating connected with the quantum dot body through the connecting group, and the coating comprises a silicon-oxygen-aluminum bond.
7. The method of preparing a quantum dot powder with a coating attached to a surface of a quantum dot according to claim 6, wherein in the step S1, a molar ratio of the initial quantum dot to the silane compound having a linking group is 1 (1-10).
8. The method for preparing quantum dot powder with coating attached to surface of quantum dot according to claim 6, wherein in the step S1, the reaction temperature is 80-120 ℃; in the step S2, the reaction temperature is 100-150 ℃.
9. The method for preparing quantum dot powder with a coating connected to the surface of a quantum dot according to claim 6, wherein the molar ratio of the silane compound containing a connecting group to the organic aluminum and/or aluminum salt is 0.1-3.
10. An optical element is characterized by comprising the quantum dot powder with the surface of the quantum dot connected with a coating according to any one of claims 1-5 or the quantum dot powder with the surface of the quantum dot connected with the coating prepared by the preparation method according to any one of claims 6-9.
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