CN115852333A - Multi-layer coated quantum dot material and preparation method thereof - Google Patents
Multi-layer coated quantum dot material and preparation method thereof Download PDFInfo
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- CN115852333A CN115852333A CN202111121966.7A CN202111121966A CN115852333A CN 115852333 A CN115852333 A CN 115852333A CN 202111121966 A CN202111121966 A CN 202111121966A CN 115852333 A CN115852333 A CN 115852333A
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Abstract
The application discloses multilayer coated quantum dot material and a preparation method thereof, the multilayer coated quantum dot material comprises quantum dot/polymer composite particles, the surfaces of the quantum dot/polymer composite particles are coated with protective layers, and the outer sides of the protective layers are coated with metal oxide films. After the perovskite quantum dots/polymer microspheres are coated by the protective layer, the defects on the surfaces of the microspheres can be obviously improved, compact spherical shells are formed, and meanwhile, the micro powder is uniformly dispersed, so that the subsequent atomic layer deposition coating is facilitated. The coated perovskite quantum dot/polymer micro powder has excellent luminescence performance, the water-blocking and oxygen-blocking performance of the material is improved by the compact coating layer formed on the surface, and the stability of the perovskite quantum dot/polymer micro powder is improved.
Description
Technical Field
The application relates to a multi-layer coated quantum dot material and a preparation method thereof, belonging to the technical field of display.
Background
The perovskite quantum dot has the excellent characteristics of simple preparation process, low cost, high quantum yield, high color purity and the like, and can greatly improve the display color gamut of a display device, so that the perovskite quantum dot is widely concerned. Currently, luminescent thin films based on in situ preparation of perovskite quantum dots have been successfully used commercially in the display field, increasing the color gamut to 100% ntsc or greater. However, the perovskite quantum dot material has a gap from the application of realizing large-scale industrialization, namely, the long-term stability in practical application has a certain problem. The main reason for the poor stability of the perovskite quantum dot material in long-term use is the invasion of water and oxygen in the actual environment, which causes the fluorescence quenching of the quantum dot, and causes the brightness attenuation and the color point change. Therefore, a method for improving the stability of perovskite quantum dot materials is urgently needed.
The synthesis methods of perovskite quantum dots reported at present comprise methods such as a hot injection method, and the synthesis methods all have the problem that a large amount of solvents and additives are used during synthesis, so that raw materials are wasted; moreover, a high-temperature or high-temperature and high-pressure environment needs to be provided during synthesis, and the quantum dots can be obtained only by multiple cleaning steps after synthesis, so that the process is complicated, a large amount of solvent is wasted, and large-scale preparation is not facilitated; in addition, the traditional synthesis method is to prepare the quantum dots firstly and then carry out subsequent treatment for improving the stability, such as the processes of inorganic matter shell layer coating, organic polymer coating and the like, by-products generated in the processes can cause the ligand on the surface of the quantum dots to fall off, and the optical performance and the stability of the quantum dots are influenced. Therefore, new preparation and surface treatment techniques are crucial to improve the stability of perovskite quantum dots.
Disclosure of Invention
In order to solve the problems, the invention provides a two-layer coating treatment technology of perovskite quantum dot/polymer composite micro powder, which comprises solution coating and atomic layer deposition coating of the perovskite quantum dot/polymer composite micro powder. The technology firstly adopts a spray drying method to prepare the perovskite quantum dot/polymer luminescent microsphere, can realize the preparation of the quantum dot and the coating of the polymer in one step, has simple and stable process, and is far superior to the process of synthesizing the quantum dot by a liquid phase. After the perovskite quantum dot/polymer microsphere is obtained, a protective layer is uniformly coated on the surface of the microsphere by a solution coating method, so that the microsphere particles are uniformly dispersed. And finally, depositing a layer of compact inorganic oxide on the surfaces of the uniformly dispersed particles by an atomic layer deposition technology to block the invasion of water and oxygen, thereby improving the stability of the perovskite quantum dot/polymer micro powder. The technology for preparing the perovskite quantum dot/polymer luminescent microsphere and the two-layer coating composite material by spraying avoids resource waste and complex synthesis procedures of the traditional liquid phase synthesis method, effectively and uniformly performs a polymer coating process and a subsequent two-layer coating process, improves the stability of luminescent micro powder, and promotes the commercial application of the perovskite quantum dot.
As one aspect of the present application, a multi-layered clad quantum dot material is provided. According to the method, the perovskite quantum dot/polymer microsphere prepared by spray drying is subjected to composite coating in a two-layer coating mode of solution coating and atomic layer deposition, so that the water-blocking and oxygen-blocking effects are improved, the stability and the solvent resistance of the perovskite quantum dot material are improved, and the perovskite quantum dot material can be dispersed in a plurality of solvent systems. The perovskite quantum dot/polymer micro powder coated by the two layers shows ultrahigh corrosion resistance, can be blended with various materials such as photoresist, UV (ultraviolet) glue, pressure sensitive glue and various organic solvents, can be used for preparing luminescent materials in various forms such as luminescent dots, lines and films by utilizing various processes such as dispensing, ink-jet printing, silk-screen printing, tape casting, photoetching and the like, can be applied to various fields such as display backlight and the like, and widens the application range of quantum dot composite materials.
The multilayer coated quantum dot material comprises quantum dot/polymer composite particles, wherein the surfaces of the quantum dot/polymer composite particles are coated with protective layers, and metal oxide thin films are coated outside the protective layers.
Optionally, the protective layer quantum dot/polymer composite particle comprises a spatial network structure formed by polymers, and the quantum dot is embedded in the spatial network structure;
optionally, the quantum dots are perovskite-type quantum dots;
optionally, the polymer comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyano cellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate, polylauryl methacrylate.
Optionally, the protective layer is silicon dioxide and/or amphoteric hydroxide;
optionally, the amphoteric hydroxide comprises at least one of aluminum hydroxide, titanium hydroxide, zirconium hydroxide.
Optionally, the metal oxide thin film comprises Al 2 O 3 Film, tiO 2 Film, hfO 2 Film, zrO 2 At least one of a film;
optionally, the particle size of the quantum dot/polymer composite particle is 1-100 μm;
the thickness of the protective layer is 10-500 nm;
the thickness of the metal oxide film coating protective layer is 1 nm-100 nm.
The preparation method of the perovskite quantum dot/polymer microsphere is simple in process and easy for industrial large-scale preparation, and the prepared powder is prepared by completely wrapping the perovskite quantum dot with the polymer to form a protective layer, so that the stability of the perovskite quantum dot material is improved. According to the solution method coating, the powder surface is coated with the protective layer through hydrolysis reaction, and after the perovskite quantum dot/polymer microsphere is coated with the protective layer, the defects on the microsphere surface can be obviously improved, a compact spherical shell is formed, and the stability is improved; meanwhile, the micro powder is uniformly dispersed by the solution coating method, so that the subsequent atomic layer deposition coating is facilitated, and the coating rate is improved. The solvent used for coating can be recycled, so that the production cost is greatly reduced. The atomic layer deposition method disclosed by the invention is widely applied in the industry, the process is mature, and the atomic layer deposition method can be used for continuously depositing the metal oxide film with the nanometer thickness or the submicron thickness on the surface of the uniformly dispersed perovskite quantum dot/polymer microsphere so as to finish the surface coating treatment process of the whole microsphere. The whole coating process does not influence the optical performance of the perovskite quantum dot/polymer microsphere.
A preparation method of a multilayer coated quantum dot material comprises the following steps:
(a) Obtaining quantum dot/polymer composite particles;
(b) Reacting a solution containing quantum dot/polymer composite particles, a protective layer raw material compound and a catalyst to obtain the quantum dot/polymer composite particles coated with the protective layer;
(c) Forming a metal oxide thin film on the quantum dot/polymer composite particles coated with the protective layer obtained in step (b) by atomic layer deposition.
Optionally, in the step (a), the perovskite quantum dot precursor polymer solution is formed into atomized micro-droplets by a two-fluid atomizer through a liquid conveying pipeline, the atomized micro-droplets enter a drying tower, and are dried by hot air blown in from an air inlet to form perovskite quantum dot/polymer microspheres, and the perovskite quantum dot polymer micro-powder enters a cyclone separator through an air outlet below a drying tank to realize powder collection.
Alternatively, the quantum adopts perovskite quantum dots.
Optionally, the perovskite quantum dot synthetic raw material comprises AX and BX t And a CX precursor; wherein A is selected from NH 2 CHNH 2 + (FA + )、CH 3 NH 3 + (MA + )、Cs + 、Rb + 、K + At least one of; b is selected from Pb 2+ 、Sn 2+ 、Bi 3+ 、Ti 3+ 、Zn 2+ 、Ni 2+ 、Cd 2+ 、Al 3+ 、Mn 2+ 、Mn 4+ 、Ge 3+ At least one of (a); c is selected from aryl or alkyl organic amine cation with carbon atom number not less than 3; x is selected from Br - 、I - 、SCN - At least one of carboxylic acid groups; m =2, 3 or 4;
optionally, the perovskite quantum dot has the structural formula AMX 3 、A 3 M 2 X 9 、A 2 MX 6 、Q 2 A m-1 M m X 3m+1 At least one of;
wherein A is NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + At least one of;
m is Pb 2+ 、Cd 2+ 、Mn 2+ 、Zn 2+ 、Sn 2+ 、Ge 2+ 、Bi 3+ At least one of;
x is at least one of halogen anions;
q is an aromatic group or an alkyl organic amine cation with the carbon atom number not less than 3;
m is any number between 1 and 100.
Optionally, the perovskite quantum dot precursors AX and BX m And CX is 0.5-10;
optionally, the solvent comprises at least one of dimethyl sulfoxide, N-hexane, cyclohexane, N-octane, octadecene, ethanol, methanol, trimethyl phosphate, triethyl phosphate, N-methylpyrrolidone, dimethylacetamide, N-dimethylformamide, isopropanol, ethyl acetate, toluene, acetone.
Optionally, the mass ratio of the solvent to the polymer matrix in the perovskite quantum dot precursor polymer solution is 100:1 to 100. The mass ratio of the quantum dot precursor material to the polymer matrix is 1:1 to 200.
Optionally, the spray drying process is carried out by a spray drying apparatus having a two-fluid atomizer. The main process parameters include: feed rate of the solution: 50 ml/h-50000 ml/h; corresponding inlet pressure of the atomizer: 0.02-1 MPa, air inlet speed: 15L/min to 100L/min; the air inlet temperature of the dryer is as follows: 50-200 ℃.
Optionally, in the step (b), the quantum dot/polymer composite particles coated with the protective layer are vigorously stirred and uniformly dispersed in a large amount of solvent, and then fully stirred to obtain a powder mixed solution; and sequentially adding a surfactant, a hydrolysis raw material, a catalyst and deionized water into the mixed solution, and fully performing hydrolysis reaction, wherein the surface of each powder particle is covered with a layer of product and a compact protective layer.
Optionally, the protective layer raw material compound in the step (b) includes at least one of an aluminum source compound, a silicon source compound, a titanium source compound, and a zirconium source compound;
optionally, the mass ratio of the powder to the protective layer raw material compound is 1:0.1 to 100;
optionally, the aluminum source compound comprises at least one of triethylaluminum, aluminum sec-butoxide, aluminum isopropoxide;
optionally, the silicon source compound comprises at least one of (3-mercaptopropyl) trimethoxysilane, bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide, 3-aminopropyltriethoxysilane, methyl orthosilicate, ethyl orthosilicate, octadecyltrimethoxysilane;
optionally, the titanium source compound comprises at least one of tetrabutyl titanate, isopropyl titanate, tetraethyl titanate;
optionally, the zirconium source compound comprises at least one of zirconium n-butoxide, zirconium t-butoxide, zirconium isopropoxide.
Optionally, the catalyst comprises at least one of methylamine, ammonia, dimethylamine;
optionally, the mass ratio of powder to catalyst is 1:0.1 to 10.
Optionally, the solution in step (b) further comprises a surfactant;
optionally, the surfactant comprises at least one of 6-mercaptohexanol, 1-hexadecanethiol, hexanethiol, oleic acid, stearic acid;
optionally, the mass ratio of powder to surfactant is 1:0.1 to 50.
Optionally, in the step (b), a solution containing the quantum dot/polymer composite particles, the protective layer raw material compound, the catalyst and water is reacted at a temperature of 20-50 ℃ and a stirring speed of 100-1000 rpm to obtain the quantum dot/polymer composite particles coated with the protective layer;
optionally, the quantum dot/polymer composite particles coated with the protective layer are separated from the solution by suction filtration in the step (b).
Optionally, the step of vacuum filtering comprises: cleaning a filter flask, assembling the filter flask and a vacuum pump, placing a filter membrane, pouring mixed liquid, starting suction filtration and collecting powder.
Optionally, a pressure regulating valve is arranged between the filter flask and the vacuum pump, so that the vacuum degree and the suction filtration speed can be regulated, and the suction filtration speed is ensured not to be too fast, so that the filter membrane is damaged.
Optionally, an anti-suck back bottle is added between the vacuum pump and the filter flask.
Optionally, the filter membrane is a microporous filter membrane, and the size of the micropores is 0.1-5 microns.
Optionally, in the step (c), a compound raw material containing a metal element is reacted with an oxidant to generate a metal oxide film in the atomic layer deposition;
optionally, in step (c), the microparticles are first contained in a centrifugally rotatable chamber to maintain the powder in a continuously moving dispersed state; introducing a compound containing the metal element into the cavity, fully reacting with the surface of the particle, and then introducing inert gas to remove the redundant compound containing the metal element and byproducts; and introducing an oxidant into the cavity, and enabling the oxidant to fully react with the compound containing the metal element on the surface of the particle, so that the oxidant and the compound react to generate a first atomic layer. The operation is repeated, and the thickness of the oxide layer is gradually increased until the surface coating treatment process of the whole particle is completed.
Optionally, the raw material of the compound containing the metal element comprises at least one of trimethyl aluminum, aluminum trichloride, titanium tetrachloride, titanium isopropoxide, zirconium tetra (dimethylamino) group, hafnium tetrachloride, hafnium nitrate and zirconium dimethylamino group;
optionally, the oxide comprises at least one of water, ozone, oxygen plasma.
Optionally, the flow rates of the metal element-containing compound and the oxidant are 10-500 standard milliliters per minute, and the flow rate of the carrier gas is 10-1000 standard milliliters per minute.
Optionally, in each atomic layer deposition reaction, the reaction time of the compound containing the metal element and the oxidant with the particles is 0.1s to 10s, and the outlet pressure of the chamber is 50Pa to 500Pa.
Optionally, the flushing time after each reaction is 0.1s to 10s, and the flow rate of the flushing gas is 10 to 1000 standard milliliters per minute.
The invention can produce the following beneficial effects:
1. according to the method, the perovskite quantum dot/polymer microsphere prepared by spray drying is subjected to composite coating in a two-layer coating mode of solution coating and atomic layer deposition, so that the water-blocking and oxygen-blocking effects are improved, the stability and the solvent resistance of the perovskite quantum dot material are improved, and the perovskite quantum dot material can be dispersed in a plurality of solvent systems. The perovskite quantum dot/polymer micro powder coated by the two layers shows ultrahigh corrosion resistance, can be blended with various materials such as photoresist, UV (ultraviolet) glue, pressure sensitive glue and various organic solvents, can be used for preparing luminescent materials in various forms such as luminescent dots, lines and films by utilizing various processes such as dispensing, ink-jet printing, silk-screen printing, tape casting, photoetching and the like, can be applied to various fields such as display backlight and the like, and widens the application range of quantum dot composite materials.
2. The method for preparing the perovskite quantum dot/polymer microsphere through spray drying is simple in process and easy for industrial large-scale preparation, and the perovskite quantum dot is completely wrapped by the polymer to form a protective layer in the prepared powder, so that the stability of the perovskite quantum dot material is improved. According to the solution method coating, the powder surface is coated with the protective layer through hydrolysis reaction, and after the perovskite quantum dot/polymer microsphere is coated with the protective layer, the defects on the surface of the microsphere can be obviously improved, a compact spherical shell is formed, and the stability is improved; meanwhile, the micro powder is uniformly dispersed by the solution coating method, so that the subsequent atomic layer deposition coating is facilitated, and the coating rate is improved. In addition, the solvent used for coating can be recycled, so that the production cost is greatly reduced. The method for atomic layer deposition in the invention has wide application in the industry and mature process. The atomic layer deposition method can continuously deposit the metal oxide film with nanometer thickness or submicron thickness on the surface of the uniformly dispersed perovskite quantum dot/polymer microsphere, and the surface coating treatment process of the whole microsphere is completed. The whole coating process does not influence the optical performance of the perovskite quantum dot/polymer microsphere.
Drawings
FIG. 1 is a schematic structural diagram of a micro powder coated with two layers of perovskite quantum dots/polymer microspheres by a solution method and an atomic layer deposition. Wherein 1 represents a perovskite quantum dot; 2 represents a polymer matrix, and the polymer matrix completely wraps the perovskite quantum dots; 3 represents a protective layer coated by a solution method; 4 represents an atomic layer deposition coated nano or submicron oxide layer;
FIG. 2 is a schematic process flow diagram of the present invention;
FIG. 3 is a photograph of a perovskite quantum dot polymer micropowder prepared by spray drying;
FIG. 4 is a fluorescence emission spectrogram of the perovskite quantum dot polymer micropowder prepared by spray drying;
FIG. 5 is a scanning electron microscope picture of the perovskite quantum dot polymer micro powder prepared by spray drying;
FIG. 6 is a scanning electron microscope image of the powder after atomic layer deposition coating;
fig. 7 is a graph of luminance decay versus aging time based on uncoated versus coated green micropowder.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. The materials used in the examples were all purchased commercially.
SEM pictures were obtained by using a Hitachi SU8220 cold field emission scanning electron microscope.
The fluorescence emission spectrum is obtained by a spectrocolorimeter of Admesy company, and an excitation light source is a blue LED with the wavelength of 455 nm.
Example 1
The structure of the multi-layer coated quantum dot material is shown in fig. 1, and the preparation method is shown in fig. 2. MAPbBr was selected in this example 3 And (3) carrying out spray drying on the perovskite raw material and polymer polyvinylidene fluoride to prepare composite powder. Precursor MABr and PbBr of quantum dot material 2 Tetrapropylammonium bromide in a molar ratio of 0.6mmol:0.6mmol: dissolving 0.3mmol of the powder in 200ml of anhydrous N, N-Dimethylformamide (DMF), adding 10g of polyvinylidene fluoride (PVDF) to form a perovskite quantum dot precursor polymer solution, stirring for 2 hours to dissolve the solution, and performing spray drying to prepare powder. The spray drying parameters are set as the feeding speed of the solution is 500ml/h, the air inlet pressure is 0.08MPa, the air inlet speed is 60L/min, and the air inlet temperature of the dryer is 85 ℃. The prepared perovskite/polymer microsphere powder is shown in figure 3, the powder is bright green, the luminescence spectrum of the powder is shown in figure 4, and the luminescence peak is 523nm. In this case, as shown in fig. 5, the scanning electron micrograph of the perovskite quantum dot/polymer powder shows that the fine powder is substantially round and has a micron size distribution.
Weighing 10g of powder, slowly pouring the powder into 2000mL of normal hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 10mL of oleic acid, 0.1mol of methyl orthosilicate and 100 mu L of water, stirring for 3h, fully hydrolyzing to obtain powder coated by a solution method, then performing vacuum filtration by using a vacuum pump with the maximum vacuum degree of 0.1MPa, separating the powder from the solvent, drying the residual solvent to obtain uniformly distributed powder, wherein the vacuum filtration methods in the subsequent embodiments are all consistent.
Followed by atomic layer deposition coating. Putting the powdery product into a centrifugal holder, controlling the holder to rotate and vacuumizing at the same time, and then heating a cavity to 80-100 ℃; introducing trimethylaluminum into the powder cavity for 5 seconds to fully contact and adsorb the trimethylaluminum and the powder surface, and then introducing inert gas to remove the redundant trimethylaluminum and byproducts for 60 seconds; and (3) introducing water into the cavity for 5 seconds, and enabling the water to fully react with the trimethylaluminum on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation is repeated, and the thickness of the oxide layer is gradually increased until the surface coating treatment process of the whole microsphere is completed. Scanning electron micrographs of the coated powder are shown in fig. 6, from which it is seen that the microspheres exhibit a rough surface, which is a coated oxide layer.
The green powder, uncoated and double coated, was loaded into a sandwich of two glass layers and subjected to an aging test in an environmental test chamber at 60 ℃ and 90% RH. The brightness decay after 240 hours of aging is shown in fig. 7, and the brightness decay of the coated green micropowder is only 5% less after 240 hours of aging, while the uncoated sample has already exceeded 15% of the decay rate. The two layers of the perovskite/polymer particles are coated with oxide films on the surfaces, so that the stability of the material is obviously improved.
Example 2
In this embodiment, FAPBR is selected 3 Performing spray drying on the perovskite raw material and polymer polymethyl methacrylate, and performing quantum dot material precursor FABr and PbBr 2 Tetrabutylammonium bromide in a molar ratio of 0.7mmol:0.6mmol:0.3mmol, and the temperature of a dryer is 85 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright green. And (3) solution method coating process: weighing 10g of powder, slowly pouring into 2000mL of n-hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 5mL of oleic acid, 0.2mol of 3-aminopropyltriethoxysilane and 200 mu L of deionized water, stirring for 3 hours, and fully hydrolyzing to obtain a solutionAnd (3) carrying out suction filtration and drying on the powder coated by the method to obtain uniformly distributed powder. Cladding Al by atomic layer deposition 2 O 3 And finishing the surface coating treatment process of the whole microsphere.
Example 3
In this example, csPbBr was selected 3 Performing spray drying on the perovskite raw material and polymer polyvinylidene fluoride, and preparing precursors CsBr and PbBr of the quantum dot material 2 Dodecyl dimethyl benzyl ammonium bromide in a molar ratio of 0.6mmol:0.6mmol:0.4mmol, and the temperature of a dryer is 100 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright green. And (3) solution method coating process: weighing 10g of powder, slowly pouring the powder into 2000mL of normal hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 10mL of oleic acid, 0.5mol of tetrabutyl titanate and 300 mu L of deionized water, stirring for 5 hours, fully hydrolyzing to obtain powder coated by a solution method, and then carrying out suction filtration and drying on residual solvent to obtain uniformly distributed powder. Coating TiO by atomic layer deposition 2 And finishing the surface coating treatment process of the whole microsphere.
Example 4
In this example, MA is selected 0.9 Cs 0.1 PbBr 3 Mixing perovskite raw material with polymer, polymer polyvinylidene fluoride and polymethyl methacrylate, and spray drying to obtain quantum dot material precursors MABr, csBr and PbBr 2 Octylamine bromide in a molar ratio of 0.6mmol:0.1mmol:0.6mmol:0.18mmol, and the temperature of a dryer is 90 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright green. And (3) solution method coating process: weighing 10g of powder, slowly pouring the powder into 2000ml of normal hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 0.3mol of tetraethoxysilane, then stirring the mixture for 5 hours in an open way for full hydrolysis to obtain powder coated by a solution method, and then carrying out suction filtration and drying on residual solvent to obtain uniformly distributed powder. Subsequent atomic layer deposition of coated ZrO 2 And finishing the surface coating treatment process of the whole microsphere.
Example 5
In this example, MA is selected 0.8 FA 0.2 PbBr 3 Performing spray drying on the perovskite raw material and the polymethyl methacrylate polymer, and performing spray drying on precursors of the quantum dot material, such as MABr, FABr and PbBr 2 Tetraoctylammonium bromide in a molar ratio of 0.48mmol:0.12mmol:0.6mmol:0.3mmol, and the temperature of a dryer is 90 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright green. Solution method coating process: weighing 10g of powder, slowly pouring the powder into 2000mL of normal hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 5mL of stearic acid, 0.5mol of n-butyl zirconium and 400 mu L of deionized water, then stirring for 5 hours in an open manner for sufficient hydrolysis to obtain powder coated by a solution method, and then carrying out suction filtration and drying on residual solvent to obtain uniformly distributed powder. Cladding Al by atomic layer deposition 2 O 3 And finishing the surface coating treatment process of the whole microsphere.
Example 6
MAPbI was selected in this example 3 Performing spray drying on a perovskite raw material and a polymer polymethyl methacrylate, and performing MAI and PbI on quantum dot material precursors 2 Tetrabutylammonium iodide in a molar ratio of 0.6mmol:0.6mmol:0.3mmol, and the temperature of a dryer is 120 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright red. And (3) solution method coating process: weighing 10g of powder, slowly pouring the powder into 2000mL of n-hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 10mL of hexanethiol and 0.2mol of ethyl orthosilicate, then stirring for 3h in an open manner for full hydrolysis to obtain powder coated by a solution method, and then carrying out suction filtration and drying on residual solvent to obtain uniformly distributed powder. Cladding Al by atomic layer deposition 2 O 3 And finishing the surface coating treatment process of the whole microsphere.
Example 7
MAPb (Br/I) was selected in this example 3 Spraying and drying perovskite raw material and polymer polymethyl methacrylate, and preparing a quantum dot material precursor MAI,PbI 2 Octylamine iodide, hydrobromic acid in a molar ratio of 0.6mmol:0.6mmol:0.3mmol:0.3mmol, and the temperature of a dryer is 110 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright red. And (3) solution method coating process: weighing 10g of powder, slowly pouring the powder into 2000mL of normal hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 10mL of oleic acid and 0.5mol of tetraethoxysilane, then stirring for 3 hours in an open way, fully hydrolyzing to obtain powder coated by a solution method, and then carrying out suction filtration and drying on residual solvent to obtain uniformly distributed powder. Coating TiO by atomic layer deposition 2 And finishing the surface coating treatment process of the whole microsphere.
Example 8
CsPbI was selected in this example 3 Carrying out spray drying on the perovskite raw material and the polymethyl methacrylate polymer, and obtaining precursors CsI and PbI of the quantum dot material 2 And octylamine iodide in a molar ratio of 0.6mmol:0.6mmol:0.3mmol, and the temperature of a dryer is 120 ℃, and perovskite quantum dot polymer composite powder is prepared. The prepared perovskite/polymer microsphere powder is bright red. And (3) solution method coating process: weighing 10g of powder, slowly pouring the powder into 2000ml of n-hexane, stirring, uniformly dispersing the powder in a solvent, sequentially adding 20ml of oleic acid and 0.5mol of 3-aminopropyltriethoxysilane, then stirring for 5 hours in an open place for full hydrolysis to obtain powder coated by a solution method, and then carrying out suction filtration and drying on residual solvent to obtain uniformly distributed powder. Cladding Al by atomic layer deposition 2 O 3 And finishing the surface coating treatment process of the whole microsphere.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A multi-layer coated quantum dot material is characterized in that the multi-layer coated quantum dot material comprises quantum dot/polymer composite particles, a protective layer and a metal oxide film;
the protective layer coats the quantum dot/polymer composite particles;
the metal oxide film is coated with a protective layer.
2. The multi-layered quantum dot material of claim 1, wherein the protective layer is silica and/or amphoteric hydroxide;
preferably, the amphoteric hydroxide comprises at least one of aluminum hydroxide, titanium hydroxide and zirconium hydroxide.
3. The multi-layer coated quantum dot material of claim 1, wherein the particle size of the quantum dot/polymer composite particle is 1-100 μm;
the thickness of the protective layer is 10-500 nm;
the thickness of the metal oxide film coating protective layer is 1 nm-100 nm.
4. The multi-layered quantum dot material as claimed in claim 1, wherein the protective layer quantum dot/polymer composite particle comprises a spatial network structure formed by polymer, and the quantum dot is embedded in the spatial network structure;
preferably, the quantum dots are perovskite quantum dots;
preferably, the polymer comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyano cellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate, polylauryl methacrylate;
preferably, the metal oxide thin film includes Al 2 O 3 Film, tiO 2 Film, hfO 2 Film, zrO 2 At least one of the films.
5. A preparation method of a quantum dot material with multilayer coating is characterized by comprising the following steps:
obtaining quantum dot/polymer composite particles;
reacting a solution containing quantum dot/polymer composite particles, a protective layer raw material compound, a catalyst and water to obtain the quantum dot/polymer composite particles coated with the protective layer;
and (c) forming a metal oxide thin film on the quantum dot/polymer composite particles coated with the protective layer obtained in the step (b) by atomic layer deposition.
6. The method according to claim 5, wherein the protective layer raw material compound in the step (b) includes at least one of an aluminum source compound, a silicon source compound, a titanium source compound, and a zirconium source compound;
preferably, the mass ratio of the quantum dot/polymer composite particles to the protective layer raw material compound is 1:0.1 to 100;
preferably, the aluminum source compound comprises at least one of triethylaluminum, aluminum sec-butoxide, and aluminum isopropoxide;
preferably, the silicon source compound comprises at least one of (3-mercaptopropyl) trimethoxysilane, bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide, 3-aminopropyltriethoxysilane, methyl orthosilicate, ethyl orthosilicate and octadecyl trimethoxysilane;
preferably, the titanium source compound comprises at least one of tetrabutyl titanate, isopropyl titanate and tetraethyl titanate;
preferably, the zirconium source compound comprises at least one of zirconium n-butoxide, zirconium t-butoxide and zirconium i-propoxide;
preferably, the quantum dot/polymer composite particles are obtained by a spray drying method in the step (a);
preferably, the quantum dots are perovskite quanta, and the perovskite isThe quantum dot synthetic raw materials comprise AX and BX m And a CX precursor; wherein A is selected from NH 2 CHNH 2 + (FA + )、CH 3 NH 3 + (MA + )、Cs + 、Rb + 、K + At least one of; b is selected from Pb 2+ 、Sn 2+ 、Bi 3 + 、Ti 3+ 、Zn 2+ 、Ni 2+ 、Cd 2+ 、Al 3+ 、Mn 2+ 、Mn 4+ 、Ge 3+ At least one of; c is selected from aryl or alkyl organic amine cation with carbon atom number not less than 3; x is selected from Br - 、I - 、SCN - At least one of carboxylic acid groups; m =2, 3 or 4;
preferably, the perovskite quantum dot precursors AX and BX m And CX is 0.5-10;
preferably, the solvent comprises at least one of dimethyl sulfoxide, N-hexane, cyclohexane, N-octane, octadecene, ethanol, methanol, trimethyl phosphate, triethyl phosphate, N-methylpyrrolidone, dimethylacetamide, N-dimethylformamide, isopropanol, ethyl acetate, toluene and acetone;
preferably, the mass ratio of the solvent to the polymer matrix in the perovskite quantum dot precursor polymer solution is 100:1 to 100; the mass ratio of the quantum dot precursor material to the polymer matrix is 1:1 to 200;
preferably, the spray drying process is carried out by a spray drying apparatus having a two-fluid atomizer; the technological parameters of spray drying include: feed rate of the solution: 50 ml/h-50000 ml/h; intake pressure of the corresponding atomizer: 0.02-1 MPa, air inlet speed: 15L/min to 100L/min; inlet air temperature of the dryer: 50-200 ℃.
7. The method of claim 5, wherein the catalyst comprises at least one of methylamine, ammonia, dimethylamine;
preferably, the mass ratio of the quantum dot/polymer composite particles to the catalyst is 1:0.1 to 10.
8. The method according to claim 5, wherein the solution in the step (b) further comprises a surfactant;
preferably, the surfactant comprises at least one of 6-mercaptohexanol, 1-hexadecanethiol, hexanethiol, oleic acid and stearic acid;
preferably, the mass ratio of the quantum dot/polymer composite particles to the surfactant is 1:0.1 to 50.
9. The preparation method according to claim 5, wherein the solution containing the quantum dot/polymer composite particles, the protective layer raw material compound, the catalyst and water in the step (b) is reacted at a temperature of 20 to 50 ℃ and a stirring speed of 100 to 1000 rpm to obtain the quantum dot/polymer composite particles coated with the protective layer;
preferably, the quantum dot/polymer composite particles coated with the protective layer are separated from the solution by suction filtration in step (b).
10. The method according to claim 5, wherein in the step (c), the compound raw material containing the metal element is reacted with an oxidant to form a metal oxide film;
preferably, the raw material of the metal element-containing compound includes at least one of trimethylaluminum, aluminum trichloride, titanium tetrachloride, titanium isopropoxide, tetrakis (dimethylamino) zirconium, hafnium tetrachloride, hafnium nitrate, and dimethylaminobenzonium;
preferably, the oxide comprises at least one of water, ozone, and oxygen plasma.
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