CN116285945A - Functional composite perovskite quantum dot material and preparation method and application thereof - Google Patents
Functional composite perovskite quantum dot material and preparation method and application thereof Download PDFInfo
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- CN116285945A CN116285945A CN202111572431.1A CN202111572431A CN116285945A CN 116285945 A CN116285945 A CN 116285945A CN 202111572431 A CN202111572431 A CN 202111572431A CN 116285945 A CN116285945 A CN 116285945A
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- perovskite quantum
- quantum dot
- precursor
- powder
- powder particles
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Abstract
The application discloses a functional composite perovskite quantum dot material and a preparation method and application thereof. The functional composite perovskite quantum dot material comprises powder particles and a metal oxide film; the powder particles comprise surface ligand-perovskite quantum dots, a matrix polymer and water-absorbing functional resin; the metal oxide film is coated on the surface of the powder particles through atomic layer deposition. The powder particles contain the water-absorbing functional resin, so that the water and oxygen blocking performance of the powder particles is effectively improved, and the stability of the perovskite quantum dots is improved.
Description
Technical Field
The application relates to a functional composite perovskite quantum dot material, and a preparation method and application thereof, and belongs to the technical field of materials.
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 the display device, so that the perovskite quantum dot is widely focused. Currently, films prepared in situ based on perovskite quantum dots have successfully achieved commercial applications in the display field, and can boost the color gamut of display devices to over 110% ntsc. In addition, the perovskite quantum dot material has potential application in the fields of fluorescent ink, optical anti-counterfeiting and the like, and receives wide attention. However, in practical applications, there is a problem in the long-term stability of perovskite quantum dots, namely, the intrusion of water oxygen in the practical environment causes fluorescence quenching, luminance decay and optical color point variation of the quantum dots. Therefore, a method for improving the water and oxygen blocking performance of the perovskite material and further improving the stability of the perovskite quantum dot is needed.
Complete encapsulation of perovskite quantum dots using polymeric materials is an effective method of enhancing perovskite stability. Currently polymer coated perovskite quantum dots include two forms: in-situ cladding methods and ex-situ cladding methods. The ex-situ coating method is to prepare perovskite quantum dots firstly and then carry out a subsequent polymer coating process (patent CN 110373180 A,CN 106753328 A,CN 110511739), and the by-products generated in the post-treatment process can cause ligand on the surfaces of the quantum dots to fall off, so that the optical performance and stability of the quantum dots are affected, and the perovskite quantum dots are difficult to disperse in a polymer matrix well, so that the effect is affected.
Disclosure of Invention
According to one aspect of the application, the functional composite perovskite quantum dot material is provided, and the powder particles contain water-absorbing functional resin, so that the water resistance and oxygen resistance of the powder particles are effectively improved, and the stability of the perovskite quantum dots is improved.
A functional composite perovskite quantum dot material comprising powder particles and a metal oxide thin film;
the powder particles comprise surface ligand-perovskite quantum dots, a matrix polymer and water-absorbing functional resin;
the metal oxide film is coated on the surface of the powder particles through atomic layer deposition.
Wherein, the surface ligand-perovskite quantum dot refers to the ligand coordinated on the surface of the perovskite quantum dot.
Optionally, the water-absorbing functional resin includes at least one of resins containing hydrophilic groups.
Optionally, the hydrophilic group includes at least one of a carboxylic acid group, a sulfonic acid group, a hydroxyl group, and an ether group.
Optionally, the water-absorbing functional resin comprises at least one of polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, polyvinylpyrrolidone and sodium polyacrylate.
Optionally, the mass ratio of the surface ligand-perovskite quantum dots, the matrix polymer and the water-absorbing functional resin is 0.1-1:1-100:0.1-100.
Optionally, the perovskite quantum dots in the surface ligand-perovskite quantum dots have a structural formula ABX 3 、A 3 B 2 X 9 、A 2 BX 6 At least one of (a) and (b); the ligand in the surface ligand-perovskite quantum dot has a structural formula CX;
wherein A is selected from NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + 、Rb + 、K + At least one of (a) and (b);
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) and (b);
c is selected from aryl or alkyl organic amine cation with carbon number not less than 3;
x is selected from Br - 、I - 、SCN - At least one of carboxylate radicals.
Optionally, the matrix polymer comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate, polylauryl methacrylate.
Optionally, the powder particles are obtained by:
atomizing the powder particle precursor solution into small liquid drops, and then drying the atomized small liquid drops to generate powder particles;
the powder particle precursor solution comprises a solvent, a surface ligand-perovskite quantum dot precursor raw material, a matrix polymer and a water-absorbing functional resin.
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, and acetone.
Optionally, the surface ligand-perovskite quantum dot precursor raw material comprises AX, BX m And CX;
wherein A is selected from NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + 、Rb + 、K + At least one of (a) and (b);
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 number not less than 3;
x is selected from Br - 、I - 、SCN - At least one of carboxylate groups;
m=2, 3 or 4.
Optionally, the AX, BX m And CX in a molar ratio of 0.5 to 10:1:0.3 to 10.
Optionally, the AX, BX m And CX in a molar ratio of 0.5 to 5: 1to 5:0.3 to 5.
Optionally, the AX, BX m And CX in a molar ratio of 0.5 to 3: 1to 3:0.3 to 3.
Optionally, in the powder particle precursor solution, the volume to mass ratio of the solvent to the matrix polymer is 300ml: 1-50 g.
Optionally, in the powder particle precursor solution, the volume to mass ratio of the solvent to the matrix polymer is 300ml:1g, 300ml:10g, 300ml:20g, 300ml:30g, 300ml:40g, 300ml: any value in 50g and a range value between any two values.
Optionally, the mass ratio of the surface ligand-perovskite quantum dot precursor raw material to the matrix polymer is 0.01-1: 1to 100.
Optionally, the mass ratio of the surface ligand-perovskite quantum dot precursor raw material to the matrix polymer is 0.01-1: 1to 50.
Optionally, the mass ratio of the surface ligand-perovskite quantum dot precursor raw material to the matrix polymer is 0.01-1: 1to 40.
Optionally, the mass ratio of the water-absorbing functional resin to the matrix polymer is 0.02-2.
Alternatively, the mass ratio of the water-absorbing functional resin to the matrix polymer is any value and a range of values between any two values of 0.02, 0.05, 0.1, 0.2, 0.5, 08, 1, 1.5, 2.
Optionally, the mass ratio of the water-absorbing functional resin to the matrix polymer is 0.04-0.5.
Optionally, the mass ratio of the water-absorbing functional resin to the matrix polymer is 0.04-0.2.
Optionally, the conditions of atomization include:
solution feed rate: 50-50000 ml/h;
intake pressure of the corresponding atomizer: 0.02-1 MPa, air inlet speed: 15-100L/min.
Optionally, the drying conditions include: air inlet temperature: 50-200 ℃.
Optionally, the metal oxide in the metal oxide film comprises Al 2 O 3 、TiO 2 、HfO 2 、ZrO 2 At least one of them.
Optionally, the thickness of the metal oxide film is 1 nm-200 nm.
Optionally, the powder particles have a particle size of 0.1 to 50 microns.
According to another aspect of the present application, there is provided a method for preparing a functional composite perovskite quantum dot material according to any one of the above, the method comprising the steps of:
and carrying out atomic layer deposition reaction on the raw materials containing the metal precursor, the oxygen precursor and the powder particles to obtain the composite material.
Optionally, the metal precursor includes at least one of a metal element-containing compound.
Optionally, the metal precursor comprises at least one of trimethylaluminum, aluminum trichloride, titanium tetrachloride, titanium isopropoxide, zirconium tetra (dimethylamino) ate, hafnium tetrachloride, hafnium nitrate, zirconium dimethylamino.
Optionally, the oxygen precursor comprises at least one of an elemental oxygen-containing species.
Optionally, the oxygen precursor includes at least one of water, ozone, and oxygen.
Optionally, the preparation method comprises the following steps:
(S1) introducing a gaseous metal precursor into a reaction bin containing powder particles for adsorption;
(S2) introducing a gaseous oxygen precursor for reaction.
Optionally, the temperature in the reaction bin is 40-100 ℃ and the vacuum degree is 0.1-300 Torr.
Optionally, the flow rates of the gaseous metal precursor and the gaseous oxygen precursor are 10 to 500 standard milliliters per minute.
Alternatively, the time of the adsorption and the reaction is independently 5 to 60 seconds.
Alternatively, the adsorption is static adsorption.
Optionally, during the adsorption and the reaction, the powder dispersion is ensured by at least one of rotation, stirring and vibration of the bin body.
Optionally, after the adsorption is finished, the method further comprises the following steps: and (5) introducing carrier gas to wash out the residual precursor and byproducts.
Optionally, the carrier gas comprises at least one of an inert gas.
Optionally, the carrier gas is introduced for 10-60 s.
Optionally, repeating steps (S1) to (S2) for 1to 500 times.
According to another aspect of the application, the application of the composite material prepared by any one of the above methods in the fields of backlight display, micro/Mini LED direct display, illumination or photovoltaic light conversion materials is provided.
The perovskite quantum dot/polymer powder is prepared in situ, functional resin such as water absorption is added, an ALD technology is applied to the surface of the powder to metal an oxide film, two layers of protection are carried out, the water and oxygen blocking performance is improved together, and the stability of the perovskite quantum dot/polymer composite material is improved.
ALD technology in the invention of the application has wide application in industry and mature process. The 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 powder, and the surface coating treatment process of the whole microsphere is completed.
The whole ALD coating process does not affect the optical properties of the perovskite quantum dot/polymer composite material itself.
The perovskite quantum dot/polymer powder coated by ALD in the invention has ultrahigh solvent corrosion resistance, water resistance and oxygen resistance, improves the environmental stability of a polymer substrate, improves the stability of a quantum dot/polymer composite material, and expands the application range of the composite material.
In the method for preparing the perovskite quantum dot/polymer powder by spray drying, the functional resin such as water absorption is added in situ in the precursor, and substances harmful to the perovskite quantum dot such as water vapor penetrating into the powder are timely absorbed, so that the influence on the perovskite quantum dot is avoided. Secondly, after the perovskite quantum dot/polymer powder is obtained, a layer of compact metal oxide is deposited on the surface of the powder particles by using an Atomic Layer Deposition (ALD) technology, so that invasion of substances such as water oxygen and the like is blocked, and the perovskite quantum dot/polymer micropowder is used as a first protective layer of the powder particles, so that the stability of the perovskite quantum dot/polymer micropowder is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme, and the scheme flow is shown in fig. 1: perovskite quantum dot/polymer powder added with functional resin is prepared by using a spray drying technology, and then oxide film deposition is carried out on the surface of the powder by using an ALD technology, so that the coating process is completed. The schematic structure of the coated sample is shown in fig. 2. The whole implementation process comprises the following steps:
perovskite quantum dot/polymer powders with added functional resins were prepared using spray drying techniques. The in-situ coating method is to dissolve the raw materials of the perovskite quantum dots and the polymer together, uniformly disperse the raw materials of the perovskite quantum dots in the polymer, and then generate and disperse the perovskite quantum dots in the polymer matrix in situ through a high-temperature process, so that the perovskite quantum dots can be effectively and completely coated. The spray drying process was as follows. Preparing a raw material solution: adding a matrix polymer solution and a functional resin into a perovskite quantum dot raw material solution, and mixing to form a powder particle precursor solution; spray drying process: the precursor solution is formed into atomized micro-droplets by a two-fluid atomizer through a transfusion pipeline, and enters a drying tower, and is dried by hot air blown in from an air inlet to form perovskite quantum dot/polymer powder, and the perovskite quantum dot polymer micro powder enters a cyclone separator through an air outlet below a drying tank to collect the powder.
The precursor solution is prepared by blending perovskite quantum dot precursor raw materials, matrix polymer, functional resin and organic solvent, and stirring and dissolving.
The perovskite quantum dot precursor raw material comprises a synthetic raw material for preparing perovskite quantum dots. The perovskite quantum dot synthesis raw material comprises AX, 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 (a) and (b); 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) and (b); c is selected from aryl or alkyl organic amine cation with carbon number not less than 3; x is selected from Br - 、I - 、SCN - At least one of carboxylate groups; m=2, 3 or 4;
the molar ratio of the perovskite quantum dot precursors AX, BXt and CX is 0.5-10:1:0.3-10;
the matrix polymer comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate and polylauryl methacrylate.
The functional resin comprises polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, polyvinylpyrrolidone, sodium polyacrylate and other macromolecular compounds with hydrophilic groups such as carboxylic acid groups, sulfonic acid groups, hydroxyl groups, ether groups and other types of functional resins.
The organic solvent can be 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.
The volume mass ratio of the solvent to the matrix polymer in the perovskite quantum dot precursor polymer solution is 100ml: 1-100 g. The mass ratio of the quantum dot precursor raw material to the matrix polymer is 1: 1to 200. The mass ratio of matrix polymer to functional value is 100: 1to 50.
The spray drying process is achieved by a spray drying apparatus having a two fluid atomizer. The main process parameters include: feed rate of solution: 50 ml/h-50000 ml/h; intake pressure of the corresponding atomizer: 0.02-1 MPa, air inlet speed: 15L/min-100L/min; inlet air temperature of the dryer: 50-200 ℃.
And drying the obtained perovskite quantum dot/polymer powder, and removing the redundant organic solvent. The drying temperature is 50-120 ℃, and the drying time is 30 min-24 h.
The size of the perovskite quantum dot/polymer powder is 0.1-50 microns.
The ALD coating procedure is as follows. Pouring the dried perovskite quantum dot/polymer powder into a reaction bin of ALD equipment, setting ALD process parameters such as deposition temperature, reaction source pulse pressure, pulse times, cycle numbers and the like according to the types of deposited oxide films, filling a metal precursor and an oxygen precursor into the reaction bin in an alternating pulse mode, and repeating the cycle until the required deposition thickness is reached, thereby completing ALD coating.
The powder is poured into a reaction bin of ALD equipment, and the reaction bin operates in a bin body rotating and dispersing mode or in a high-speed mechanical stirring and mechanical vibration mode, so that powder dispersion is ensured. In the operation process, the whole reaction bin is gradually heated to 40-100 ℃.
The volume of the powder filled in the reaction bin is not more than 1/3 of the total volume of the reaction bin, and the mass of the powder filled in the reaction bin is 1-50 g.
And introducing a gaseous metal precursor into the reaction bin, keeping static to enable the metal precursor and the polymer matrix to be fully adsorbed, and then introducing carrier gas into the reaction bin to flush and remove the residual precursor and reaction byproducts.
And introducing an oxygen precursor into the reaction bin to react with the metal precursor adsorbed on the surface of the polymer matrix, and then introducing a carrier gas into the reaction bin to flush and remove the residual precursor and reaction byproducts. And finishing the first metal oxide atomic layer coating.
And respectively and circularly filling the two reaction precursors for a plurality of times, wherein the thickness of the metal oxide is gradually increased until the set thickness is reached, and the powder coating process is completed.
The oxide film deposited by the ALD technique comprises Al 2 O 3 、TiO 2 、HfO 2 、ZrO 2 And metal oxide thin films.
The deposition thickness of the metal oxide is 1 nm-200 nm.
The metal precursor is a compound raw material containing metal elements and comprises precursors such as trimethylaluminum, aluminum trichloride, titanium tetrachloride, titanium isopropoxide, tetra (dimethylamino) zirconium, hafnium tetrachloride, hafnium nitrate, dimethylamino zirconium and the like.
The oxygen precursor refers to a raw material containing oxygen, and comprises water, ozone, oxygen and the like.
The flow rates of the metal precursor and the oxygen precursor are 10-500 standard milliliters per minute, and the flow rate of the carrier gas is 10-1000 standard milliliters per minute.
The deposition mode of the reaction source and the powder is a static mode, namely, the precursor is kept in a reaction bin for 5-60 s, the precursor is fully adsorbed on the surface of the polymer, and then carrier gas is introduced to wash out the residual precursor and byproducts.
The carrier gas is high-purity nitrogen or argon.
The gas flushing time after each reaction is 10 s-60 s, and the flow rate of the flushing gas is 10-1000 standard milliliters per minute.
The invention discloses a technology for preparing functional composite perovskite quantum dot polymer powder in situ by using a spray drying technology, wherein functional resins such as water absorption and the like are added into a precursor to prepare the powder, an oxide film is deposited on the surface of the powder by using an ALD technology, so that the water and oxygen blocking performance of powder particles is effectively improved, the stability of perovskite quantum dots is improved, and the application range of the perovskite quantum dot powder is widened. The method comprises the following steps: mixing a matrix resin and a functional resin with a perovskite quantum dot precursor solution, and preparing perovskite quantum dot/polymer powder by a spray drying technology; and then depositing a metal oxide film on the surface of the perovskite quantum dot/polymer powder by adopting an Atomic Layer Deposition (ALD) technology to finish the surface coating treatment process of the powder particles.
The beneficial effects that this application can produce include:
(1) The functional composite perovskite quantum dot material provided by the application contains the water-absorbing functional resin in the powder particles, so that the water-blocking and oxygen-blocking performances of the powder particles are effectively improved, and the stability of the perovskite quantum dots is improved.
(2) The functional composite perovskite quantum dot material provided by the application is obtained by coating the surface of the powder particle with the compact metal oxide film by using an ALD technology, so that the stability of the powder particle is improved, and the application range of the polymer material is expanded.
Drawings
Fig. 1: the process flow diagram of the application.
Fig. 2: ALD technology is used for coating a structural schematic of a sample on the surface of a polymer. 1 represents a surface ligand-perovskite quantum dot. 2 represents a matrix formed by mixing a matrix polymer and a functional resin; and 3 represents an atomic layer deposition coated nano-or submicron-scale oxide layer.
Fig. 3: photograph of surface ligand-perovskite quantum dot/polymer powder prepared in example 1.
Fig. 4: photoluminescence spectra of surface ligand-perovskite quantum dot/polymer powder
Fig. 5: scanning electron microscope pictures of the surface ligand-perovskite quantum dot/polymer powder prepared by spray drying.
Fig. 6: scanning electron microscope pictures of the ALD deposited coated powder.
Fig. 7: and (3) a decay comparison curve of the luminescence brightness of the powder coated by adding sodium polyacrylate and ALD and the untreated modified powder along with aging time.
Fig. 8: schematic of a device for spray drying preparation of surface ligand-perovskite quantum dots/polymer powder in the examples of the present application.
In FIG. 8, 1, precursor tank 2, atomizer 3, drying column
4. Cyclone separator 5, powder outlet 6, induced draft fan
7. Solvent recovery port 8, condensing tower 9, and air heater
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
SEM pictures were obtained using a cold field emission scanning electron microscope test from SU8220, hitachi.
The fluorescence emission spectrum is obtained by adopting a spectrum colorimeter test of Admesy company, and the excitation light source is a blue LED with 455 nm.
A schematic process flow diagram of ALD coating of the present application is shown in fig. 1.
The ALD technology of the application is used for coating a film sample on the surface of a polymer, and a structural schematic diagram of the film sample is shown in FIG. 2, wherein 1 represents a surface ligand-perovskite quantum dot. 2 represents a matrix formed by mixing a matrix polymer and a functional resin; and 3 represents an atomic layer deposition coated nano-or submicron-scale oxide layer.
A schematic diagram of a device for preparing the surface ligand-perovskite quantum dot/polymer composite powder material by spray drying is shown in fig. 8. The surface ligand-perovskite quantum dot precursor solution is put into a precursor tank (1), and atomized into small liquid drops in a drying tower (3) by an atomizer (2). And (3) introducing hot air produced by the hot air machine (9) into a drying tower, and drying the atomized droplets to generate the surface ligand-perovskite quantum dot/polymer composite material ultrafine powder. The superfine powder of the surface ligand-perovskite quantum dot/polymer composite material generated in the drying tower and solvent vapor enter a cyclone separator (4) for dry-wet separation, and the superfine powder of the surface ligand-perovskite quantum dot/polymer composite material is collected by a powder outlet (5) below the cyclone separator. Moisture in the cyclone separator enters a condensing tower (8) through an induced draft fan (6) to condense solvent, the solvent is collected by a solvent recovery port (7), and air is discharged. The spray drying method is used for preparing all the superfine powder raw materials of the surface ligand-perovskite quantum dot/polymer composite material in situ to generate the product, the solvent is recoverable, no waste gas is discharged in the whole process, the cost of the product is reduced, and the environment-friendly requirement is compounded.
The molecular weights of the polymers used in the examples are as follows:
the polymethyl methacrylate has a molecular weight of 30000 to 200000.
The molecular weight of the sodium polyacrylate is 3000-7000000.
The molecular weight of polyethylene glycol is 1000-10000.
The molecular weight of polyvinylidene fluoride is 100000 ～ 1000000.
Example 1:
in this example tetrapropylammonium bromide-MAPbBr was chosen 3 And spray-drying the perovskite quantum dot precursor raw material and the matrix polymer polymethyl methacrylate, and the water-absorbing functional resin sodium polyacrylate to prepare composite powder. 0.58g of surface ligand-perovskite quantum dot precursor raw material (the composition is MABr, pbBr 2 Tetrapropylammonium bromide, molar ratio 1mmol:1mmol:0.4 mmol) was dissolved in 300ml of N, N Dimethylformamide (DMF), 15g of polymethyl methacrylate and 1g of sodium polyacrylate were added to form a precursor solution (i.e., the mass ratio of sodium polyacrylate to polymethyl methacrylate added was 0.067), and after 2 hours of stirring and dissolution, spray drying was performed to prepare a powder. The spray drying parameters were set to a feed rate of 500ml/h for the solution, an air inlet pressure of 0.08MPa, an air inlet rate of 60L/min, and an air inlet temperature of 85℃for the dryer.
The surface ligand-perovskite/polymer powder prepared is shown in fig. 3, the powder is bright green, and the luminescence spectrum is shown in fig. 4. At this time, a scanning electron micrograph of the surface ligand-perovskite quantum dot/polymer powder is shown in fig. 5, and the particle size of the powder is 5 μm.
10g of powder 70Drying at the temperature of 2 hours, and then carrying out atomic layer deposition coating. Placing the powdery product into a reaction bin of ALD equipment, vacuumizing (the vacuum degree is 1 torr) while controlling rotary stirring (the rotating speed is 20 r/min), and then heating the cavity to 70 ℃; introducing gaseous trimethylaluminum into the powder reaction bin, adsorbing for 10 seconds, enabling the gaseous trimethylaluminum to be fully contacted and adsorbed with the surface of the powder, and then introducing inert gas to remove redundant trimethylaluminum and byproducts for 60 seconds; and introducing gaseous water into the cavity for 10 seconds, and fully reacting the gaseous water with trimethylaluminum on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation was repeated for 300 cycles with gradually increasing oxide layer thickness until the surface coating treatment of the entire polymer powder was completed. The scanning electron micrograph of the coated powder is shown in FIG. 6, from which it is seen that the surface structure changes, which is ALD deposited Al 2 O 3 The oxide layer has a thickness of 60nm.
The optical stability of the surface ligand-perovskite quantum dot/polymer powder before and after coating was evaluated. The uncoated powder, the powder coated by the functional resin and ALD, and the powder coated by ALD are packaged in the middle of 2 layers of PET films, and are placed in an environment test box with humidity of 60 ℃ and 90% RH for aging experiments. After 200 hours of aging, the brightness was reduced by only a little 5% after 350 hours of aging of the powder coated with functional resin and ALD, as shown in FIG. 7, while the untreated sample had been reduced by more than 25%. The addition of functional resin and surface ALD coated oxide film in the quantum dot/polymer powder is proved to obviously improve the stability of perovskite quantum dots.
Example 2.
In this example tetrabutylammonium bromide-FAPbBr was selected 3 Spray drying perovskite quantum dot precursor raw material and matrix polymer polymethyl methacrylate, water-absorbing functional resin polyethylene glycol, and mixing 0.67g surface ligand-perovskite quantum dot precursor raw material (comprising FABr, pbBr 2 Tetrabutylammonium bromide in a molar ratio of 1.1mmol:1mmol:0.5 mmol) was dissolved in 300ml N, N dimethylformamide and 20g of polymethylpropyl were addedMethyl acrylate and 1g of polyethylene glycol form a precursor solution (i.e. the mass ratio of the added polyethylene glycol to polymethyl methacrylate is 0.05), and after stirring and dissolution for 2 hours, spray drying is carried out to prepare powder. The spray drying parameters were set to a feed rate of 500ml/h for the solution, an air inlet pressure of 0.08MPa, an air inlet rate of 60L/min, and an air inlet temperature of 90℃for the dryer.
The prepared surface ligand-perovskite/polymer microsphere powder is bright green. 1g of the powder was dried at 70℃for 2 hours, followed by atomic layer deposition coating. Placing the powdery product into a reaction bin of ALD equipment, vacuumizing (the vacuum degree is 1 torr) while controlling rotary stirring (the rotating speed is 30 r/min), and then heating the cavity to 75 ℃; introducing gaseous trimethylaluminum into the powder reaction bin, adsorbing for 5 seconds, enabling the gaseous trimethylaluminum to be fully contacted and adsorbed with the surface of the powder, and then introducing inert gas to remove redundant trimethylaluminum and byproducts for 60 seconds; and introducing gaseous water into the cavity for 5 seconds, and fully reacting the gaseous water with trimethylaluminum on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation was repeated and run for 150 cycles to obtain an alumina layer coated powder of about 30nm thickness.
Example 3
In this example, dodecyldimethylbenzyl ammonium bromide-CsPbBr was selected 3 Spray drying perovskite quantum dot precursor raw material and matrix polymer polyvinylidene fluoride, water-absorbing functional resin polyethylene glycol, and mixing 0.73g surface ligand-perovskite quantum dot precursor raw material (CsBr, pbBr 2 Dodecyl dimethyl benzyl ammonium bromide, molar ratio 1mmol:1mmol:0.4 mmol) was dissolved in 300ml N, N dimethylformamide, 25g polyvinylidene fluoride and 2g polyethylene glycol were added to form a precursor solution (i.e., the mass ratio of polyethylene glycol to polyvinylidene fluoride added was 0.08), and after 2 hours of stirring and dissolution, spray drying was performed to prepare a powder. The spray drying parameters were set to a feed rate of 500ml/h for the solution, an air inlet pressure of 0.08MPa, an air inlet rate of 60L/min, and an air inlet temperature of 80℃for the dryer.
The surface ligand-perovskite/polymer powder prepared was bright green. 5g of the powder was dried at 70℃for 2 hours, followed by atomic layer deposition coating. Placing the powdery product into a reaction bin of ALD equipment, vacuumizing (the vacuum degree is 1 torr) while controlling rotary stirring (the rotating speed is 40 r/min), and then heating the cavity to 70 ℃; introducing gaseous titanium tetrachloride into the powder reaction bin, adsorbing for 10 seconds, enabling the gaseous titanium tetrachloride to be fully contacted and adsorbed with the surface of the powder, and then introducing inert gas to remove redundant titanium tetrachloride and byproducts for 60 seconds; and introducing gaseous water into the cavity for 10 seconds, and fully reacting the gaseous water with titanium tetrachloride on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation was repeated and run for 200 cycles to obtain a powder coated with a layer of titanium oxide having a thickness of about 4 nm.
Example 4
In this example Xin Anxiu-MA is selected 0.9 Cs 0.1 PbBr 3 Spray drying perovskite quantum dot precursor raw material and matrix polymer polyvinylidene fluoride, water-absorbing functional resin sodium polyacrylate, mixing 0.55g quantum dot material precursor raw material (composition MABr, csBr, pbBr 2 Xin Anxiu, molar ratio 0.9mmol:0.1mmol:1mmol:0.3 mmol) was dissolved in 300ml N, N dimethylformamide, then 30g polyvinylidene fluoride and 5g sodium polyacrylate were added to form a precursor solution (i.e., the mass ratio of sodium polyacrylate to polyvinylidene fluoride added was 0.16), and after stirring and dissolution for 2 hours, spray drying was performed to prepare a powder. The spray drying parameters were set to a feed rate of 500ml/h for the solution, an air inlet pressure of 0.08MPa, an air inlet rate of 60L/min, and an air inlet temperature of 90℃for the dryer.
The surface ligand-perovskite/polymer powder prepared was bright green. 20g of the powder was dried at 70℃for 2 hours, followed by atomic layer deposition coating. Placing the powdery product into a reaction bin of ALD equipment, vacuumizing (the vacuum degree is 1 torr) while controlling rotary stirring (the rotating speed is 50 r/min), and then heating the cavity to 85 ℃; introducing gaseous tetra (dimethylamino) zirconium into the powder reaction bin, adsorbing for 20 seconds, enabling the gaseous tetra (dimethylamino) zirconium to be fully contacted and adsorbed with the surface of the powder, and then introducing inert gas to remove redundant tetra (dimethylamino) zirconium and byproducts for 80 seconds; and introducing gaseous water into the cavity for 20 seconds, and fully reacting the gaseous water with tetra (dimethylamino) zirconium on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation was repeated and run for 200 cycles to obtain a zirconia layer coated powder of about 10nm thickness.
Example 5
In this example tetrabutylammonium iodide-MAPbI was selected 3 Spray drying perovskite quantum dot precursor raw material and matrix polymer polymethyl methacrylate, water-absorbing functional resin polyethylene glycol, mixing 0.8g quantum dot material precursor raw material (MAI, pbI composition 2 Tetrabutylammonium iodide, molar ratio 1mmol:1mmol:0.5 mmol) was dissolved in 300ml N, N dimethylformamide, and then 20g polymethyl methacrylate and 1g polyethylene glycol were added to form a precursor solution (i.e., the mass ratio of polyethylene glycol to polymethyl methacrylate added was 0.05), and after stirring and dissolution for 2 hours, spray drying was performed to prepare a powder. The spray drying parameters were set to a feed rate of 500ml/h for the solution, an air inlet pressure of 0.08MPa, an air inlet rate of 60L/min, and an air inlet temperature of 90℃for the dryer.
The surface ligand-perovskite/polymer powder prepared was bright red. 10g of the powder was dried at 70℃for 2 hours, followed by atomic layer deposition coating. Placing the powdery product into a reaction bin of ALD equipment, vacuumizing (the vacuum degree is 1 torr) while controlling rotary stirring (the rotating speed is 60 r/min), and then heating the cavity to 70 ℃; introducing gaseous trimethylaluminum into the powder reaction bin, adsorbing for 10 seconds, enabling the gaseous trimethylaluminum to be fully contacted and adsorbed with the surface of the powder, and then introducing inert gas to remove redundant trimethylaluminum and byproducts for 60 seconds; and introducing gaseous water into the cavity for 10 seconds, and fully reacting the gaseous water with trimethylaluminum on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation was repeated for 300 cycles to obtain Al with a thickness of about 60nm 2 O 3 And (3) coating powder.
Example 6
In this example, octylamine iodide/hydrobromic acid-MAPb (Br/I) was selected 3 Perovskite quantum dot precursor raw material and matrix polymer polymethyl methacrylateSpray drying methyl acrylate and water absorbing functional resin polyglycol, and mixing 0.79g of precursor material of surface ligand-perovskite quantum dot material (MAI, pbI composition 2 Octyl amine iodine, hydrobromic acid in a molar ratio of 1mmol:1mmol:0.5mmol:0.5 mmol) was dissolved in 300ml N, N dimethylformamide, 10g polymethyl methacrylate and 1g polyethylene glycol were added to form a precursor solution (i.e., the mass ratio of polyethylene glycol to polymethyl methacrylate added was 0.1), and after stirring and dissolution for 2 hours, spray drying was performed to prepare powder. The spray drying parameters were set to a feed rate of 500ml/h for the solution, an air inlet pressure of 0.08MPa, an air inlet rate of 60L/min, and an air inlet temperature of 90℃for the dryer.
50g of the powder was dried at 70℃for 2 hours, followed by atomic layer deposition coating. Placing the powdery product into a reaction bin of ALD equipment, vacuumizing (the vacuum degree is 1 torr) while controlling rotary stirring (the rotating speed is 60 r/min), and then heating the cavity to 70 ℃; introducing gaseous trimethylaluminum into the powder reaction bin, adsorbing for 10 seconds, enabling the gaseous trimethylaluminum to be fully contacted and adsorbed with the surface of the powder, and then introducing inert gas to remove redundant trimethylaluminum and byproducts for 60 seconds; and introducing gaseous water into the cavity for 10 seconds, and fully reacting the gaseous water with trimethylaluminum on the surface of the particles, wherein the two precursors react to generate a first atomic layer. The operation was repeated for 400 cycles to obtain Al with a thickness of about 80nm 2 O 3 And (3) coating powder.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. The functional composite perovskite quantum dot material is characterized by comprising powder particles and a metal oxide film;
the powder particles comprise surface ligand-perovskite quantum dots, a matrix polymer and water-absorbing functional resin;
the metal oxide film is coated on the surface of the powder particles through atomic layer deposition.
2. The functional composite perovskite quantum dot material according to claim 1, wherein the water-absorbing functional resin comprises at least one of resins containing hydrophilic groups;
preferably, the hydrophilic group includes at least one of a carboxylic acid group, a sulfonic acid group, a hydroxyl group, and an ether group;
preferably, the water-absorbing functional resin comprises at least one of polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, polyvinylpyrrolidone and sodium polyacrylate.
3. The functional composite perovskite quantum dot material according to claim 1, wherein perovskite quantum dots in the surface ligand-perovskite quantum dots have a structural formula ABX 3 、A 3 B 2 X 9 、A 2 BX 6 At least one of (a) and (b); the surface ligand in the surface ligand-perovskite quantum dot has a structural formula CX;
wherein A is selected from NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + 、Rb + 、K + At least one of (a) and (b);
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) and (b);
c is selected from aryl or alkyl organic amine cation with carbon number not less than 3;
x is selected from Br - 、I - 、SCN - At least one of carboxylate radicals.
4. The functional composite perovskite quantum dot material of claim 1, wherein the matrix polymer comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer, polyacrylonitrile, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, polymethyl methacrylate, and polylauryl methacrylate.
5. The functional composite perovskite quantum dot material according to claim 1, wherein the powder particles are obtained by:
atomizing the powder particle precursor solution into small liquid drops, and then drying the atomized small liquid drops to generate powder particles;
the powder particle precursor solution comprises a solvent, a surface ligand-perovskite quantum dot precursor raw material, a matrix polymer and a water-absorbing functional resin;
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 surface ligand-perovskite quantum dot precursor raw material comprises AX, BX m And CX;
wherein A is selected from NH 2 CHNH 2 + 、CH 3 NH 3 + 、Cs + 、Rb + 、K + At least one of (a) and (b);
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) and (b);
c is selected from aryl or alkyl organic amine cation with carbon number not less than 3;
x is selected from Br - 、I - 、SCN - In carboxylate radicalOne less;
m=2, 3 or 4;
preferably, the AX, BX m And CX in a molar ratio of 0.5 to 10:1:0.3 to 10;
preferably, in the powder particle precursor solution, the volume-to-mass ratio of the solvent to the matrix polymer is 300ml: 1-50 g;
the mass ratio of the surface ligand-perovskite quantum dot precursor raw material to the matrix polymer is 0.01-1: 1to 100;
the mass ratio of the water-absorbing functional resin to the matrix polymer is 0.02-2;
preferably, the conditions of atomization include:
solution feed rate: 50-50000 ml/h;
intake pressure of the corresponding atomizer: 0.02-1 MPa, air inlet speed: 15-100L/min;
preferably, the drying conditions include: air inlet temperature: 50-200 ℃.
6. The functional composite perovskite quantum dot material of claim 1, wherein the metal oxide in the metal oxide thin film comprises Al 2 O 3 、TiO 2 、HfO 2 、ZrO 2 At least one of (a) and (b);
preferably, the thickness of the metal oxide film is 1 nm-200 nm;
preferably, the powder particles have a particle size of 0.1 to 50 microns.
7. The method for preparing the functional composite perovskite quantum dot material according to any one of claims 1to 6, which is characterized by comprising the following steps:
and carrying out atomic layer deposition reaction on the raw materials containing the metal precursor, the oxygen precursor and the powder particles to obtain the composite material.
8. The production method according to claim 7, wherein the metal precursor includes at least one of metal-containing compounds;
preferably, the metal precursor comprises at least one of trimethylaluminum, aluminum trichloride, titanium tetrachloride, titanium isopropoxide, zirconium tetra (dimethylamino) oxide, hafnium tetrachloride, hafnium nitrate, zirconium dimethylamino oxide;
preferably, the oxygen precursor comprises at least one of the oxygen-containing species;
preferably, the oxygen precursor includes at least one of water, ozone, and oxygen.
9. The preparation method according to claim 7, characterized in that the preparation method comprises the steps of:
(S1) introducing a gaseous metal precursor into a reaction bin containing powder particles for adsorption;
(S2) introducing a gaseous oxygen precursor for reaction;
preferably, the temperature in the reaction bin is 40-100 ℃ and the vacuum degree is 0.1-300 Torr;
preferably, the time of the adsorption and the reaction is independently 5 to 60 seconds;
preferably, the adsorption is static adsorption;
preferably, during the adsorption and the reaction, the powder dispersion is ensured by at least one of rotation, stirring and vibration of the bin body;
preferably, optionally, the adsorption further comprises the following steps after the adsorption is finished: introducing carrier gas to wash out the residual precursor and byproducts;
optionally, the carrier gas comprises at least one of an inert gas;
optionally, the introducing time of the carrier gas is 10-60 s;
preferably, the steps (S1) to (S2) are repeated 1to 500 times.
10. The composite material prepared by the preparation method of any one of claims 1to 6 and any one of claims 7 to 9, and the application of the composite material in the fields of backlight display, micro/Mini LED direct display, illumination or photovoltaic light conversion materials.
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