CN111233031B - Perovskite quantum dot and preparation method thereof - Google Patents
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Abstract
The invention provides a perovskite quantum dot and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing a perovskite crystal material with a dispersion solvent to obtain a dispersion liquid; (2) and (2) carrying out ultrasonic treatment on the dispersion liquid obtained in the step (1) to obtain the perovskite quantum dot. The preparation method is simple and efficient, has low cost, can realize large-scale production, and the finally obtained perovskite quantum dots have high yield and purity, the particle size is 1-20 nm, the particle size is uniform and narrow in distribution, other impurity residues are not contained in the system, the application requirements of the perovskite quantum dots in high-performance devices can be fully met, and the preparation method has great experimental significance and practical significance for realizing industrial application and accelerating the industrial process of the perovskite quantum dots.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a perovskite quantum dot and a preparation method thereof.
Background
The perovskite material is a kind of material having the property of reacting with calcium titanate (CaTiO) 3 ) Materials of the same crystal structure, first discovered by Gustav Rose in 1839, later named by russian mineralogist l.a.perovski. The perovskite material has a general structural formula of ABO 3 Or ABX 3 Wherein A represents a cation, B represents a transition metal element, and X is a halogen element; the perovskite material has a cubic crystal structure, and the special crystal structure endows the perovskite material with a plurality of unique physicochemical properties, such as light absorption and electro-catalysisChemical property, etc., and has great application prospect in the chemical and physical fields.
The large family of perovskites now includes hundreds of species, ranging from conductors, semiconductors to insulators, and many of which are artificially synthesized. Since 2009, halide perovskite materials were innovatively introduced into the field of solar cells, achieving a solar conversion rate of 3.8% for the first time, and perovskite materials, such as perovskite solar cells, Perovskite Light Emitting Diodes (PLEDs), lasers, field effect transistors, and photodetectors, have become research hotspots in the field of optoelectronics due to their excellent optoelectrical properties and low-cost processing techniques. The material has become a star material in the field of materials at present, and is an indispensable functional material in the future photoelectric field. Regarding the size of the perovskite material, on one hand, people are dedicated to preparing the perovskite crystal material with large size so as to fully exert the unique performance of the perovskite crystal material; on the other hand, the perovskite nano material and the perovskite quantum dot material with smaller sizes are prepared, so that the quantum confinement effect generated by the small sizes is utilized. Compared with large-sized perovskite crystalline materials, the exciton binding energy of perovskite quantum dots is remarkably enhanced, which tends to cause high absolute quantum yield due to the size-dependent quantum confinement effect.
At present, the preparation method of perovskite nano-materials is mainly based on chemical synthesis methods, including Chemical Vapor Deposition (CVD), thermal injection, ligand-assisted precipitation, in-situ preparation strategy, and the like. For example, CN110144210A discloses a preparation method of bromide perovskite quantum dots, which comprises the following steps: firstly, dissolving methylamine or formamidine ammonium bromide, metal bromide, N-octylamine and oleic acid in N, N-dimethylformamide, and stirring to obtain a perovskite quantum dot precursor solution; then adding the perovskite quantum dot precursor solution into toluene and fully stirring to obtain a clear yellow-green perovskite quantum dot solution; and centrifugally purifying the perovskite quantum dot solution, and passivating the perovskite quantum dot solution by using a mixed solution of dodecyl phosphoric acid and a weak polar solvent to obtain a passivated perovskite quantum dot solution. CN108504355A discloses a titanium ore quantum dot preparation method and a perovskite quantum dot solution, wherein the preparation method specifically comprises the following steps: adding a first solution containing cesium oleate, a second solution containing lead halide and a third solution containing didodecyldimethylammonium bromide into a nonpolar alkyl solution according to a preset proportion, and stirring to obtain a perovskite quantum dot solution; the perovskite quantum dot solution contains pure phase cesium lead halide.
In the existing perovskite quantum dot preparation technology, a bottom-up chemical synthesis method has the characteristics of flexible operation and controllable product appearance, but has the defects of harsh reaction conditions, complex post-treatment and difficult large-scale preparation. More importantly, the raw materials in the chemical synthesis process are difficult to realize 100% conversion, and the obtained quantum dots inevitably contain unreacted raw material compounds, so that the yield of the quantum dots is low, the impurity content is high, the purification process is complex, and the purity of the perovskite quantum dots cannot meet the application requirement of higher performance.
Therefore, research and development of a strategy for preparing the high-purity perovskite quantum dots simply, efficiently, at low cost and in high yield on a large scale are realized, so that industrial application is realized, the industrial process is accelerated, and the method has great theoretical and practical significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of perovskite quantum dots, which can effectively solve the problems of complex preparation process, high cost, low yield and difficulty in realizing large-scale production of the perovskite quantum dots in the prior art, and obtain the perovskite quantum dots with high yield, high purity and uniform appearance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a perovskite quantum dot, comprising the steps of:
(1) mixing a perovskite crystal material with a dispersion solvent to obtain a dispersion liquid;
(2) and (2) carrying out ultrasonic treatment on the dispersion liquid obtained in the step (1) to obtain the perovskite quantum dot.
The preparation method of the perovskite quantum dot provided by the invention is a top-down preparation strategy, and the perovskite quantum dot with nano-grade uniform appearance and size is obtained by taking a perovskite crystal material with macroscopic size as a raw material through the combination and cooperation of physical methods such as dispersion, ultrasound and the like. The preparation method is simple and efficient, the cost is low, large-scale production can be realized, the particle size of the finally obtained perovskite quantum dot is 1-20 nm, the particle size distribution is narrow, the purity of the perovskite quantum dot is high, other impurities cannot be left in the system, and the application requirement of the perovskite quantum dot in a high-performance device can be fully met.
In the present invention, the perovskite crystal material of step (1) is selected from any one of inorganic perovskite crystal material, organic perovskite crystal material or organic-inorganic hybrid perovskite crystal material or a combination of at least two of them.
In the invention, the perovskite crystal material in the step (1) is a perovskite crystal material having the same structure with CaTiO 3 Materials of the same crystal structure.
Preferably, the perovskite crystal material in the step (1) is selected from CaTiO 3 、BiFeO 3 、ABX 3 Or Cs 4 PbX' 6 Any one or a combination of at least two of them.
Wherein A is selected from Cs + 、CH 3 NH 3 + Or CH (NH) 2 ) 2 + B is selected from Pb 2+ Or Sn 2+ X, X' are each independently selected from Cl - 、Br - Or I - Any one or a combination of at least two of them.
Preferably, the perovskite crystal material of step (1) is selected from CaTiO 3 、BiFeO 3 、CsPbCl 3 、CsPbBr 3 、CsPbI 3 、Cs 4 PbCl 6 、Cs 4 PbBr 6 、Cs 4 PbI 6 、Cs 4 PbBr 6 ·CsPbBr 3 、CH 3 NH 3 PbCl 3 、CH 3 NH 3 PbBr 3 、CH 3 NH 3 PbI 3 、CH(NH 2 ) 2 PbCl 3 、CH(NH 2 ) 2 PbBr 3 、CH(NH 2 ) 2 PbI 3 Or CH 3 NH 3 Pb(Cl,Br) 3 Any one of them.
Preferably, the two-dimensional planar size of the perovskite crystal material in the step (1) is 0.1 to 10000 μm, such as 0.5 μm, 1 μm, 5 μm, 10 μm, 50 μm, 100 μm, 200 μm, 400 μm, 600 μm, 800 μm, 1000 μm, 2000 μm, 4000 μm, 6000 μm, 8000 μm or 9000 μm, and the specific point values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive of the specific point values included in the range.
In the invention, the perovskite crystal material in the step (1) is a pretreated perovskite crystal material.
Preferably, the method of pre-treatment comprises grinding and/or ball milling, further preferably ball milling.
Preferably, the ball milling comprises dry ball milling or wet ball milling, and more preferably dry ball milling.
Preferably, the dry ball milling method comprises the following steps: and mixing the perovskite crystal material, the grinding aid material and the ball milling balls, carrying out ball milling, separating the ball milling balls and the grinding aid material to obtain the pretreated perovskite crystal material.
As a preferred technical scheme of the invention, the perovskite crystal material in the step (1) is a perovskite crystal material which is subjected to pretreatment, and the pretreatment method is preferably dry ball milling, namely, the perovskite crystal material with larger size is mixed with a grinding aid material and ball milling balls and then ball milling is carried out. The grinding aid material is added to greatly increase the number of stress points acting on the surface of the perovskite crystal material, and the grinding aid material is used as a medium, so that the generated acting force is extremely high, and the effect of crushing the perovskite crystal material is achieved.
Preferably, the ball milling time is 0.5-120 h, such as 1h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 22h, 25h, 28h, 30h, 32h, 35h, 38h, 40h, 42h, 45h, 48h, 50h, 60h, 80h, 100h, 110h or 115h, and the specific values therebetween are limited by space and for simplicity, the invention does not list the specific values included in the range, and further preferably 1-24 h.
As a preferable technical scheme of the invention, the ball milling time is 0.5-120 h, which is beneficial to obtaining the perovskite quantum dots with high yield. If the ball milling time is less than 0.5h, the ball milling is not thorough, and the perovskite crystal material is not completely crushed, so that the yield of the perovskite quantum dots is reduced; if the ball milling time is more than 120h, the crushing effect tends to be extreme, energy waste is caused, and the initial purpose of high efficiency and energy conservation is achieved.
Preferably, the grinding aid material is selected from any one or a combination of at least two of silicon dioxide, titanium dioxide, silicon carbide, zirconium dioxide, aluminum oxide or zinc oxide.
The grinding aid material is easy to remove, impurities cannot be introduced into the perovskite crystal material, the hardness of the grinding aid material is high, and the grinding aid material has good grinding and stripping effects on the perovskite crystal material.
Preferably, the particle size of the grinding aid material is 50-10000 nm, such as 55nm, 60nm, 80nm, 100nm, 300nm, 500nm, 700nm, 900nm, 1000nm, 1200nm, 1400nm, 1500nm, 1700nm, 1800nm, 2000nm, 5000nm, 7000nm or 9000nm, and the specific values therebetween are limited by space and for the sake of brevity, the invention does not provide an exhaustive list of specific values included in the range, and more preferably 50-2000 nm.
Preferably, the mass ratio of the perovskite crystal material to the grinding aid material is 1 (1-100), such as 1:3, 1:5, 1:7, 1:9, 1:10, 1:12, 1:15, 1:18, 1:20, 1:22, 1:24, 1:26, 1:28, 1:30, 1:35, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:95, and the like, and more preferably 1 (5-30).
According to the preferred technical scheme, the mass ratio of the perovskite crystal material to the grinding aid material is 1 (1-100), so that the auxiliary ball milling effect of the grinding aid material can be fully exerted, the process is simplified, the cost is saved, and a good ball milling effect is realized. If the mass ratio of the perovskite crystal material to the grinding aid material is more than 1:1, the grinding aid material is too little to play a role of assisting ball milling; if the mass ratio of the perovskite crystal material to the grinding aid material is less than 1:100, unnecessary resource waste is caused, the burden of later impurity removal is increased, and the initial purpose of high efficiency and energy conservation is violated.
Preferably, the material of the ball grinding ball comprises any one or a combination of at least two of agate, zirconium dioxide, stainless steel, prepared steel, hard tungsten carbide, silicon nitride or sintered corundum.
Preferably, the ball grinding balls have a diameter of 0.5 to 20mm, such as 0.8mm, 1mm, 1.5mm, 2mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm, 18mm or 19mm, and the specific values therebetween are not exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the mass ratio of the perovskite crystal material to the ball milling ball is 1 (10-1000), for example, 1:20, 1:30, 1:40, 1:45, 1:50, 1:55, 1:60, 1:70, 1:90, 1:100, 1:120, 1:150, 1:180, 1:200, 1:220, 1:250, 1:280, 1:300, 1:320, 1:350, 1:400, 1:500, 1:700, 1:900 or 1:950, and the like, and more preferably 1 (50-300).
Preferably, the dry ball milling further comprises the steps of ball milling ball separation and grinding aid material separation.
Preferably, the method for ball milling ball separation is screening.
Preferably, the method of grinding aid material separation is centrifugation.
Preferably, the rotation speed of the centrifugation is 1000-6000 r/min, such as 1500r/min, 2000r/min, 2500r/min, 3000r/min, 3500r/min, 4000r/min, 4500r/min, 5000r/min or 5500r/min and the like; the centrifugation time is 10-60 min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55 min.
The centrifugation comprises the following specific steps: and dispersing a mixture of the perovskite crystal material and the grinding aid material (after ball grinding is separated) in a solvent, centrifuging at the rotating speed of 1000-6000 r/min for 10-60 min, and obtaining the grinding aid material as the lower-layer precipitate.
In the present invention, the dispersion solvent in the step (1) is selected from any one or a combination of at least two of N-methylpyrrolidone, N-vinylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone, γ -butyrolactone, formamide, N-methylformamide, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, tetramethylurea, benzene, toluene, p-xylene, N-hexane, cyclohexane, chlorobenzene, bromobenzene, benzonitrile, benzaldehyde, benzyl benzoate, dibenzyl ether, tetrahydrofuran, butanone, methanol, ethanol, or isopropanol.
Preferably, the perovskite crystal material of step (1) is selected from CsPbCl 3 、CsPbBr 3 、CsPbI 3 、Cs 4 PbCl 6 、Cs 4 PbBr 6 、Cs 4 PbI 6 、Cs 4 PbBr 6 ·CsPbBr 3 、CH 3 NH 3 PbCl 3 、CH 3 NH 3 PbBr 3 、CH 3 NH 3 PbI 3 、CH(NH 2 ) 2 PbCl 3 、CH(NH 2 ) 2 PbBr 3 、CH(NH 2 ) 2 PbI 3 Or CH 3 NH 3 Pb(Cl,Br) 3 Is selected from any one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylformamide (NMF), 1, 3-dimethyl-2-imidazolidinone (DMI), or Tetramethylurea (TMU), or a combination of at least two thereof.
In the present invention, the perovskite crystal material has a special molecular structure and crystal structure, and the combined atoms of the perovskite crystal material interact with each other through ionic bonds, so that the selection of the dispersion solvent has a great influence on the dispersion result. If a solvent (such as water) with larger polarity is selected as a dispersing solvent, ultrasonic dispersion is carried out after the solvent is mixed with the perovskite crystal material, the perovskite crystal molecules are directly cracked, and the stable nano-scale perovskite quantum dots cannot be obtained. If a nonpolar solvent (for example, toluene and/or n-hexane) is selected as a dispersion solvent and subjected to ultrasonication, the perovskite crystal material cannot be broken to 10nm or less, that is, perovskite quantum dots cannot be obtained.
As a preferred technical scheme, the invention selects a weak polar aprotic solvent (such as NMP, DMF, DMSO, NMF, DMI or TMU and the like) as a dispersion solvent to be mixed and ultrasonically treated with the perovskite crystal material, the perovskite crystal material is ultrasonically crushed to a molecular cluster, the complete perovskite molecular structure is kept, and a stable intermediate adduct solution is formed with the weak polar aprotic solvent. By the Lewis acid-base theory, an aprotic solvent containing lone pair electrons is used as Lewis base, and stable acid-base adduct molecules are formed between the aprotic solvent and perovskite molecules used as Lewis acid, so that stable acid-base adduct solution is obtained. The acid-base adduct solution is dried by simple spin coating to obtain perovskite quantum dots and perovskite quantum dot films with extremely small sizes, and the interaction brought by the acid-base adduct limits the nucleation growth of the perovskite quantum dots in the drying process, so that the perovskite quantum dots with small particle sizes and uniform appearance are obtained.
In the present invention, the concentration of the perovskite crystal material in the dispersion of step (1) is 1-100 mg/mL, such as 2mg/mL, 5mg/mL, 8mg/mL, 10mg/mL, 13mg/mL, 15mg/mL, 18mg/mL, 20mg/mL, 25mg/mL, 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL, 50mg/mL, 60mg/mL, 80mg/mL, 90mg/mL or 95mg/mL, and the specific values therebetween are not exhaustive, and for brevity and simplicity, the present invention does not list the specific values included in the range, preferably 1-20 mg/mL.
As a preferable technical scheme of the invention, the concentration of the perovskite crystal material in the dispersion liquid in the step (1) is 1-100 mg/mL, and the perovskite crystal material can be effectively crushed and stripped under the action of ultrasonic waves. If the concentration of the perovskite crystal material in the dispersion liquid is less than 1mg/mL, the concentration of the dispersion liquid is low, the effect of the ultrasonic on the material is not obvious, and the final yield and the ultrasonic crushing effect are influenced; if the concentration of the perovskite crystal material in the dispersion is more than 100mg/mL, the dispersion reaches a supersaturated state, resulting in waste of the material.
In the present invention, the ultrasound in step (2) includes water bath type ultrasound and/or probe type ultrasound, preferably probe type ultrasound.
In the present invention, the power of the ultrasound in step (2) is 50-1000W, such as 60W, 80W, 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W, 500W, 550W, 600W, 650W, 700W, 750W, 800W, 850W, 900W or 950W, and the specific point values between the above point values are limited to space and for the sake of brevity, and the present invention is not exhaustive of the specific point values included in the range.
Preferably, the ultrasonic treatment time in step (2) is 0.5-120 h, such as 1h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 22h, 25h, 28h, 30h, 32h, 35h, 38h, 40h, 42h, 45h, 48h, 50h, 60h, 80h, 100h, 110h or 115h, and specific point values between the above point values are limited to space and simplicity, and the invention does not exhaust the specific point values included in the range, and further preferably 1-50 h.
As a preferable technical scheme of the invention, the power of the ultrasonic dispersion in the step (2) is 50-1000W, the time is 0.5-120 h, and the particle size and the yield of the perovskite quantum dots can be effectively controlled. If the power of the ultrasound is less than 50W, the power is too low, and the ultrasound effect is not obvious; if the power of supersound is greater than 1000W, the effect of supersound dispersion tends to the saturation, and is little to final yield influence, can cause the waste of the energy moreover, has the initial purpose of violating high-efficient energy-conservation.
In the invention, the perovskite quantum dots in the step (2) are perovskite quantum dot acid-base adduct solution or perovskite quantum dot dispersion liquid, and perovskite quantum dot dispersion liquid is preferred.
Preferably, the perovskite quantum dot acid-base adduct solution is obtained and then spin-coated, dried and filmed to obtain a perovskite quantum dot thin film, or a perovskite quantum dot-polymer composite thin film material and a perovskite quantum dot-polymer composite fiber material can be prepared by a simple solution method.
Preferably, step (2) further comprises purification of the perovskite quantum dots.
Preferably, the purification method comprises centrifugation and/or vacuum filtration, and a liquid phase is retained after purification, so that the perovskite quantum dot dispersion liquid is obtained.
Preferably, the pore diameter of the filter membrane of the vacuum filtration is 0.01-0.04 μm, such as 0.015 μm, 0.02 μm, 0.025 μm, 0.03 μm or 0.035 μm.
Preferably, the rotation speed of the centrifugation is 1000-6000 r/min, such as 1200r/min, 1500r/min, 1800r/min, 2000r/min, 2300r/min, 2500r/min, 2800r/min, 3000r/min, 3200r/min, 3500r/min, 3800r/min, 4000r/min, 4200r/min, 4500r/min, 4700r/min, 5000r/min, 5200r/min, 5500r/min, 5700r/min or 5900 r/min.
Preferably, the centrifugation time is 10-60 min, such as 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, 32min, 35min, 38min, 40min, 42min, 45min, 48min, 50min, 52min, 55min, 57min or 59 min.
In the invention, the purification is to separate out perovskite crystal particles with large particle size which are not completely broken in the system.
In the invention, the perovskite quantum dot is a perovskite quantum dot acid-base adduct solution or a perovskite quantum dot dispersion liquid, and the preparation method specifically comprises the following steps:
(1) mixing the perovskite crystal material subjected to ball milling and/or grinding pretreatment with a dispersion solvent to obtain a dispersion liquid with the concentration of the perovskite crystal material being 1-100 mg/mL;
(2) and (2) carrying out ultrasonic treatment on the dispersion liquid obtained in the step (1) for 0.5-120 h under the power of 50-1000W, carrying out optional purification treatment of centrifugation and/or vacuum filtration, and retaining a liquid phase to obtain the perovskite quantum dot acid-base adduct solution or the perovskite quantum dot dispersion liquid.
In another aspect, the present invention provides a perovskite quantum dot obtained by the preparation method as described above.
Preferably, the particle size of the perovskite quantum dot is 1-20 nm, such as 2nm, 4nm, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm or 19nm, and the specific values therebetween are limited by space and for the sake of brevity, the invention does not exhaust the specific values included in the range, and more preferably 1-5 nm.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the perovskite quantum dot provided by the invention is a top-down preparation strategy, and the perovskite quantum dot with nano-grade uniform appearance and size is obtained by taking a perovskite crystal material with macroscopic size as a raw material through the combination and cooperation of physical methods such as dispersion, ultrasound and the like. The preparation method is simple and efficient, has low cost, can realize large-scale production, the particle size of the finally obtained perovskite quantum dot is 1-20 nm, the particle size distribution is narrow, the purity of the perovskite quantum dot is high, other impurity residues are not contained in the system, the application requirement of the perovskite quantum dot in a high-performance device can be fully met, and the preparation method has great experimental significance and practical significance for realizing industrial application and accelerating the industrial process of the perovskite quantum dot.
Drawings
FIG. 1 shows the perovskite crystal material Cs as the starting material in example 1 4 PbBr 6 ·CsPbBr 3 Scanning electron microscope images of;
FIG. 2 shows Cs obtained in example 1 4 PbBr 6 ·CsPbBr 3 Transmission electron microscopy images of perovskite quantum dots;
FIG. 3 shows Cs obtained in example 1 4 PbBr 6 ·CsPbBr 3 An enlarged transmission electron microscope image of the perovskite quantum dots;
FIG. 4 shows Cs obtained in example 1 4 PbBr 6 ·CsPbBr 3 An infrared spectrogram of acid-base adduct solution of perovskite quantum dot, wherein 1 is a test curve of dispersing solvent NMP, and 2 is Cs 4 PbBr 6 ·CsPbBr 3 The test curve of the acid-base adduct solution of the perovskite quantum dot is that A is 1675cm -1 C ═ O peak at;
FIG. 5 shows Cs obtained in example 1 4 PbBr 6 ·CsPbBr 3 Partial enlarged infrared spectrum of perovskite quantum dot acid-base adduct solution, wherein 1 is a test curve of a dispersion solvent NMP, and 2 is Cs 4 PbBr 6 ·CsPbBr 3 Test curve of acid-base adduct solution of perovskite quantum dot。
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a method for preparing a perovskite quantum dot, where the perovskite quantum dot is Cs 4 PbBr 6 ·CsPbBr 3 The perovskite quantum dot acid-base adduct solution comprises the following specific steps:
(1) 0.8g of Cs with an average size of 700. mu.m 4 PbBr 6 ·CsPbBr 3 Mixing the perovskite crystal material with N-methylpyrrolidone (NMP) to obtain Cs 4 PbBr 6 ·CsPbBr 3 A dispersion having a perovskite crystal material concentration of 10 mg/mL;
(2) performing ultrasonic treatment on the dispersion liquid obtained in the step (1) for 10h under the power of 300W, then centrifuging the dispersion liquid for 30min at the centrifugal rotating speed of 6000r/min, removing perovskite crystal particles which are not completely crushed to obtain Cs 4 PbBr 6 ·CsPbBr 3 Acid-base adduct solution of perovskite quantum dots.
Mixing the Cs 4 PbBr 6 ·CsPbBr 3 Dropping the perovskite quantum dot dispersion liquid on a cover glass with good hydrophilicity treatment for spin coating at the rotating speed of 2500r/min for 60s, heating to 70 ℃ and drying to obtain Cs 4 PbBr 6 ·CsPbBr 3 Perovskite quantum dot thin film.
The raw material perovskite crystalline material Cs used in this example was tested by scanning electron microscopy (SEM, S4800) 4 PbBr 6 ·CsPbBr 3 The surface topography of (a); cs obtained in this example was tested by a transmission electron microscope (TEM, F20) 4 PbBr 6 ·CsPbBr 3 The surface morphology of the perovskite quantum dots; the test results are shown in FIGS. 1 to 3.
FIG. 1 shows the raw perovskite crystal material Cs in this example 4 PbBr 6 ·CsPbBr 3 Scanning electron micrograph of (1), from1, the perovskite crystal material has an average size of about 700 μm and a large size.
FIG. 2 shows Cs obtained in this example 4 PbBr 6 ·CsPbBr 3 As can be seen from fig. 2, the perovskite quantum dots have an average size of about 3nm and are relatively uniform in size.
FIG. 3 shows Cs obtained in this example 4 PbBr 6 ·CsPbBr 3 An enlarged transmission electron microscope image of the perovskite quantum dot shows that Cs is shown in FIG. 3 4 PbBr 6 ·CsPbBr 3 The perovskite quantum dots show obvious lattice stripes, which shows that the prepared perovskite quantum dots have high quality and no obvious defects.
Cs obtained in this example 4 PbBr 6 ·CsPbBr 3 Concentrating the perovskite quantum dot acid-base adduct solution, and testing by using a Fourier infrared spectrometer (Spectrum One) to obtain Cs 4 PbBr 6 ·CsPbBr 3 The infrared spectrum of the acid-base adduct solution of perovskite quantum dot is shown in FIG. 4, wherein 1 is the test curve of dispersion solvent NMP, and 2 is Cs 4 PbBr 6 ·CsPbBr 3 The test curve of the acid-base adduct solution of the perovskite quantum dot is that A is 1675cm -1 C ═ O peak at; FIG. 5 shows Cs 4 PbBr 6 ·CsPbBr 3 An enlarged partial infrared spectrum (i.e., an enlarged view of region a in fig. 4) of the perovskite quantum dot acid-base adduct solution, wherein 1 is a test curve of a dispersion solvent NMP, and 2 is Cs 4 PbBr 6 ·CsPbBr 3 Test curves of acid-base adduct solutions of perovskite quantum dots. As is clear from FIGS. 4 and 5, Cs is compared with NMP, which is a dispersion solvent 4 PbBr 6 ·CsPbBr 3 Acid-base adduct solution of perovskite quantum dot in 1675cm -1 Peak at position C ═ O and 2877cm -1 The C-H peak at the position has obvious displacement and broadening, according to the theoretical analysis of acid-base adducts, the lead atom (Pb) in the perovskite as Lewis acid acts on the oxygen atom (O) in NMP with Lewis base with lone pair electrons, and further the C ═ O peak of NMP is red shifted and broadened, thus further illustrating the formation of the acid-base adducts; and alsoThis interaction is favored, so that the perovskite molecules are strongly restricted during the dry nucleation process, thereby forming perovskite quantum dots.
Example 2
This example provides a method for preparing a perovskite quantum dot, where the perovskite quantum dot is Cs 4 PbBr 6 ·CsPbBr 3 The perovskite quantum dot acid-base adduct solution comprises the following specific steps:
(1) mixing Cs 4 PbBr 6 ·CsPbBr 3 The perovskite crystal material is pretreated by a ball milling method, 1g of Cs with the average size of 700 mu m is taken 4 PbBr 6 ·CsPbBr 3 Mixing the perovskite crystal material, 20g of silicon dioxide with the average particle size of 400nm and 100g of agate balls with the diameter of 0.5mm, carrying out ball milling for 12h, and removing the ball milling balls through screening by a screen after ball milling to obtain pretreated Cs 4 PbBr 6 ·CsPbBr 3 A perovskite crystal material primary product; mixing the perovskite crystal material with N-methylpyrrolidone (NMP) to obtain a dispersion liquid with the concentration of the perovskite crystal material being 10 mg/mL;
(2) performing ultrasonic treatment on the dispersion liquid obtained in the step (1) for 10h under the power of 300W, and then centrifuging the dispersion liquid at the centrifugal rotating speed of 6000r/min for 30min to remove grinding aids and perovskite crystal particles which are not completely crushed to obtain Cs 4 PbBr 6 ·CsPbBr 3 Acid-base adduct solution of perovskite quantum dots.
Example 3
This example differs from example 1 in that the starting material in step (1) was used with equal mass of CsPbBr 3 Perovskite crystal material is replaced to obtain CsPbBr 3 Acid-base adduct solution of perovskite quantum dots.
Example 4
This example differs from example 2 in that Cs in step (1) is added 4 PbBr 6 ·CsPbBr 3 Equal mass CsPbBr for perovskite crystal material 3 Perovskite crystal material is replaced to obtain CsPbBr 3 Acid-base adduct solution of perovskite quantum dots.
Example 5
This example differs from example 2 only in that NMP in step (1) is replaced with an equal volume of toluene.
Example 6
This example differs from example 2 only in that NMP in step (1) is replaced with an equal volume of n-hexane.
Example 7
The present embodiment is different from embodiment 1 only in that the power of the ultrasound in step (2) is 50W and the time of the ultrasound is 120 h.
Example 8
The present example is different from example 1 only in that the power of the ultrasound in step (2) is 1000W and the time of the ultrasound is 0.5 h.
Example 9
This example is different from example 1 only in that the power of the ultrasound in step (2) is 40W.
Example 10
The present embodiment is different from embodiment 1 only in that the power of the ultrasound in step (2) is 40W and the time of the ultrasound is 125 h.
Example 11
This example differs from example 1 only in that, in step (1), the concentration of the perovskite crystal material in the dispersion liquid is 1 mg/mL.
Example 12
This example differs from example 1 only in that, in step (1), the concentration of the perovskite crystal material in the dispersion liquid was 0.8 mg/mL.
Comparative example 1
This comparative example differs from example 1 only in that no sonication is performed in step (2).
Comparative example 2
This comparative example differs from example 2 only in that no sonication is performed in step (2).
And (3) performance testing:
and (3) product size testing: the perovskite quantum dots obtained in examples 1 to 12 and comparative examples 1 to 2 were subjected to morphology characterization by a transmission electron microscope to observe the size distribution, and the results are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the preparation methods provided in the embodiments 1 to 4 of the present invention can controllably prepare small-sized perovskite quantum dots with a particle size range of 1 to 5 nm.
The size of the product prepared in examples 5 to 6 does not reach 20nm or less, that is, perovskite quantum dots with ideal particle size are not obtained, which shows that the selection of the dispersion solvent has a great influence on the particle size of the quantum dots in the preparation process of the quantum dots, and the dispersion solvent highly matching the perovskite crystal material needs to be selected according to the type of the perovskite crystal material. But the material is effectively crushed by ball milling and ultrasonic energy, and the perovskite material with macroscopic scale is crushed into the perovskite material with nanometer scale (20-50 nm).
In comparative example 1, the nano-scale perovskite material cannot be obtained without the ultrasonic treatment in the step (2); in comparative example 2, where only the ball milling treatment was performed without the ultrasonic treatment as described in step (2), perovskite quantum dots having a particle size of less than 20nm could not be obtained as well. Therefore, in the preparation method provided by the invention, the ultrasonic step has a decisive role in the formation of the quantum dots.
In conclusion, the perovskite quantum dots with the particle size of 1-5 nm can be obtained by the preparation method provided by the invention, and the average size of the perovskite quantum dots reaches 3 nm. The size of the perovskite crystal material, the type of the dispersion solvent, the concentration of the dispersion, the ultrasonic time and the ultrasonic power all have influences on the product size and the yield. The optimized experimental conditions can ensure the size and yield of the product to the maximum extent, and can not cause unnecessary waste, simplify the process and save the cost.
The applicant states that the present invention is illustrated by the above examples to a perovskite quantum dot of the present invention and a preparation method thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (41)
1. The preparation method of the perovskite quantum dot is characterized by comprising the following steps:
(1) mixing a perovskite crystal material with a dispersion solvent to obtain a dispersion liquid;
the perovskite crystal material is selected from ABX 3 Or Cs 4 PbX' 6 Any one or a combination of at least two of; wherein A is selected from Cs + 、CH 3 NH 3 + Or CH (NH) 2 ) 2 + B is selected from Pb 2+ Or Sn 2+ X, X' are each independently selected from Cl - 、Br - Or I - Any one or a combination of at least two of;
the dispersing solvent is selected from any one or the combination of at least two of N-methyl pyrrolidone, N-vinyl pyrrolidone, N-cyclohexyl pyrrolidone, N-octyl pyrrolidone, N-dodecyl pyrrolidone, formamide, N-methyl formamide, N-dimethyl acetamide, dimethyl sulfoxide, 1, 3-dimethyl-2-imidazolidinone or tetramethylurea;
(2) and (2) carrying out ultrasonic treatment on the dispersion liquid obtained in the step (1) to obtain the perovskite quantum dots, wherein the power of the ultrasonic treatment is 50-1000W.
2. The production method according to claim 1, wherein the perovskite crystal material of step (1) is selected from CsPbCl 3 、CsPbBr 3 、CsPbI 3 、Cs 4 PbCl 6 、Cs 4 PbBr 6 、Cs 4 PbI 6 、Cs 4 PbBr 6 ·CsPbBr 3 、CH 3 NH 3 PbCl 3 、CH 3 NH 3 PbBr 3 、CH 3 NH 3 PbI 3 、CH(NH 2 ) 2 PbCl 3 、CH(NH 2 ) 2 PbBr 3 、CH(NH 2 ) 2 PbI 3 Or CH 3 NH 3 Pb(Cl,Br) 3 Any one of them.
3. The production method according to claim 1, wherein the perovskite crystal material of the step (1) has a two-dimensional plane size of 0.1 to 10000 μm.
4. The production method according to claim 1, wherein the perovskite crystal material of step (1) is a perovskite crystal material that has been subjected to pretreatment.
5. The method of claim 4, wherein the pre-treating comprises milling and/or ball milling.
6. The method of claim 4, wherein the pre-treatment is ball milling.
7. The method of claim 5, wherein the ball milling comprises dry ball milling or wet ball milling.
8. The method of claim 5, wherein the ball milling is dry ball milling.
9. The preparation method according to claim 7, wherein the dry ball milling method comprises the following steps: and mixing the perovskite crystal material, the grinding aid material and the ball milling balls, carrying out ball milling, separating the ball milling balls and the grinding aid material to obtain the pretreated perovskite crystal material.
10. The preparation method of claim 9, wherein the ball milling time is 0.5-120 h.
11. The preparation method of claim 9, wherein the ball milling time is 1-24 h.
12. The preparation method of claim 9, wherein the grinding aid material is selected from any one of silicon dioxide, titanium dioxide, silicon carbide, zirconium dioxide, aluminum oxide or zinc oxide or a combination of at least two of the silicon dioxide, the titanium dioxide, the silicon carbide, the zirconium dioxide, the aluminum oxide or the zinc oxide.
13. The preparation method of claim 9, wherein the grinding aid material has a particle size of 50-10000 nm.
14. The preparation method of claim 9, wherein the grinding aid material has a particle size of 50-2000 nm.
15. The preparation method according to claim 9, wherein the mass ratio of the perovskite crystal material to the grinding aid material is 1 (1-100).
16. The preparation method according to claim 9, characterized in that the mass ratio of the perovskite crystal material to the grinding aid material is 1 (5-30).
17. The method according to claim 9, wherein the material of the ball grinding balls comprises any one or a combination of at least two of agate, zirconia, stainless steel, prepared steel, hard tungsten carbide, silicon nitride, or sintered corundum.
18. The method of claim 9, wherein the ball grinding balls have a diameter of 0.5 to 20 mm.
19. The preparation method according to claim 9, wherein the mass ratio of the perovskite crystal material to the ball grinding balls is 1 (10-1000).
20. The preparation method according to claim 9, wherein the mass ratio of the perovskite crystal material to the ball grinding balls is 1 (50-300).
21. The preparation method according to claim 9, characterized in that the dry ball milling further comprises ball milling ball separation and grinding aid material separation steps;
the ball grinding ball separation method is screening.
22. The method of claim 21, wherein the grinding aid material separation method is centrifugation.
23. The method for preparing the compound of claim 22, wherein the rotation speed of the centrifugation is 1000-6000 r/min, and the time of the centrifugation is 10-60 min.
24. The production method according to claim 1, wherein the perovskite crystal material of step (1) is selected from CsPbCl 3 、CsPbBr 3 、CsPbI 3 、Cs 4 PbCl 6 、Cs 4 PbBr 6 、Cs 4 PbI 6 、Cs 4 PbBr 6 ·CsPbBr 3 、CH 3 NH 3 PbCl 3 、CH 3 NH 3 PbBr 3 、CH 3 NH 3 PbI 3 、CH(NH 2 ) 2 PbCl 3 、CH(NH 2 ) 2 PbBr 3 、CH(NH 2 ) 2 PbI 3 Or CH 3 NH 3 Pb(Cl,Br) 3 And a dispersing solvent selected from any one of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-methylformamide, 1, 3-dimethyl-2-imidazolidinone, or tetramethylurea, or a combination of at least two thereof.
25. The production method according to claim 1, wherein the concentration of the perovskite crystal material in the dispersion liquid in the step (1) is 1 to 100 mg/mL.
26. The production method according to claim 1, wherein the concentration of the perovskite crystal material in the dispersion liquid in the step (1) is 1 to 20 mg/mL.
27. The production method according to claim 1, wherein the ultrasound of step (2) includes bath type ultrasound and/or probe type ultrasound.
28. The production method according to claim 1, wherein the ultrasound of step (2) is a probe-type ultrasound.
29. The preparation method according to claim 1, wherein the time of the ultrasonic treatment in the step (2) is 0.5 to 120 hours.
30. The preparation method according to claim 1, wherein the time of the ultrasonic treatment in the step (2) is 1-50 h.
31. The production method according to claim 1, wherein the perovskite quantum dot in the step (2) is a perovskite quantum dot acid-base adduct solution or a perovskite quantum dot dispersion.
32. The production method according to claim 1, wherein the perovskite quantum dot of step (2) is a perovskite quantum dot dispersion liquid.
33. The production method according to claim 1, wherein the step (2) further comprises purification of the perovskite quantum dot.
34. The preparation method of claim 33, wherein the purification method comprises centrifugation and/or vacuum filtration, and a liquid phase is retained after purification to obtain the perovskite quantum dot dispersion liquid.
35. The method as claimed in claim 34, wherein the aperture of the vacuum filtration membrane is 0.01-0.04 μm.
36. The method of claim 34, wherein the centrifugation is performed at a rotation speed of 1000 to 6000 r/min.
37. The method of claim 34, wherein the centrifugation time is 10-60 min.
38. The preparation method according to claim 1, wherein the perovskite quantum dot is a perovskite quantum dot acid-base adduct solution or a perovskite quantum dot dispersion solution, and the preparation method specifically comprises the following steps:
(1) mixing the perovskite crystal material subjected to ball milling and/or grinding pretreatment with a dispersion solvent to obtain a dispersion liquid with the concentration of the perovskite crystal material being 1-100 mg/mL;
(2) and (2) carrying out ultrasonic treatment on the dispersion liquid obtained in the step (1) for 0.5-120 h under the power of 50-1000W, carrying out optional purification treatment of centrifugation and/or vacuum filtration, and retaining a liquid phase to obtain the perovskite quantum dot acid-base adduct solution or the perovskite quantum dot dispersion liquid.
39. A perovskite quantum dot, wherein the perovskite quantum dot is obtained by the preparation method according to any one of claims 1 to 38.
40. The perovskite quantum dot of claim 39, wherein the particle size of the perovskite quantum dot is 1 to 20 nm.
41. The perovskite quantum dot of claim 39, wherein the particle size of the perovskite quantum dot is 1 to 5 nm.
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