CN117963977A - Method for preparing sphere-like superlattice microcavity by self-assembled rhombic dodecahedron perovskite nanocrystalline - Google Patents
Method for preparing sphere-like superlattice microcavity by self-assembled rhombic dodecahedron perovskite nanocrystalline Download PDFInfo
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Abstract
A method for preparing self-assembled spherical superlattice microcavity by synthesizing rhombic dodecahedral nanocrystalline comprises the steps of obtaining rhombic dodecahedral CsPbBr 3 nanocrystalline with good monodispersity by a thermal injection method, centrifugally separating and purifying, dispersing in toluene solution, dripping a proper amount of diluted nanocrystalline solution on a substrate, standing at low temperature for slow evaporation, orderly arranging and gathering rhombic dodecahedral nanocrystalline in the solution under the interaction between ligands and solvents, and self-assembling to form a superlattice with a regular morphology structure. The dimensions of the self-assembled superlattice structure are approximately several hundred nanometers to several micrometers. The regular rhombic dodecahedron nanocrystalline has good application prospect in the fields of photocatalysis and display due to the weak size limiting effect and the multifaceted property; meanwhile, the spherical superlattice has higher stacking factor due to the close stacking property of the structure, and the regular geometric morphology combined with the self-assembled superlattice structure can be used as an optical feedback surface to form a microcavity.
Description
Technical Field
The invention relates to preparation of rhombic dodecahedron nanocrystals and perovskite microcavities, which is different from traditional cubic perovskite nanocrystals, in particular to a method for preparing a sphere-like superlattice microcavity from self-assembled rhombic dodecahedron CsPbBr 3 nanocrystals.
Background
Due to the rapid development of laser technology and low cost synthesis of nanocrystals, combining features that are easy to integrate with semiconductor devices in existing microelectronic technologies, semiconductor lasers based on processable solutions have become a long-term challenge and research hotspot for next-generation displays, light sources and communication technologies.
Metal halide perovskite quantum dot materials because of their excellent optical properties: having large oscillator intensities and high quantum yields and long coherence times becomes an exciting class of quantum emitters. However, the cavity enhanced super fluorescence realized by the perovskite quantum dots at present also has the problem of higher threshold value, and the cubic nanocrystals of the long-chain organic ligands have higher gain threshold value due to the influence of the crystal structure and defects of the cubic nanocrystals. Resulting in a large gain threshold. The higher gain threshold severely affects the further development of cavity enhanced superfluorescence.
In view of the above, we have introduced polyhedral nanocrystals, which stabilize new facets by synthesizing new ligands by modified thermal injection methods to form row-stabilized dodecahedral nanocrystals. The superlattice structure synthesized by self-assembly of the diamond-shaped dodecahedron nanocrystalline with lower non-radiation recombination is used as an optical microcavity, so that the gain medium and the resonant cavity are integrated, and the coupling problem of the semiconductor laser quantum dots and the optical cavity and the pain point of overhigh gain threshold are improved. The method has very important significance for the application of the quantum dot laser in the aspects of quantum light sources and communication.
Disclosure of Invention
The invention aims to improve the prior technical problems and provides a preparation method for synthesizing multi-face perovskite nanocrystalline by self-assembling spherical perovskite superlattice. The rhombic dodecahedral nanocrystalline synthesized by the method has good monodispersity and uniform shape rule; the preparation process is simple, the repeatability is high, and the self-assembled superlattice structure is arranged regularly and orderly; meanwhile, compared with oleic acid oleylamine modified nanocrystalline, the nano-crystal has lower Auger recombination rate, has lower gain threshold when being used as an optical microcavity, and is more beneficial to the development and application of laser materials.
The technical scheme of the invention is as follows:
The method for preparing the sphere-like superlattice microcavity by self-assembled rhombic dodecahedron perovskite nanocrystalline is characterized by comprising the following steps of:
Step1, preparation of cesium oleate precursor liquid: uniformly mixing cesium carbonate powder, oleic acid and octadecene, stirring, heating the mixture until cesium carbonate is dissolved, heating to 150 ℃, and annealing and naturally cooling to obtain cesium oleate precursor liquid;
Step 2, preparing the rhombic dodecahedron CsPbBr 3 colloidal quantum dot: adding a certain proportion of lead oxide and benzoyl bromide, stirring and mixing quantitative oleic acid and octadecene, heating the mixture, heating to 220 ℃, injecting quantitative oleylamine, annealing to obtain a clear yellow solution, cooling to 165-220 ℃, injecting cesium oleate precursor liquid, and annealing to obtain a rhombic dodecahedral CsPbBr 3 colloidal quantum dot crude solution;
Step 3, purifying the rhombic dodecahedron CsPbBr 3 colloidal quantum dots: purifying the rhombic dodecahedron CsPbBr 3 colloidal quantum dot crude solution, dispersing the centrifuged precipitate in toluene solvent, and adding a proper amount of methyl acetate; centrifuging again, and repeating the process twice; dissolving the precipitate in a certain amount of toluene solvent, putting the solution into a sample bottle, and preserving the solution for at least 24 hours at low temperature, wherein the supernatant in the sample bottle is the superlattice quantum dot solution;
Step 4, preparing a spherical superlattice microcavity: and adding a proper amount of superlattice quantum dot solution into toluene for dilution and dispersion, dripping the superlattice quantum dot solution into a tube, placing a substrate into the tube, storing the substrate at a low temperature Wen Biguang, forming a solid-liquid interface between the surface of the substrate and the nanocrystalline solution, and performing self-assembly along with solvent volatilization to obtain the spheroidal superlattice microcavity.
Preferably, the preparation of the cesium oleate precursor liquid in the step 1 is specifically: 1.2mmol of cesium carbonate powder, 2ml of oleic acid and 18ml of octadecene are weighed, mixed uniformly, stirred and the mixture is heated until cesium carbonate is completely dissolved, then the temperature is raised to 150 ℃ for annealing for a certain time, and natural cooling is carried out, thus obtaining cesium oleate precursor liquid.
Preferably, in the step 3, the molar ratio of lead oxide to benzoyl bromide is 1:3.
Preferably, in the step 2, the volume ratio of oleic acid to octadecene to oleylamine is 2:10:1.
Preferably, the heating in steps 1 and 2 is performed in a nitrogen atmosphere.
Preferably, the annealing time after the oleylamine is injected in the step 2 is 11-15min, and the annealing time after the cesium oleate precursor liquid is injected is 10-15min.
Preferably, the amount of the solution in the dropping tube in the step 4 is 100ml, the deposited piece is a monocrystalline silicon piece, and the low-temperature deposition temperature is 6-8 ℃.
The self-assembled rhombic dodecahedral perovskite nanocrystalline preparation sphere-like superlattice microcavity is characterized in that perovskite nanocrystalline particles used for self-assembly have regular dodecahedral morphology, the particle size is 13-15nm, and the perovskite nanocrystalline particles have monodispersity and size uniformity; the superlattice microcavity formed by self-assembly has spherical morphology, regular and ordered internal structure, high stacking factor and adjustable diameter of 400nm-4um, and can form laser with low threshold after excitation.
Compared with the prior art, the invention has the following technical effects:
The present invention stabilizes new facets by varying the bromine source and lead source used to synthesize the quantum dots, wherein the bromine source (benzoyl bromide) releases HBr through a continuous nucleophilic substitution reaction, initially forming primary ammonium bromide with oleylamine, generating tertiary ammonium ions with prolonged annealing time, resulting in the formation of dodecahedral nanocrystals. When the rhombic dodecahedron quantum dot is prepared, the temperature of the injection of the oleylamine and the precursor liquid, the annealing time and the purification step can influence the size and the morphology of the rhombic dodecahedron nanocrystal, and the assembled primitive is changed, so that the assembled superlattice structure is changed; factors such as solvent type, evaporation time and temperature in the self-assembly process can also influence the regularity and the morphology size of the superlattice structure, and finally influence the quality of the superlattice structure. The synthesis conditions should be reasonably controlled to form a superlattice structure of desired dimensions and rules.
The three-dimensional all-inorganic perovskite quantum dot self-assembled spherical superlattice microcavity prepared finally has regular morphology, ordered arrangement and smoother surface, and the size is adjustable from hundreds of nanometers to micrometers.
The invention obtains the size-adjustable spherical superlattice microcavity structure in a self-assembly mode, and the preparation process is simple, low in cost and good in repeatability. The prepared superlattice is formed by long-range order and compact arrangement of quantum dots, and has high gain coefficient and low non-radiative recombination. The high-quality low-threshold single-mode laser can be simultaneously used as a gain medium and a resonant cavity.
Drawings
FIG. 1 is a TEM image of a rhombic dodecahedron CsPbBr 3 quantum dot according to the invention, a is the morphology of a monodisperse rhombic dodecahedron quantum dot; b is a high resolution transmission electron microscope pattern of single diamond dodecahedral quantum dots.
Fig. 2 is an SEM image of a rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavity in accordance with the invention.
Fig. 3 is a TEM pattern of rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavities of different sizes of the present invention. a is 400nm; b is 800nm; c is 3um.
Fig. 4 is a graph of single mode lasing of a rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavity according to the invention as a function of power.
Fig. 5 is a graph comparing threshold curves of a rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavity and a cubic hexahedral perovskite quantum dot self-assembled superlattice microcavity of the present invention. The upper part is a rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavity, and the threshold value is 15.5 mu J cm -2; the lower part is a cubic hexahedral perovskite quantum dot self-assembled superlattice microcavity, and the threshold value is 31.8 mu J cm -2.
Detailed Description
In order to further explain the preparation of the rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavity, the embodiment is implemented according to the technical scheme of the invention, and a specific implementation scheme is provided.
Example 1
(1) 200Mg of cesium carbonate powder, 1ml of oleic acid and 8ml of octadecene are weighed and added into a three-necked flask to be uniformly mixed, the mixture is continuously stirred and heated to 120 ℃ under the protection of nitrogen, the temperature is kept for 30min, the mixture is heated to 150 ℃, and the mixture is naturally cooled to room temperature after being kept for 10min, so as to be used as a cesium oleate precursor.
(2) 0.4Mmol of lead oxide, 1.2mmol of benzoyl bromide, 2ml of oleic acid and 10ml of octadecene were weighed into a three-necked flask, and the mixture was heated to 120℃with continuous stirring and kept under nitrogen atmosphere for 30min. Then 1ml of oleylamine is injected after the temperature is raised to 220 ℃, the solution is changed from orange red to clear yellow after annealing for 11min, then 1ml of cesium oleate precursor liquid is rapidly injected after the temperature is reduced to 170 ℃, and the rhombic dodecahedral CsPbBr 3 colloidal quantum dot crude solution is obtained after annealing for 15min and cooling to room temperature by using an ice water bath.
(3) The obtained crude solution was subjected to centrifugal separation and purification, and the rotational speed of the centrifuge was set to 8500rpm. The time is set to10 min; dispersing the centrifuged precipitate in hexane solvent, and adding appropriate amount of methyl acetate (the ratio of solvent to methyl acetate is 4:1); setting the rotating speed to 9000rpm, and centrifuging again for 5 min; dissolving the precipitate in a certain amount of toluene solvent, and placing the solution into a sample bottle for low-temperature preservation; and taking the supernatant by a pipetting gun after 24 hours to obtain the quantum dot solution for preparing the superlattice.
(4) Taking 10ul of the prepared quantum dot solution, dripping on an ultrathin carbon support film, and observing morphology by TEM, wherein the obtained twelve-sided nanometer crystal edge is about 14nm and shows good monodispersity and size uniformity as shown in a of figure 1; the high resolution transmission electron microscope pattern shown in fig. 1 b shows that the synthesized rhombic dodecahedron quantum dot shape is good.
(5) The quantum dot solution concentration obtained by diluting a proper amount of colloid solution in toluene is 15mg/ml by a pipette. And (3) dripping 100ul of diluted solution into a tube, placing a substrate into the tube, placing a sample at 6-8 ℃ and keeping at Wen Biguang, forming a solid-liquid interface between the substrate and the nanocrystalline solution, and gradually forming a spherical superlattice microcavity structure on the substrate along with slow volatilization of toluene.
(6) The morphology of the spherical superlattice microcavity is observed through SEM, as shown in fig. 2, the quantum dots are closely arranged together to form a spherical self-assembled structure with high stacking factor, the shape is more regular, and the diameter of the spherical superlattice microcavity is approximately 3.5 μm.
Example 2
The embodiment mainly examines the influence of reaction raw materials, oil amine injection temperature, annealing time, cs precursor liquid injection temperature, quantum dot solution concentration, evaporation time and evaporation temperature on the process of forming the spherical superlattice microcavity in the process of self-assembling the perovskite quantum dot into the spherical superlattice microcavity. For specific experimental steps, please refer to example 1, which is different in that: the reaction raw materials, the temperature of the injected oleylamine, the annealing time, the temperature of the injected Cs precursor liquid, the concentration of the quantum dot solution, the evaporation time and the evaporation temperature were respectively changed, and specific experimental parameters are shown in table 1.
Table 1 preparation of the perovskite quantum dot self-assembled spherical superlattice microcavity experimental conditions described above:
According to experimental results, the change of a bromine source lead source can influence the synthesis of quantum dots, lead halide can be more easily synthesized into cubic hexahedral nanocrystals, benzoyl bromide and lead oxide can be synthesized into rhombic dodecahedron nanocrystals, and the change of the appearance of nanocrystalline elements used for assembly can influence the appearance of an assembled superlattice microcavity structure; meanwhile, the temperature of the injection of the oleylamine and the time of the first annealing can also influence the morphology of the nanocrystalline, the injection of the oleylamine needs to be carried out at the temperature of 220 ℃, the time of the first annealing needs to be more than 10 minutes, the rhombic dodecahedron nanocrystalline can be synthesized subsequently, otherwise, the synthesized nanocrystalline is wide in size distribution and various in morphology, and the assembly result is not ideal; the temperature of the injected Cs precursor solution also affects the size of the synthesized quantum dots, thereby affecting the size of the assembled superlattice microcavity structure; the concentration of the solution used for assembly, the evaporation time and the temperature of the solution affect the quality and morphology of the assembled structure. In the case of a proper assembly concentration (15-20 mg/ml), the evaporation time of the solution is prolonged by low temperature, and a tightly assembled regular structure is more easily obtained.
By controlling and varying the factors influencing the assembly described above, we can control the diameter of the spherical superlattice microcavity structure. The microcavity structure is transferred to an ultrathin carbon support film, and morphology observation is carried out through TEM, and as shown in fig. 3, three graphs a, b and c show that the size of the spherical superlattice microcavity structure is 400 mu m, 800 mu m and 3 mu m respectively. The size of the spherical superlattice microcavity structure is controllable by changing the assembly influencing factors, and the size is between 400 and 4 mu m.
Application examples:
This example examined whether the CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice sample obtained in example 1 could be used as a laser microcavity, producing lasing under pumping.
The experimental setup of this example was an ultrafast transient spectrometer (model HR event & FLS 980). The specific experimental steps are as follows: firstly, placing a monocrystalline silicon wafer deposited with a sample on a sample stage of a micro-fluorescence spectrometer, adjusting the height of the sample stage, selecting a 50-time lens, and finding a CsPbBr 3 spherical superlattice structure under a microscope. The 400nm femtosecond laser (Libra-USP-10 k-HE) was then turned on and the laser was introduced into the spectrometer. And adjusting a microscope lens, focusing the light spots, performing spectrum detection, and pumping under low power to obtain a fluorescence spectrum of the sample. Next, the single-mode lasing can be obtained in the superlattice microcavity by gradually increasing the excitation power, the experimental result is shown in fig. 4, fig. 4 is a graph showing the single-mode lasing in the rhombic dodecahedral CsPbBr 3 perovskite quantum dot self-assembled superlattice microcavity along with the power, the sharp narrow peaks protruding in the graph prove the appearance of laser, and the obtained CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice sample can be used as a laser microcavity and generate lasing under pumping.
According to the condition of the serial number 1 in the table 1, we also assembled a superlattice structure with a traditional cubic hexahedral nanocrystal, and used the superlattice structure as a laser microcavity to perform a comparison experiment with a spherical superlattice microcavity assembled with rhombic dodecahedral quantum dots. The experimental results are shown in FIG. 5. Fig. 5 is a graph comparing threshold curves of two microcavity structures. The upper part is a rhombic dodecahedron CsPbBr 3 perovskite quantum dot self-assembled spherical superlattice microcavity, and the measured threshold value is 15.5 mu J cm -2; the lower part is a cubic hexahedral perovskite quantum dot self-assembled superlattice microcavity, the measured threshold value is 31.8 mu J cm -2, and the lasing threshold value is reduced by about 50 percent, so that the self-assembled superlattice quantum dot self-assembled perovskite quantum dot self-assembled superlattice microcavity has more excellent optical performance.
Claims (8)
1. The method for preparing the spheroidal superlattice microcavity by self-assembled rhombic dodecahedron perovskite nanocrystalline is characterized by comprising the following steps of:
Step1, preparation of cesium oleate precursor liquid: uniformly mixing cesium carbonate powder, oleic acid and octadecene, stirring, heating the mixture until cesium carbonate is dissolved, heating to 150 ℃, and annealing and naturally cooling to obtain cesium oleate precursor liquid;
Step 2, preparing the rhombic dodecahedron CsPbBr 3 colloidal quantum dot: adding a certain proportion of lead oxide and benzoyl bromide, stirring and mixing quantitative oleic acid and octadecene, heating the mixture, heating to 220 ℃, injecting quantitative oleylamine, annealing to obtain a clear yellow solution, cooling to 165-220 ℃, injecting cesium oleate precursor liquid, and annealing to obtain a rhombic dodecahedral CsPbBr 3 colloidal quantum dot crude solution;
Step 3, purifying the rhombic dodecahedron CsPbBr 3 colloidal quantum dots: purifying the rhombic dodecahedron CsPbBr 3 colloidal quantum dot crude solution, dispersing the centrifuged precipitate in toluene solvent, and adding a proper amount of methyl acetate; centrifuging again, and repeating the process twice; dissolving the precipitate in a certain amount of toluene solvent, putting the solution into a sample bottle, and preserving the solution for at least 24 hours at low temperature, wherein the supernatant in the sample bottle is the superlattice quantum dot solution;
Step 4, preparing a spherical superlattice microcavity: and adding a proper amount of superlattice quantum dot solution into toluene for dilution and dispersion, dripping the superlattice quantum dot solution into a tube, placing a substrate into the tube, storing the substrate at a low temperature Wen Biguang, forming a solid-liquid interface between the surface of the substrate and the nanocrystalline solution, and performing self-assembly along with solvent volatilization to obtain the spheroidal superlattice microcavity.
2. The method for preparing a spheroidal superlattice microcavity from self-assembled rhombic dodecahedral perovskite nanocrystals according to claim 1, wherein the preparation of cesium oleate precursor liquid is specifically as follows: 1.2mmol of cesium carbonate powder, 2ml of oleic acid and 18ml of octadecene are weighed, mixed uniformly, stirred and the mixture is heated until cesium carbonate is completely dissolved, then the temperature is raised to 150 ℃ for annealing for a certain time, and natural cooling is carried out, thus obtaining cesium oleate precursor liquid.
3. The method for preparing a spheroidal superlattice microcavity from self-assembled rhombic dodecahedral perovskite nanocrystals according to claim 1, wherein the molar ratio of lead oxide to benzoyl bromide in step 3 is 1:3.
4. The method for preparing a spheroidal superlattice microcavity from self-assembled rhombic dodecahedral perovskite nanocrystals according to claim 1, wherein the volume ratio of oleic acid, octadecene and oleylamine in step2 is (2): (10): (1).
5. The method for preparing a sphere-like superlattice microcavity from self-assembled rhombic dodecahedral perovskite nanocrystals according to claim 1, wherein the heating in steps 1 and 2 is performed in a nitrogen atmosphere.
6. The method for preparing the spheroidal superlattice microcavity from the self-assembled rhombic dodecahedron perovskite nanocrystals according to claim 1, wherein the annealing time after injection of oleylamine in step 2 is 11-15min, and the annealing time after injection of cesium oleate precursor liquid is 10-15min.
7. The method for preparing the spheroidal superlattice microcavity from the self-assembled rhombic dodecahedron perovskite nanocrystals according to claim 1, wherein the amount of the solution in the dropping tube in step 4 is 100ml, the deposition sheet is a monocrystalline silicon sheet, and the low-temperature deposition temperature is 6-8 ℃.
8. The preparation of sphere-like superlattice microcavities from self-assembled rhombic dodecahedral perovskite nanocrystals according to claim 1, wherein the perovskite nanocrystalline particles for self-assembly have regular dodecahedral morphology with particle size of 13-15nm, monodispersity and size uniformity; the superlattice microcavity formed by self-assembly has spherical morphology, regular and ordered internal structure, high stacking factor and adjustable diameter of 400nm-4um, and can form laser with low threshold after excitation.
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