CN114591725A - Perovskite quantum dot and preparation method and application thereof - Google Patents
Perovskite quantum dot and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a perovskite quantum dot and a preparation method and application thereof. The preparation method comprises the following steps: the preparation method comprises the following steps: (1) mixing the pretreatment agent solution with the mesoporous material to obtain a pretreated mesoporous material; (2) mixing a mesoporous material with a perovskite quantum dot precursor material, and dynamically sintering to obtain the perovskite quantum dot material; the chemical general formula of the perovskite quantum dot is CsBX3B comprises Pb and/or Sn, and X comprises any one or combination of at least two of Cl, Br or I. In the process of preparing the perovskite quantum dots, the invention passes through the mediumThe hole material is matched with dynamic sintering, and the two materials have synergistic effect, so that the quantum dot material fully enters the mesoporous material, and the phenomena of uneven mixing, uneven temperature, adhesion of particles and the like in the sintering process are avoided, and the obtained quantum dots synchronously realize the improvement of fluorescence efficiency, the red shift of fluorescence wavelength, the reduction of half-peak width and the improvement of stability.
Description
Technical Field
The invention belongs to the technical field of perovskite quantum dots, and relates to a perovskite quantum dot and a preparation method and application thereof.
Background
With the development of science and technology, the quantum dot display technology has become one of the most important components of modern photoelectric products. The popularization and development of photoelectric products increasingly demand the display performance, stability, environmental protection and other aspects of materials. Compared with the traditional semiconductor quantum dots, the lead-halogen perovskite quantum dots gradually become powerful competitors in the display field in recent years due to the characteristics of excellent optical properties, lower synthesis cost, environmental friendliness and the like.
The all-inorganic lead-containing perovskite quantum dots have the advantages of high fluorescence quantum dot efficiency, narrow emission, wide color gamut and the like, so that the all-inorganic lead-containing perovskite quantum dots are widely researched and applied to photoelectric devices. The prior lead-halogen perovskite quantum dot material is difficult to maintain good stability under severe conditions such as humidity, oxygen environment, ultraviolet light, thermal atmosphere and the like, and the practical application in the display field is greatly influenced. At present, the thermal injection method and the dissolution-precipitation method are mostly adopted to synthesize the all-inorganic lead-containing perovskite quantum dot, and the synthesized quantum dot has good monodispersity, high fluorescence quantum dot efficiency, narrow-band emission and adjustable luminescence, but the water and thermal stability of the perovskite quantum dot synthesized by using oleic acid and oleylamine modification are poor (J.Am.Chem.Soc.2016,138, 5749; Angew.Chem.int.Edit.,2017, DOI:10.1002/anie.201703703), which directly influences the application performance and the prospect of the perovskite quantum dot. Although the literature reports that the stability of the quantum dots in humid air can be improved by using methods such as X-ray radiation, mesoporous silica adsorption, and silica coating, the water and thermal stability of the quantum dots still cannot meet the requirements of practical application. The core-shell structure is considered as one of effective means for improving the stability of the quantum dot, the quantum dot is isolated from the external environment through the coating layer, and the weather resistance and the service life of the quantum dot can be greatly improved.
In the preparation process of the existing mesoporous material calcination method, perovskite precursors or bulk materials enter the pore channels of the mesoporous material through melting or gas state, so that the condition of uneven products inevitably occurs under the static sintering method.
For example, CN111454713A discloses a perovskite quantum dot powder, a preparation method thereof, and a perovskite quantum dot functional material, wherein the preparation method of the perovskite quantum dot powder comprises: dissolving cesium salt and metal salt in ultrapure water to obtain a solution, wherein the metal salt is a lead salt, a tin salt or a germanium salt; adding molecular sieve powder into the solution to obtain mixed feed liquid; spray drying the mixed material liquid to obtain a dried material; and calcining the dried material to obtain the perovskite quantum dot powder.
The above documents adopt a static sintering method, which inevitably results in non-uniform products, including (1) even if a proper temperature is selected, the quantum dots generated in the mesoporous material have gradient distribution in the vertical direction, so that the products are not uniform and cannot be produced in an enlarged manner; (2) due to material stacking and blocking, perovskite components cannot freely and sufficiently enter pore channels of the mesoporous material, and uneven distribution of quantum dots in a final product is also caused; (3) the heat transfer process of static sintering causes the closing time of the mesoporous material to be inconsistent, the size of the quantum dot is not uniform, so that the luminous half-peak width is increased, and the display effect is reduced; (4) under the static sintering environment, the collapse of the mesoporous material can bring the adhesion of adjacent blocks, thereby enlarging the particle size and distribution range and bringing dispersion problems to subsequent application.
Therefore, how to improve the stability of the perovskite quantum dot is an urgent technical problem to be solved.
Disclosure of Invention
The invention aims to provide a perovskite quantum dot and a preparation method and application thereof. According to the invention, in the process of preparing the perovskite quantum dots, the mesoporous material is combined with dynamic sintering, and the two synergistic effects are combined, so that the quantum dot material fully enters the mesoporous material, the phenomena of uneven mixing, uneven temperature, particle adhesion and the like in the sintering process are avoided, the perovskite quantum dot material with uniform concentration and size is obtained, the obtained quantum dots synchronously realize the improvement of fluorescence efficiency, the red shift of fluorescence wavelength, the reduction of half-peak width and the improvement of stability, and the preparation method is suitable for mass production.
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 the pretreatment agent solution with the mesoporous material to obtain a pretreated mesoporous material;
(2) mixing the pretreated mesoporous material obtained in the step (1) with a perovskite quantum dot precursor material, and dynamically sintering to obtain the perovskite quantum dot material;
wherein, the dynamic sintering in the step (2) comprises any one or the combination of at least two of rotary sintering, stirring sintering or conical mixed heating furnace sintering; the chemical general formula of the perovskite quantum dot is CsBX3B comprises Pb and/or Sn, and X comprises any one or combination of at least two of Cl, Br or I.
The perovskite quantum dot precursor material in the invention includes but is not limited to metal salt for preparing quantum dot material or precursor material directly in bulk phase, such as bulk phase CsPbBr3A material.
Compared with the static sintering provided by the invention, the dynamic sintering provided by the invention, such as the common muffle furnace sintering, and the common tube furnace sintering, is static sintering, i.e. the dynamic state is relative motion. The sintering process in the invention is dynamic sintering in the whole process.
In the invention, the dynamic sintering can be realized by various treatment modes, the rotary sintering equipment can be realized by adopting a rotary tube furnace, and a baffle plate for mixing materials is arranged on the inner wall of a heating pipe; the stirring sintering equipment can adopt a stirring type reaction kettle; the conical mixing and sintering equipment can adopt a conical mixer.
According to the invention, in the process of preparing the perovskite quantum dot, the mesoporous material is combined with dynamic sintering, and the two synergistic effects enable the quantum dot material to fully enter the mesoporous material, so that the phenomena of uneven mixing, uneven temperature, particle adhesion and the like in the sintering process are avoided, the perovskite quantum dot material with uniform concentration and size is obtained, the stability of the perovskite quantum dot material is improved, and the perovskite quantum dot material is suitable for mass production.
The quantum dots are uniformly mixed, and particles are free from adhesion, so that the fluorescence efficiency is improved; the quantum dots fully enter the mesoporous material pore passage and grow up, so that the luminescence wavelength is red-shifted; the quantum dots have consistent sizes and weakened self-absorption, so that the half-peak width is reduced; the mesoporous material is completely coated by heating uniformly, and the stability is improved.
According to the invention, through dynamic sintering, the chances of materials being heated and contacted with each other are equalized, the phenomena of nonuniform temperature and material mixing in the sintering process are eliminated, the problems of nonuniform concentration distribution and nonuniform size of quantum dots caused by static sintering are also eliminated, the problem of particle adhesion in the process of pore closing collapse of the mesoporous material is also reduced, uniform nucleation and growth of perovskite quantum dots in the sintering process are realized, the preparation process of raw materials is simplified, and the perovskite quantum dots can be simply mixed without being poured into pore channels of the mesoporous material in advance.
In the invention, if the mesoporous material is not pretreated, the collapse temperature of the mesoporous material cannot be reduced, so that the complete collapse of the mesoporous material cannot be realized, the coating effect on the quantum dots is limited, and the halogen element in the pretreatment agent is consistent with the halogen element in the prepared perovskite quantum dots, so that a halogen-rich environment can be provided in the preparation process, and the repair and passivation of the halogen defect on the surface of the quantum dots are realized.
In the invention, too much pretreatment agent can block the pore channel to influence the result, and too little pretreatment agent can not play a role in passivating the quantum dot defects.
Preferably, the mesoporous material in step (1) has a pore size of 20nm or less, such as 20nm, 18nm, 15nm, 13nm, 10nm, 9nm, 8nm, 7nm, 6nm, 5nm, 4nm, 3nm or 2nm, preferably 3-10 nm.
According to the invention, the aperture size of the mesoporous material is within the range of 3-10 nm, so that the size of quantum dots can be better controlled, the quantum confinement effect is realized, and meanwhile, the quantum dots are more densely coated and have better stability.
Preferably, the mesoporous material in step (1) comprises any one or a combination of at least two of MCM molecular sieve, SBA molecular sieve, ZSM molecular sieve, NaY molecular sieve, Zeolite molecular sieve, porous silica or porous alumina, preferably any one or a combination of at least two of porous silica, porous alumina or MCM molecular sieve.
Preferably, the chemical formula of the pretreating agent in the pretreatment solution is MX, and M includes an alkali metal element.
Preferably, the solvent in the pretreating agent solution comprises any one of water, methanol or acetone or a combination of at least two of them.
Preferably, the mass ratio of the pretreatment agent to the mesoporous material is 1 (1-5), such as 1:1, 1:2, 1:3, 1:4, or 1: 5.
In the step (2), the mass ratio of the perovskite quantum dot precursor material to the pretreated mesoporous material is preferably 1 (1-10), for example, 1:1, 1:2, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, and preferably 1 (3-5).
In the invention, the proportion of the precursor material is too low to generate too few quantum dots, and the proportion is too high to generate the bulk phase perovskite material, so that the quantum dot material cannot be obtained, and in the range of 1 (3-5), the coating of high-quality quantum dots can be better realized, and the material utilization rate is improved.
Preferably, the dynamic sintering of step (2) is rotary sintering.
Preferably, the atmosphere for dynamic sintering in step (2) comprises an atmospheric atmosphere or a protective atmosphere, preferably a protective atmosphere.
In the present invention, when the halogen element, particularly I element, is contained in the perovskite quantum dot material, the oxidation of the halogen element can be prevented in a protective atmosphere.
Preferably, the dynamic sintering of step (2) comprises sequentially performing a first dynamic sintering and a second dynamic sintering.
According to the invention, the consistency of the components and the size of the quantum dots can be better realized by sequentially performing primary dynamic sintering and secondary dynamic sintering, namely performing a two-step dynamic sintering process, the adhesion of particles after sintering is prevented from being increased, the precursor material or perovskite material can enter the mesoporous material in the primary dynamic sintering process, the mesoporous material can be collapsed in the secondary dynamic sintering process, the perovskite quantum dot material can be coated, the perovskite quantum dots can be generated in the cooling process, and if the primary dynamic sintering process is replaced by static sintering or the secondary sintering process is replaced by static sintering, the luminescence property, the uniformity and the particle size of the prepared perovskite quantum dots can be negatively influenced, so that the applicability of the perovskite quantum dots is influenced.
In the invention, two dynamic sintering processes can be continuously completed, or the intermediate product can be cooled and taken out after the primary dynamic sintering, and the secondary dynamic sintering is carried out again after cleaning and filling.
Among them, it is preferable that the two dynamic sinterings are separately performed. The two dynamic sintering processes are separately carried out, so that the influence of unreacted substance residue and the temperature rise process of the two dynamic sintering processes on the proportion of the quantum dot material is avoided, and meanwhile, the mesoporous material can be filled again in the middle of the two sintering processes.
Preferably, in the primary dynamic sintering, the rotation speed of stirring sintering is more than or equal to 100r/min, such as 100r/min, 130r/min, 150r/min, 180r/min, 200r/min, 250r/min or 300 r/min.
Preferably, in the primary dynamic sintering, the rotating speed of the rotary sintering is more than or equal to 5r/min, such as 5r/min, 6r/min, 7r/min, 8r/min, 9r/min, 10r/min, 11r/min, 12r/min, 13r/min, 14r/min or 15 r/min.
In the invention, in the one-time dynamic sintering process, the rotating speed of rotary sintering is not required to be too high, uniform mixing and uniform temperature are realized, and the quantum dot material can fully enter a pore channel of the mesoporous material in a molten and volatile state.
Preferably, in the primary dynamic sintering, the rotation speed of the conical mixing heating furnace is more than or equal to 20r/min, such as 20r/min, 25r/min, 30r/min, 35r/min, 40r/min, 45r/min, 50r/min, 55r/min or 60 r/min.
Preferably, said CsBX3When X does not include I, the sintering temperature of the first dynamic sintering is 350-650 ℃, such as 350 ℃, 380 ℃, 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 630 ℃ or 650 ℃, preferably 570 ℃ -590℃。
In the invention, the temperature of one-time dynamic sintering is too low, so that the melting volatilization of the precursor or the perovskite material cannot be realized, while the sintering temperature is too high, so that the excessive volatilization loss of the perovskite material and the premature collapse of the mesoporous material can be caused, and the material can better enter the pore channel of the mesoporous material within the range of 570-590 ℃.
Preferably, said CsBX3When X in (A) at least includes I, the sintering temperature of the first dynamic sintering is 350-550 ℃, for example 350 ℃, 380 ℃, 400 ℃, 430 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃ or 500 ℃, preferably 450-500 ℃.
In the present invention, CsBX3When X in the formula (II) at least comprises I, the sintering temperature is properly reduced, and the temperature is too high, which can cause CsPbI3Excessive volatilization loss.
Preferably, the intermediate product after the primary dynamic sintering is subjected to filling treatment.
In the invention, the quantum dots can be passivated and coated more densely by filling, such as aluminum isopropoxide and nitrate can be filled.
Preferably, in the secondary dynamic sintering, the rotation speed of stirring sintering is more than or equal to 200r/min, such as 200r/min, 230r/min, 250r/min, 280r/min, 300r/min, 330r/min, 350r/min, 380r/min or 400 r/min.
Preferably, in the secondary dynamic sintering, the rotation speed of the rotary sintering is more than or equal to 15r/min, such as 15r/min, 16r/min, 17r/min, 18r/min, 19r/min, 20r/min, 21r/min, 22r/min, 23r/min, 24r/min, 25r/min, 26r/min, 27r/min, 28r/min, 29r/min or 30r/min, and the like.
Preferably, in the secondary dynamic sintering, the rotation speed of the conical mixed sintering is more than or equal to 40r/min, such as 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min or 100 r/min. .
In the invention, during secondary dynamic sintering, the intermediate product after primary sintering treatment can be selectively heated to the secondary sintering temperature along with the furnace; optionally, after reaching the secondary sintering temperature, adding the intermediate product; and the material is preferably fed after the secondary sintering temperature is reached, so that the negative influence of overlong heating time in the temperature rise process on the components and the concentration of the quantum dots can be avoided.
In the secondary dynamic sintering process, no matter which sintering method is adopted, the rotating speed cannot be too low, and the particles are adhered and the size of the particles is increased in the collapse process of the mesoporous material due to too low rotating speed; and may cause a change in the composition of the quantum dots due to uneven heating.
Preferably, the temperature of the secondary dynamic sintering is 350 to 1000 ℃, such as 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, preferably 600 to 700 ℃.
In the present invention, the temperature of the secondary dynamic sintering is higher than that of the primary dynamic sintering, and the temperature is selected to achieve complete collapse of the mesoporous material, and is related to the intrinsic collapse temperature of the mesoporous material, the type and dosage of the MX pretreating agent, and the duration at the temperature.
As a preferred technical scheme, the preparation method comprises the following steps:
the preparation method comprises the following steps:
(1) mixing the mesoporous material with the pretreatment solution to obtain a pretreated mesoporous material;
(2) mixing the pretreated mesoporous material in the step (1) with a perovskite quantum dot precursor material according to the mass ratio of (3-5) to (1), carrying out primary dynamic sintering at the rotating speed of more than or equal to 5r/min under a protective atmosphere, wherein the primary dynamic sintering is rotary sintering, carrying out filling treatment on a product after the primary dynamic sintering, and then carrying out secondary dynamic sintering at the rotating speed of more than or equal to 15r/min, wherein the secondary dynamic sintering is rotary sintering at the temperature of 600-700 ℃, so as to obtain the perovskite quantum dot material;
the chemical general formula of the pretreating agent in the pretreatment solution is MX, M comprises an alkali metal element, the mass ratio of the pretreating agent to the mesoporous material is 1 (1-5), and the chemical general formula of the perovskite quantum dot is CsBX3B comprises Pb and/or Sn, and X comprises any one or combination of at least two of Cl, Br or I; the CsBX3When X does not include IThe sintering temperature of the primary dynamic sintering is 570-590 ℃; the CsBX3When the X at least comprises I, the sintering temperature of the primary dynamic sintering is 450-500 ℃.
In a second aspect, the present invention provides a perovskite quantum dot prepared by the preparation method of the perovskite quantum dot according to the first aspect.
The quantum dots prepared by the method are uniform in material mixing, particles are free of adhesion, the quantum dots can fully enter pore channels of the mesoporous material and grow up uniformly, the fluorescence efficiency of the quantum dots is obviously improved, and the light-emitting wavelength is red-shifted; self-absorption of quantum dots with consistent sizes is weakened, and half-peak width is reduced; meanwhile, the stability of the composite material is also improved.
In a third aspect, the present invention also provides a use of a perovskite quantum dot, the use comprising using the perovskite quantum dot as described in the second aspect in a photovoltaic product.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, in the process of preparing the perovskite quantum dot, the mesoporous material is combined with dynamic sintering, and the two synergistic effects enable the quantum dot material to fully enter the mesoporous material, so that the phenomena of uneven mixing, uneven temperature, particle adhesion and the like in the sintering process are avoided, the perovskite quantum dot material with consistent luminous performance, uniform concentration and uniform size is obtained, the stability of the perovskite quantum dot material can be improved through filling, and the perovskite quantum dot material is suitable for mass production.
(2) The quantum dots prepared by the method are uniform in material mixing, particles are free of adhesion, the quantum dots can fully enter pore channels of the mesoporous material and grow up uniformly, the fluorescence efficiency of the quantum dots is obviously improved, and the light-emitting wavelength is red-shifted; self-absorption of quantum dots with consistent sizes is weakened, and half-peak width is reduced; meanwhile, the stability of the composite material is also improved. The fluorescence efficiency of the quantum dot provided by the invention can reach more than 51% (the efficiency of the non-red light quantum dot can reach more than 53%), and the T90 phenomenon can occur only when the luminous efficiency of the quantum dot is aged for more than 180h in the accelerated aging experiment process at 85 ℃; the rotation speed in the dynamic sintering process is further regulated, the fluorescence efficiency of the non-red light quantum dots can reach more than 57%, the fluorescence wavelength is closer to 520nm, and the half-peak width is less than 22nm, namely the quantum dots obtained by the preparation method provided by the invention synchronously realize the improvement of the fluorescence efficiency, the red shift of the fluorescence wavelength, the reduction of the half-peak width and the improvement of the stability.
Drawings
Fig. 1 is a comparative graph of appearance of perovskite quantum dots provided in example 3 (right) and comparative example 1 (left).
Fig. 2 is an SEM image of the perovskite quantum dots provided in example 3.
Fig. 3 is an SEM image of the perovskite quantum dot provided in comparative example 1.
Fig. 4 is a graph comparing the peak position and full width at half maximum (FWHM) of the fluorescence spectrum of the perovskite quantum dots provided in example 1 and comparative example 3.
Fig. 5 is a graph comparing accelerated aging at 85 ℃ of the perovskite quantum dots provided in example 1 and comparative example 3.
FIG. 6 shows that the perovskite quantum dots provided by example 1 and comparative example 3 are 300mW/cm2Accelerated aging contrast plot under blue light.
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 perovskite quantum dot in the form of CsPbBr3@ SBA-15 Quantum dots (here @ indicates that SBA-15 in the final product is CsPbBr3The coating material of (a).
The preparation method of the perovskite quantum dot comprises the following steps:
(1) weighing KBr and SBA-15 molecular sieves, adding sufficient water into a beaker according to the mass ratio of 1:1, uniformly stirring, and drying to obtain pretreated SBA-15 powder for later use;
(2) reacting CsBr and PbBr2Mixing the powder according to a molar ratio of 1:1, and uniformly mixing the powder with the SBA-15 powder pretreated in the step (1) in a mortar according to a ratio of 1: 3;
(3) placing the precursor in a rotary tube furnace, heating the rotary tube furnace to 570 ℃ at a speed of 5 ℃/min, and then keeping the temperature for 30 minutes, wherein the rotary tube furnace rotates at a speed of 10r/min (one-time dynamic sintering process);
(4) and continuously heating to 700 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 30 minutes, cooling to room temperature along with the furnace, rotating the rotary tube furnace at the rotating speed of 30r/min (secondary dynamic sintering process) during the period, preparing the perovskite quantum dots, and cleaning and drying for later use.
Example 2
This example provides a perovskite quantum dot in the form of CsPbBrI2@ MCM-41 Quantum dots (here @ indicates that MCM-41 in the final product is used as CsPbBrI2The coating material of (a).
The preparation method of the perovskite quantum dot comprises the following steps:
(1) weighing KBr and MCM-41 molecular sieve, adding sufficient water into a beaker according to the mass ratio of 1:3, uniformly stirring, and drying to obtain pretreated MCM-41 powder for later use;
(2) mixing CsBr and PbI2Mixing the powder according to a molar ratio of 1:1, and uniformly mixing the powder with the MCM-41 powder pretreated in the step (1) in a mortar according to a ratio of 2: 3;
(3) placing the precursor in a rotary tube furnace, replacing the precursor for 3 times by using nitrogen, ensuring that the sintering atmosphere is the nitrogen atmosphere, heating the rotary tube furnace to 460 ℃ at the speed of 5 ℃/min, and then keeping the temperature for 30 minutes, wherein the rotary tube furnace rotates at the rotating speed of 13r/min (one-time dynamic sintering process);
(4) and continuously heating to 700 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 30 minutes, cooling to room temperature along with the furnace, rotating the rotary tube furnace at the rotating speed of 25r/min (secondary dynamic sintering process) during the period, preparing the perovskite quantum dot, and cleaning and drying for later use.
Example 3
This example provides a perovskite quantum dot in the form of CsPbBr3/Al2O3@ MCM-41 Quantum dots (here Al)2O3As a filler material; @ denotes MCM-41 work in the final productAs a cladding material).
The preparation method of the perovskite quantum dot comprises the following steps:
(1) weighing KBr and MCM-41 molecular sieve, adding sufficient water into a beaker according to the mass ratio of 1:2, uniformly stirring, and drying to obtain pretreated MCM-41 powder for later use;
(2) bulk phase CsPbBr3Uniformly mixing the powder and the MCM-41 powder pretreated in the step (1) in a mortar according to the ratio of 1: 5;
(3) putting the precursor into a stirring type reaction kettle, heating to 590 ℃ at the rotating speed of 120r/min and the speed of 5 ℃/min, keeping the temperature for 30 minutes (primary dynamic sintering process), cooling along with the furnace, and taking out;
(4) dipping the product after the primary dynamic sintering in 30ml of 95% ethanol solution, adding 0.2g of aluminum isopropoxide, performing ultrasonic dispersion and continuously stirring for 8 hours, performing centrifugal separation and drying;
(5) and (3) heating the stirring type reaction kettle to 750 ℃, putting the dried substance in the step (4) into the stirring type reaction kettle at the temperature, keeping the temperature for 30 minutes at the rotating speed of 250r/min, cooling to room temperature along with the furnace (secondary dynamic sintering process), preparing the perovskite quantum dots, and washing and drying for later use.
Example 4
This example provides a perovskite quantum dot in the form of CsPbBr3@ MCM-41 Quantum dots (here @ indicates that MCM-41 in the final product is used as CsPbBr3The coating material of (a).
The preparation method of the perovskite quantum dot comprises the following steps:
(1) weighing KBr and MCM-41 molecular sieve, adding sufficient water into a beaker according to the mass ratio of 1:2, uniformly stirring, and drying to obtain pretreated MCM-41 powder for later use;
(2) bulk phase CsPbBr3Uniformly mixing the powder and the MCM-41 powder pretreated in the step (1) in a mortar according to the ratio of 1: 5;
(3) putting the precursor into a stirring type reaction kettle, heating to 590 ℃ at a rotating speed of 150r/min and a heating rate of 5 ℃/min, keeping the temperature for 30 minutes (a primary dynamic sintering process), cooling along with a furnace, and taking out;
(4) cleaning the material prepared in the step (3) with ethanol, removing the material with the unreacted phase on the surface, performing centrifugal separation, and drying for later use;
(5) and (4) putting the dried substance in the step (4) into a stirring type reaction kettle, heating to 700 ℃ at a rotating speed of 230r/min and a heating rate of 10 ℃/min, keeping the temperature for 30 minutes, cooling to room temperature along with a furnace (secondary dynamic sintering process), preparing to obtain the perovskite quantum dot, and cleaning and drying for later use.
Example 5
The difference between this example and example 1 is that the rotation speed of the rotary tube furnace in step (4) of this example is 10 r/min.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this example and example 4 is that the rotation speed of the stirred tank reactor in step (4) of this example is 180 r/min.
The remaining preparation methods and parameters were in accordance with example 4.
Comparative example 1
The present comparative example differs from example 3 in that the sintering process in steps (3) and (5) of the present comparative example was static sintered in a conventional muffle furnace.
The remaining preparation methods and parameters were in accordance with example 3.
Fig. 1 shows an appearance versus scale plot of perovskite quantum dots provided by example 3 (right) and comparative example 1 (left), and as can be seen from fig. 1 (comparing from the color map referring to the figure), the color of the sample in example 3 is uniformly yellowish, whereas the color of the sample in comparative example 1 is not uniform, and is obviously yellow-white alternated; it is illustrated that the perovskite quantum dots are not sufficiently and uniformly generated inside the mesoporous material in the preparation process of comparative example 1.
Fig. 2 shows an SEM image of the perovskite quantum dot provided in example 3, fig. 3 shows an SEM image of the perovskite quantum dot provided in comparative example 1, and as can be seen from the comparison between fig. 2 and fig. 3, the sample particles in example 3 are less sticky and smaller in size, indicating that the perovskite quantum dot material obtained by the preparation method provided by the present invention has a better degree of dispersion and a uniform size.
Fig. 4 shows a comparison of the peak position and the full width at half maximum (FWHM) of the fluorescence spectrum of the perovskite quantum dots provided in example 1 and comparative example 3, and it can be seen from fig. 4 that the full width at half maximum of the quantum dots after dynamic sintering in example 3 is narrower, indicating that the sample size and composition are more consistent.
Fig. 5 shows a comparison graph of accelerated aging at 85 ℃ of the perovskite quantum dots provided by example 1 and comparative example 3, and it can be seen from fig. 5 that the perovskite quantum dots obtained by dynamic sintering in example 3 have better coating effect and better stability at high temperature.
FIG. 6 shows that the perovskite quantum dots provided by example 1 and comparative example 3 are at 300mW/cm2The accelerated aging under blue light is compared with the graph, and as can be seen from fig. 6, the perovskite quantum dot obtained by dynamic sintering in example 3 has good stability.
It can be shown from fig. 1 to fig. 6 that compared with the conventional static sintering method, the dynamic sintering method of the present invention can obtain perovskite quantum dot materials with uniform luminescent properties, uniform concentration and size, and good stability.
Comparative example 2
The comparative example is different from example 1 in that the pretreatment of the mesoporous material of step (1) is not performed in the comparative example.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 3
The comparative example differs from example 1 in that a conventional muffle furnace was used for static sintering in step (3) of the comparative example.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
The comparative example differs from example 1 in that a conventional muffle furnace was used for static sintering in step (4) of the comparative example.
The remaining preparation methods and parameters were in accordance with example 1.
The perovskite quantum dots provided in examples 1-6 and comparative examples 1-4 were tested under the following conditions:
the results of accelerated aging tests at a high temperature of 85 ℃ are shown in Table 1.
TABLE 1
Note: the meaning of T90 is the time for the luminous efficiency to decay to 90% of the initial value.
From the data results of examples 1 and 5, and examples 4 and 6, it is clear that the rotation speed during the secondary dynamic sintering process is too low, which is not favorable for the particle dispersion of the quantum dots, and increases self-absorption, resulting in a decrease in fluorescence efficiency and an increase in half-peak width.
From the data results of example 3 and comparative example 1, it is difficult to simultaneously achieve the effects of high fluorescence efficiency, narrow half-peak width and high stability by using the conventional static sintering.
It is understood from the data results of example 1 and comparative example 2 that the problems of the fluorescence efficiency reduction and the stability great reduction can occur without the pretreatment of the mesoporous material, mainly because of the lack of halogen environment and incomplete collapse of the mesoporous material.
From the data results of example 1 and comparative examples 3 and 4, it is understood that, when two-step dynamic sintering is performed, if one dynamic sintering is replaced by static sintering, a decrease in fluorescence efficiency, a blue shift in wavelength, and a broadening of half-peak width occur, and if two-step dynamic sintering is replaced by static sintering, a small decrease in fluorescence efficiency and deterioration in dispersibility occur.
In conclusion, in the process of preparing the perovskite quantum dot, the mesoporous material is combined with dynamic sintering, and the two synergistic effects enable the quantum dot material to fully enter the mesoporous material, so that the phenomena of uneven mixing, uneven temperature, adhesion of particles and the like in the sintering process are avoided, the perovskite quantum dot material with consistent luminous performance, uniform concentration and uniform size is obtained, the stability of the perovskite quantum dot material is improved, and the perovskite quantum dot material is suitable for mass production. The fluorescence efficiency of the quantum dot provided by the invention can reach more than 51% (the efficiency of the non-red light quantum dot can reach more than 53%), and the T90 phenomenon can occur only when the luminous efficiency of the quantum dot is aged for more than 180h in the accelerated aging experiment process at 85 ℃; the rotating speed in the dynamic sintering process is further regulated, the fluorescence efficiency of the non-red light quantum dots can reach more than 57%, the fluorescence wavelength is closer to 520nm, and the half-peak width is less than 22 nm.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of perovskite quantum dots is characterized by comprising the following steps:
(1) mixing the pretreatment agent solution with the mesoporous material to obtain a pretreated mesoporous material;
(2) mixing the pretreated mesoporous material obtained in the step (1) with a perovskite quantum dot precursor material, and dynamically sintering to obtain the perovskite quantum dot material;
wherein, the dynamic sintering in the step (2) comprises any one or the combination of at least two of rotary sintering, stirring sintering or conical mixed heating furnace sintering; the chemical general formula of the perovskite quantum dot is CsBX3B comprises Pb and/or Sn, and X comprises any one of Cl, Br or I or a combination of at least two of the Cl, Br and I.
2. The preparation method of the perovskite quantum dot according to claim 1, wherein the pore size of the mesoporous material in the step (1) is less than or equal to 20nm, preferably 3-10 nm;
preferably, the mesoporous material in step (1) comprises any one or a combination of at least two of MCM molecular sieve, SBA molecular sieve, ZSM molecular sieve, NaY molecular sieve, Zeolite molecular sieve, porous silica or porous alumina, preferably any one or a combination of at least two of porous silica, porous alumina or MCM molecular sieve;
preferably, the chemical formula of the pretreating agent in the pretreatment solution is MX, and M includes an alkali metal element;
preferably, the solvent in the pretreating agent solution comprises any one of water, methanol or acetone or a combination of at least two of the above;
preferably, the mass ratio of the pretreating agent to the mesoporous material is 1 (1-5).
3. The preparation method of the perovskite quantum dot according to claim 1 or 2, characterized in that in the step (2), the mass ratio of the perovskite quantum dot precursor material to the pretreated mesoporous material is 1 (1-10), preferably 1 (3-5);
preferably, the dynamic sintering of step (2) is rotary sintering;
preferably, the atmosphere for dynamic sintering in step (2) comprises an atmospheric atmosphere or a protective atmosphere, preferably a protective atmosphere;
preferably, the dynamic sintering of step (2) comprises sequentially performing a first dynamic sintering and a second dynamic sintering.
4. The preparation method of the perovskite quantum dot as claimed in claim 3, wherein in the primary dynamic sintering, the rotation speed of stirring sintering is more than or equal to 100 r/min;
preferably, in the primary dynamic sintering, the rotating speed of the rotary sintering is more than or equal to 5 r/min;
preferably, in the primary dynamic sintering, the sintering speed of the conical mixing heating furnace is more than or equal to 20 r/min.
5. The method for preparing perovskite quantum dots according to claim 3 or 4, wherein CsBX3When the medium X does not include I, the sintering temperature of primary dynamic sintering is 350-650 ℃, and preferably 570-590 ℃;
preferably, said CsBX3When the medium X at least comprises I, the sintering temperature of the primary dynamic sintering is 350-550 ℃, and preferably 450-500 ℃;
preferably, the substance after the primary dynamic sintering is subjected to a treatment and filling treatment.
6. The preparation method of the perovskite quantum dot as claimed in any one of claims 3 to 5, wherein in the secondary dynamic sintering, the rotation speed of stirring sintering is more than or equal to 200 r/min;
preferably, in the secondary dynamic sintering, the rotating speed of the rotary sintering is more than or equal to 15 r/min;
preferably, in the secondary dynamic sintering, the rotating speed of the conical mixed sintering is more than or equal to 40 r/min.
7. The method for preparing perovskite quantum dots according to any one of claims 3 to 6, wherein the temperature of the secondary dynamic sintering is 350 to 1000 ℃, preferably 600 to 700 ℃.
8. The method for preparing perovskite quantum dots according to any one of claims 1 to 7, wherein the method for preparing comprises the steps of:
(1) mixing the mesoporous material with the pretreatment solution to obtain a pretreated mesoporous material;
(2) mixing the pretreated mesoporous material in the step (1) with a perovskite quantum dot precursor material according to the mass ratio of (3-5) to (1), carrying out primary dynamic sintering at the rotating speed of more than or equal to 5r/min under a protective atmosphere, wherein the primary dynamic sintering is rotary sintering, carrying out filling treatment on a product after the primary dynamic sintering, and then carrying out secondary dynamic sintering at the rotating speed of more than or equal to 15r/min, wherein the secondary dynamic sintering is rotary sintering at the temperature of 600-700 ℃, so as to obtain the perovskite quantum dot material;
the chemical general formula of the pretreating agent in the pretreatment solution is MX, M comprises an alkali metal element, the mass ratio of the pretreating agent to the mesoporous material is 1 (1-5), and the chemical general formula of the perovskite quantum dot is CsBX3B comprises Pb and/or Sn, and X comprises any one or combination of at least two of Cl, Br or I; the CsBX3When the middle X does not include I, the sintering temperature of the primary dynamic sintering is 570-590 ℃; the CsBX3Middle X at least bagWhen I is included, the sintering temperature of the primary dynamic sintering is 450-500 ℃.
9. A perovskite quantum dot, wherein the perovskite quantum dot is prepared by the preparation method of the perovskite quantum dot according to any one of claims 1 to 8.
10. Use of a perovskite quantum dot according to claim 9 in a photovoltaic product.
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