CN111534301A - CsPbBr3Preparation method of perovskite quantum dots - Google Patents
CsPbBr3Preparation method of perovskite quantum dots Download PDFInfo
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Abstract
The invention relates to the technical field of photoelectric materials, in particular to CsPbBr3A preparation method of perovskite quantum dots. The preparation method provided by the invention utilizes the excellent ion exchange characteristic of sodium titanosilicate to convert Cs into Cs+The rivet is arranged on the molecular structure of the sodium titanosilicate, so that the synthesized CsPbBr3Fixing the position of the perovskite quantum dot; meanwhile, the sodium titanosilicate prepared by a hydrothermal method has a nanopore structure, and the CsPbBr is limited by the nanopore structure3The growth of perovskite quantum dots realizes the nanoscale CsPbBr3The multi-core growth of the perovskite quantum dots, thereby preparing the blue perovskite CsPbBr3And (4) quantum dots.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to CsPbBr3A preparation method of perovskite quantum dots.
Background
All-inorganic perovskite quantum dot CsPbX3The (X is halogen) has the advantages of high yield, high monodispersity, wide excitation spectrum range, adjustable emission spectrum, short fluorescence life, low preparation cost and the like, and is an excellent nano luminescent material. Has good prospect in the fields of illumination and displays. The luminous intensity and the stabilization time of the inorganic perovskite quantum dots in red and green LED devices reach the commercial degree. However, the research on blue LEDs is relatively backward and limits the further application of all-inorganic perovskite quantum dots.
At present, the method for preparing inorganic perovskite quantum dots emitting blue light generally comprises the following steps: preparation of high quality CsPbCl3Quantum dots, then incorporating a small amount of bromide ions. In general, PbCl2The dissolution is difficult, and the assistance of trioctylphosphine and high temperature conditions are needed to realize the dissolution.
Disclosure of Invention
The invention aims to provide CsPbBr3The preparation method of the perovskite quantum dot does not need the assistance of trioctylphosphine, and has mild reaction conditions; CsPbBr prepared by using preparation method3The perovskite quantum dot emits blue light, and has high luminous intensity and high luminous stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides CsPbBr3The preparation method of the perovskite quantum dot comprises the following steps:
mixing tetrabutyl titanate, ethyl orthosilicate, a NaOH solution, isopropanol and a template agent, and carrying out hydrothermal reaction to obtain sodium titanosilicate;
mixing the sodium titanosilicate and the CsBr solution, and carrying out ion exchange to obtain ion-exchanged sodium titanosilicate;
the titanium sodium silicate and PbBr after ion exchange are added2Mixing the solution with octadecene, and carrying out in-situ reaction to obtain CsPbBr3Perovskite quantum dots.
Preferably, the concentration of the NaOH solution is (1-10) mol/L;
the volume ratio of tetrabutyl titanate to ethyl orthosilicate to NaOH solution to isopropanol to the template agent is (1-10): (1-10): (1-10): (0.1-1): (0.1-0.5).
Preferably, the temperature of the hydrothermal reaction is 100-300 ℃, and the time of the hydrothermal reaction is 1-10 days.
Preferably, the concentration of the CsBr solution is (0.5-3) mol/L;
the volume ratio of the mass of the sodium titanosilicate to the CsBr solution is (0.5-3) g: (10-50) mL.
Preferably, the ion exchange is carried out under stirring conditions;
the stirring time is 12-48 h.
Preferably, the PbBr is2The solution comprises octadecene, oleylamine, oleic acid and PbBr2；
Octadecene, oleylamine, oleic acid and PbBr2The dosage ratio of (1-10) mL: (1-10) mL: (1-10) mL: (0.1-0.5) g.
Preferably, the ion-exchanged sodium titanosilicate and PbBr are2PbBr in solution2And octadecene in a dosage ratio of (0.1-1) g: (0.1-0.5) g: (1-10) mL.
Preferably, the ion-exchanged sodium titanosilicate and PbBr are2The mixing of the solution and octadecene comprises the following steps:
mixing the ion-exchanged sodium titanosilicate and octadecene, and heating to obtain a dispersion liquid;
under nitrogen atmosphere, PbBr is added2The solution was added to the dispersion.
Preferably, the heating comprises: under the vacuum condition, firstly heating to 100-150 ℃, then preserving heat for 10-60 minutes, and then heating to 150-200 ℃.
Preferably, the in-situ reaction is carried out under a nitrogen atmosphere and under stirring conditions;
the temperature of the in-situ reaction is 150-200 ℃, and the time of the in-situ reaction is 5-10 minutes.
The invention provides CsPbBr3The preparation method of the perovskite quantum dot comprises the following steps: mixing tetrabutyl titanate, ethyl orthosilicate, a NaOH solution, isopropanol and a template agent, and carrying out hydrothermal reaction to obtain sodium titanosilicate; mixing the sodium titanosilicate and the CsBr solution, and carrying out ion exchange to obtain ion-exchanged sodium titanosilicate; the titanium sodium silicate and PbBr after ion exchange are added2Mixing the solution with octadecene, and carrying out in-situ reaction to obtain CsPbBr3Perovskite quantum dots. The preparation method provided by the invention utilizes the excellent ion exchange characteristic of sodium titanosilicate to convert Cs into Cs+The rivet is arranged on the molecular structure of the sodium titanosilicate, so that the synthesized CsPbBr3The position of the perovskite quantum dot is fixed, the sodium titanosilicate prepared by a hydrothermal method has a nanopore structure, and the CsPbBr is limited by the nanopore structure3The growth of perovskite quantum dots realizes the nanoscale CsPbBr3The multi-core growth of the perovskite quantum dots, thereby preparing the blue perovskite CsPbBr3And (4) quantum dots. The function of the sodium titanosilicate: first, the ion exchange of sodium titanosilicate for cesium ions rivets CsPbBr3Quantum dots of CsPbBr3The quantum dots can be distributed in a dispersed manner, and agglomeration is reduced (the agglomeration of the quantum dots can seriously affect the fluorescence performance of the quantum dots). Secondly, the sodium titanosilicate has a nano-scale pore channel structure, so that CsPbBr can be limited3Size of quantum dot such that CsPbBr3At least one dimension of the quantum dots is below 4 nm. Thus CsPbBr3The quantum dots emit blue light.
Drawings
FIG. 1 is a pore volume-pore diameter distribution diagram of sodium titanosilicate prepared in example 1;
FIG. 2 is an SEM photograph of CST + Cs obtained by the methods of examples 1-3;
FIG. 3 shows CsPbBr prepared in example 13An emission spectrum of the perovskite quantum dots under an ultraviolet lamp of 370 nm;
FIG. 4 shows CsPbBr prepared in example 23A physical map of perovskite quantum dots;
FIG. 5 shows CsPbBr prepared in example 2 using 365nm UV flashlight3Perovskite quantum dot insertionA luminous object graph after line illumination;
FIG. 6 shows CsPbBr prepared in example 33CIE color coordinates of the perovskite quantum dots;
FIG. 7 shows sodium titanosilicate (CST) prepared in example 1 and CST prepared in example 2&CsPbBr3XRD pattern of (a);
FIG. 8 shows CsPbBr prepared in example 33TEM images of perovskite quantum dots;
FIG. 9 shows CST prepared in example 3&CsPbBr3And pure CsPbBr3A graph of the photoluminescence retention rate of (a) versus time;
FIG. 10 shows the CST prepared in example 3&CsPbBr3And pure CsPbBr3The photoluminescence retention rate of (a) and the temperature.
Detailed Description
The invention provides CsPbBr3The preparation method of the perovskite quantum dot comprises the following steps:
mixing tetrabutyl titanate, ethyl orthosilicate, a NaOH solution, isopropanol and a template agent, and carrying out hydrothermal reaction to obtain sodium titanosilicate;
mixing the sodium titanosilicate and the CsBr solution, and carrying out ion exchange to obtain ion-exchanged sodium titanosilicate;
the titanium sodium silicate and PbBr after ion exchange are added2Mixing the solution with octadecene, and carrying out in-situ reaction to obtain CsPbBr3Perovskite quantum dots.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes tetrabutyl titanate, tetraethoxysilane, NaOH solution, isopropanol and template agent to carry out hydrothermal reaction to obtain the sodium titanosilicate.
In the invention, the concentration of the NaOH solution is preferably (1-10) mol/L, more preferably (2-8) mol/L, and most preferably (4-6) mol/L. In the present invention, the kind of the template agent is preferably amine acetate or a 10% aqueous solution of hydroxylamine hydrochloride.
In the invention, the volume ratio of the tetrabutyl titanate, the ethyl orthosilicate, the NaOH solution, the isopropanol and the template agent is preferably (1-10): (1-10): (1-10): (0.1-1): (0.1 to 0.5), more preferably (2 to 8): (2-8): (2-8): (0.2-0.8): (0.2-0.4), most preferably (4-6): (4-6): (4-6): (0.4-0.6): (0.25-0.3).
In the present invention, the mixing preferably comprises: after tetrabutyl titanate and ethyl orthosilicate are uniformly mixed, NaOH solution, isopropanol and template agent are sequentially added, and the mixture is uniformly stirred until a large amount of white floccules are generated. In the invention, in the mixing process, tetrabutyl titanate and ethyl orthosilicate undergo alkaline hydrolysis reaction.
In the invention, the temperature of the hydrothermal reaction is preferably 100-300 ℃, more preferably 150-250 ℃, and most preferably 180-220 ℃; the time of the hydrothermal reaction is preferably 1 to 10 days, more preferably 2 to 8 days, and most preferably 4 to 7 days.
After the hydrothermal reaction is finished, the method also preferably comprises the steps of carrying out solid-liquid separation on a product system obtained by the hydrothermal reaction, and then sequentially washing, filtering and drying the obtained solid; the solid-liquid separation is not particularly limited in the present invention, and may be carried out in a manner known to those skilled in the art. In the invention, the washing is preferably carried out 7-8 times by using deionized water. The suction filtration and drying are not particularly limited in the present invention, and may be carried out in a manner known to those skilled in the art.
In the invention, the tetrabutyl titanate is used as a raw material for generating the sodium titanosilicate, the use amount of the tetrabutyl titanate is limited in the range, so that purer titanosilicate can be better ensured, the generation of amorphous phase and quartz phase titanosilicate can be better avoided, and the subsequent post-treatment is more favorably carried out; the template agent is used as a filler to support the hollow framework of the product from the space; the ammonium acetate or the hydroxylamine hydrochloride aqueous solution with the mass concentration of 10 percent has strong protonation in a liquid phase as a template agent, so that the arrangement of silicate ions can be guided from charges, and meanwhile, the properties (ionic strength, polarity and the like) of a reaction liquid phase can be effectively improved, thereby being beneficial to synthesizing the sodium titanosilicate.
After the sodium titanosilicate is obtained, the sodium titanosilicate and the CsBr solution are mixed for ion exchange, and the ion-exchanged sodium titanosilicate is obtained.
In the invention, the concentration of the CsBr solution is preferably (0.5-3) mol/L, more preferably (1-2.5) mol/L, and most preferably (1.5-2) mol/L. In the invention, the ratio of the mass of the sodium titanosilicate to the volume of the CsBr solution is preferably (0.5-3) g: (10-50) mL, more preferably (1.0-2.5) g: (20-40) mL, most preferably (1.5-2.0) g: (25-35) mL. The present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art.
In the present invention, the ion exchange is preferably carried out under stirring; the stirring time is preferably (12-48) h, more preferably (20-40) h, and most preferably (25-35) h. The stirring rate is not particularly limited in the present invention, and the stirring may be performed at a rate well known to those skilled in the art.
After the ion exchange is finished, the invention also preferably comprises the steps of washing and drying the obtained solid product in sequence; the washing is preferably carried out for 7-8 times by using deionized water; the drying temperature is preferably 80-100 ℃, and more preferably 80 ℃; the drying time is not particularly limited in the present invention, and the obtained product may be dried to a drying degree well known to those skilled in the art using a time well known to those skilled in the art.
In the invention, Cs in the sodium titanosilicate and CsBr solution is mixed+Will be mixed with Na+Ion exchange reaction is carried out to make Cs+Embedding into crystal lattice of sodium titanosilicate to make Cs+The stabilizing rivet is arranged in the pore canal of the sodium titanosilicate crystal.
After the ion-exchanged sodium titanosilicate is obtained, the invention uses the ion-exchanged sodium titanosilicate and PbBr2Mixing the solution with octadecene, and carrying out in-situ reaction to obtain CsPbBr3Perovskite quantum dots.
In the present invention, the PbBr is2The solution preferably comprises octadecene, oleylamine, oleic acid and PbBr2(ii) a Octadecene, oleylamine, oleic acid and PbBr2The preferable dosage ratio of (1-10) mL: (1-10) mL: (1-10) mL: (0.1-0.5) g, more preferably (2-8) mL: (2-8) mL: (2-8) mL: (0.2-0.4) g, most preferably (4-6) mL: (4-6) mL: (4-6) mL: (0.2-0.3) g. In the present invention, the PbBr is2The method of preparation of the solution preferably comprises the steps of: mixing the octadecene, oleylamine, oleic acid and PbBr2After mixing, heating under vacuum to make PbBr2Dissolving completely to obtain the PbBr2And (3) solution. In the invention, the heating temperature is preferably 100-200 ℃, and more preferably 100-150 ℃.
In the invention, the ion-exchanged sodium titanosilicate and PbBr are adopted2PbBr in solution2And octadecene is preferably used in a ratio of (0.1-1) g: (0.1-0.5) g: (1-10) mL, more preferably (0.2-0.8) g: (0.2-0.4) g: (2-8) mL, most preferably (0.4-0.6) g: (0.4-0.6) g: (4-6) mL.
In the invention, the ion-exchanged sodium titanosilicate and PbBr are adopted2The mixing of the solution and octadecene preferably comprises the following steps:
mixing the ion-exchanged sodium titanosilicate and octadecene, and heating to obtain a dispersion liquid;
under nitrogen atmosphere, PbBr is added2The solution was added to the dispersion.
In the present invention, the heating preferably includes: under the vacuum condition, firstly heating to 100-150 ℃, then preserving heat for 10-60 minutes, and then heating to 150-200 ℃; more preferably, it comprises: under the vacuum condition, firstly heating to 110-130 ℃, then preserving heat for 20-50 minutes, and then heating to 160-190 ℃; most preferably comprising: under the vacuum condition, firstly heating to 110-120 ℃, then preserving heat for 30-40 minutes, and then heating to 170-180 ℃.
In the present invention, the in-situ reaction is preferably performed under a nitrogen atmosphere and under stirring; the temperature of the in-situ reaction is preferably 100-200 ℃, more preferably 120-180 ℃, and most preferably 150-160 ℃; the time of the in-situ reaction is preferably 5-10 minutes, and more preferably 10 minutes.
After the in-situ reaction is finished, the method also preferably comprises the steps of sequentially carrying out ice water bath and solid-liquid separation on the obtained product system to obtain a solid product; and washing, centrifuging and drying the solid product in sequence. The solid-liquid separation method is not particularly limited, and the method known to those skilled in the art can be adopted. In the invention, the washing is preferably carried out by sequentially adopting n-hexane and isopropanol; the washing method of the present invention is not particularly limited, and the washing may be performed in a manner known to those skilled in the art. The centrifugation is not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art. In the present invention, the washing and centrifuging process is preferably repeated 2 to 3 times. In the present invention, the drying is preferably performed at room temperature.
In the present invention, PbBr is generated during the in situ reaction2The solution is fully dissolved in octadecylene solution in a heating mode to become lead ions and bromine ions, and after the lead ions and the bromine ions are mixed with the sodium titanosilicate subjected to ion exchange, because chemical reactions are carried out towards a direction with lower energy, a more stable substance can be formed, the lead ions and the bromine ions can be automatically combined by finding cesium ions to form CsPbBr3Perovskite quantum dots.
In the invention, CsPbBr prepared by the preparation method is utilized3The perovskite quantum dots comprise CsPbBr3Perovskite quantum dots and sodium titanosilicate; the CsPbBr3Perovskite quantum dots are distributed in the nanometer pore canal of the sodium titanosilicate; the CsPbBr3The mass ratio of the perovskite quantum dots to the sodium titanosilicate is preferably 1: (0.5 to 10), more preferably 1: (1-4).
The following examples are provided to illustrate CsPbBr according to the present invention3The preparation method of perovskite quantum dots is explained in detail, but the perovskite quantum dots are not understood to limit the protection scope of the invention.
Example 1
Uniformly mixing 3mL of tetrabutyl titanate and 1mL of ethyl orthosilicate, adding the mixture into 4mL of NaOH solution with the concentration of 3mol/L, adding 0.5mL of isopropanol and 0.5mL of amine acetate, uniformly stirring until a large amount of white floccules are observed, carrying out hydrothermal reaction (170 ℃, 10 days), washing the obtained product with deionized water for 8 times, carrying out suction filtration and drying to obtain sodium titanosilicate (marked as CST);
dispersing 1g of sodium titanate in 25mL of CsBr aqueous solution with the concentration of 1mol/L, stirring at room temperature for 22h, washing with deionized water for 7 times, and drying (80 ℃) to obtain ion-exchanged sodium titanosilicate (marked as CST + Cs);
10mL octadecene, 2mL oleylamine, 2mL oleic acid and 0.1469g PbBr2Mixing, heating at 120 deg.C under vacuum to make PbBr2Fully dissolving, cooling to room temperature in nitrogen atmosphere to obtain PbBr2A solution;
mixing 10mL octadecene with 0.3336g CST + Cs, heating (100 deg.C) under vacuum for 30min, heating to 150 deg.C, and injecting PbBr under nitrogen atmosphere2Reacting the solution for 10min under the condition of stirring, cooling in an ice-water bath, washing and centrifuging the product twice by using normal hexane and isopropanol, and drying at room temperature to obtain CsPbBr3Perovskite quantum dots (denoted as CST)&CsPbBr3CST and CsPbBr3In a mass ratio of 1: 1).
Example 2
Uniformly mixing 3mL of tetrabutyl titanate and 1mL of ethyl orthosilicate, adding the mixture into 4mL of NaOH solution with the concentration of 3mol/L, adding 0.5mL of isopropanol and 0.5mL of amine acetate, uniformly stirring until a large amount of white floccules are observed, carrying out hydrothermal reaction (170 ℃, 7 days), washing the obtained product with deionized water for 8 times, carrying out suction filtration and drying to obtain sodium titanosilicate (marked as CST);
dispersing 1g of sodium titanate in 25mL of CsBr aqueous solution with the concentration of 1mol/L, stirring at room temperature for 22h, washing with deionized water for 8 times, and drying (80 ℃) to obtain ion-exchanged sodium titanosilicate (recorded as CST + Cs);
10mL octadecene, 2mL oleylamine, 2mL oleic acid and 0.07345g PbBr2Mixing, heating at 120 deg.C under vacuum to PbBr2Fully dissolving, cooling to room temperature in nitrogen atmosphere to obtain PbBr2A solution;
mixing 10mL octadecene with 0.3336g CST + Cs, heating (150 deg.C) under vacuum for 30min, heating to 150 deg.C, and injecting PbBr under nitrogen atmosphere2Reacting the solution for 5min under the condition of stirring, cooling in an ice-water bath, washing and centrifuging the product twice by using normal hexane and isopropanol, and drying at room temperature to obtain CsPbBr3Perovskite quantum dots (denoted as CST)&CsPbBr3CST and CsPbBr3In a mass ratio of 2:1, yellow powder, as shown in fig. 4).
Example 3
Uniformly mixing 3mL of tetrabutyl titanate and 1mL of tetraethoxysilane, adding the mixture into 4mL of NaOH solution with the concentration of 3mol/L, adding 0.5mL of isopropanol and 0.5mL of hydroxylamine hydrochloride solution with the mass concentration of 10%, uniformly stirring until a large amount of white floccules are observed to be generated, carrying out hydrothermal reaction (300 ℃, 1 day), washing the obtained product with deionized water for 8 times, carrying out suction filtration and drying to obtain sodium titanosilicate (marked as CST);
dispersing 1g of sodium titanate in 25mL of CsBr aqueous solution with the concentration of 1mol/L, stirring at room temperature for 22h, washing with deionized water for 8 times, and drying (80 ℃) to obtain ion-exchanged sodium titanosilicate (recorded as CST + Cs);
10mL octadecene, 2mL oleylamine, 2mL oleic acid and 0.07345g PbBr2Mixing, heating at 120 deg.C under vacuum to make PbBr2Fully dissolving, cooling to room temperature in nitrogen atmosphere to obtain PbBr2A solution;
mixing 10mL octadecene with 0.3336g CST + Cs, heating (150 deg.C) under vacuum for 30min, heating to 150 deg.C, and injecting PbBr under nitrogen atmosphere2Reacting the solution for 3min under the condition of stirring, cooling in an ice-water bath, washing and centrifuging the product twice by using normal hexane and isopropanol, and drying at room temperature to obtain CsPbBr3Perovskite quantum dots (denoted as CST)&CsPbBr3CST and CsPbBr3In a mass ratio of 4: 1).
Test example
Preparation of example 1The prepared sodium titanosilicate is subjected to pore size test, the test result is shown in figure 1, and as can be seen from figure 1, the pore size of the sodium titanosilicate with the radius of 6nm is the largest; the specific surface area of the sodium titanosilicate is 232.3986m2Per g, pore area 13.0320m2Per g, external specific surface area 219.3667m2Per gram, the average adsorption pore diameter is 8.3864 nm;
SEM test is carried out on CST + Cs obtained in the embodiments 1-3, the test result is shown in figure 2, and as can be seen from figure 2, the ion exchange reaction of cesium ions does not change the basic nanostructure of sodium titanosilicate, and the ion exchange effect distribution of the cesium ions is relatively uniform;
CsPbBr prepared in example 13The perovskite quantum dots are irradiated by an ultraviolet lamp, the wavelength of the ultraviolet lamp is 370nm, the test result is shown in figure 3, and the CsPbBr can be known from figure 33After the perovskite quantum dots are irradiated by an ultraviolet lamp, an obvious emission peak is formed at the position of 358nm, the half-peak width is about 20nm, and the emission peak meets the emission half-peak width (12-40 nm) of the perovskite quantum dots;
CsPbBr prepared in example 2 using 365nm UV flashlight3Perovskite quantum dots, CsPbBr3Perovskite quantum dot blue light (as shown in fig. 5);
FIG. 6 shows CsPbBr prepared in example 33The perovskite quantum dots have CIE color coordinates (0.1642,0.0196) and belong to the blue light region.
FIG. 7 shows sodium titanosilicate (CST) prepared in example 1 and CST prepared in example 2&CsPbBr3As can be seen from fig. 7, the CST is&CsPbBr3Middle CsPbBr3Has obvious diffraction peak and is in tetragonal phase CsPbBr3The important diffraction peaks of the standard diffraction pattern (PDF card number: 18-0364) of the crystal are consistent, which indicates that the synthesized CsPbBr3The quantum dots are of a tetragonal phase perovskite structure;
FIG. 8 shows CsPbBr prepared in example 33TEM image of perovskite quantum dot, from FIG. 8, obvious diffraction fringe can be observed, the spacing is 0.21nm, and CsPbBr3The crystal surfaces of the tetragonal phase perovskite quantum dots (211) are corresponding, and the test result shows thatThe test result is consistent with the test result of XRD diffraction peak;
FIGS. 9 and 10 are CST prepared in example 3, respectively&CsPbBr3And pure CsPbBr3Photoluminescence (PL) map (purchased from pentley corporation) and the specific procedure: the prepared CST is subjected to&CsPbBr3And pure CsPbBr3Respectively and directly placing in the air, respectively taking 0.1g of samples every other day to carry out PL spectrum detection, and recording data when detection parameters are the same. Wherein FIG. 9 is the CST prepared in example 3&CsPbBr3And pure CsPbBr3A graph of the photoluminescence retention rate of (a) versus time; the prepared CST is subjected to&CsPbBr3And pure CsPbBr3Respectively taking 0.1g of the sample, placing the sample in an oven, adjusting the temperature of the oven, performing cold-hot circulation (heating from 0 ℃ to 100 ℃ and then cooling from 100 ℃ to 0 ℃), keeping the same time, taking out the sample at each temperature of 10 ℃, performing PL spectrum detection, and recording data, wherein the detection parameters are the same. FIG. 10 shows the CST prepared in example 3&CsPbBr3And pure CsPbBr3FIG. 9 shows the relationship between the photoluminescence retention and the temperature of CST&CsPbBr3PL Peak after 15 days also had 80% of the initial Peak value, while pure CsPbBr3After 5 days, the perovskite quantum dots decayed to 5% of the original initial value, from which it can be seen that CST&CsPbBr3The air storage stability of the CsPbBr is relatively pure3Perovskite quantum dots are improved a lot; as can be seen from FIG. 10, CST&CsPbBr3Has relatively pure CsPbBr thermal stability3The perovskite quantum dots are greatly improved by cold-hot circulation (heating from 0 ℃ to 100 ℃ and then cooling from 100 ℃ to 0 ℃), CST&CsPbBr3The luminous intensity of the fluorescent material can be restored to 84% before the experiment. However for pure CsPbBr3The emission intensity of the quantum dot powder of (2) was only able to return to 33% before the experiment. It is clear that CST&CsPbBr3The thermal stability of the composite is greatly superior to that of pure CsPbBr3Thermal stability of (2).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. CsPbBr3The preparation method of the perovskite quantum dot is characterized by comprising the following steps:
mixing tetrabutyl titanate, ethyl orthosilicate, a NaOH solution, isopropanol and a template agent, and carrying out hydrothermal reaction to obtain sodium titanosilicate;
mixing the sodium titanosilicate and the CsBr solution, and carrying out ion exchange to obtain ion-exchanged sodium titanosilicate;
the titanium sodium silicate and PbBr after ion exchange are added2Mixing the solution with octadecene, and carrying out in-situ reaction to obtain CsPbBr3Perovskite quantum dots.
2. The method according to claim 1, wherein the concentration of the NaOH solution is (1-10) mol/L;
the volume ratio of tetrabutyl titanate to ethyl orthosilicate to NaOH solution to isopropanol to the template agent is (1-10): (1-10): (1-10): (0.1-1): (0.1-0.5).
3. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 100 to 300 ℃ for 1 to 10 days.
4. The preparation method according to claim 1, wherein the CsBr solution has a concentration of (0.5 to 3) mol/L;
the volume ratio of the mass of the sodium titanosilicate to the CsBr solution is (0.5-3) g: (10-50) mL.
5. The method of claim 1, wherein the ion exchange is carried out under stirring;
the stirring time is 12-48 h.
6. The method of claim 1, wherein the method comprisesPbBr2The solution comprises octadecene, oleylamine, oleic acid and PbBr2；
Octadecene, oleylamine, oleic acid and PbBr2The dosage ratio of (1-10) mL: (1-10) mL: (1-10) mL: (0.1-0.5) g.
7. The method of claim 1, wherein the ion-exchanged sodium titanosilicate, PbBr, is2PbBr in solution2And octadecene in a dosage ratio of (0.1-1) g: (0.1-0.5) g: (1-10) mL.
8. The method of claim 1 or 7, wherein the ion-exchanged sodium titanosilicate, PbBr, is2The mixing of the solution and octadecene comprises the following steps:
mixing the ion-exchanged sodium titanosilicate and octadecene, and heating to obtain a dispersion liquid;
under nitrogen atmosphere, PbBr is added2The solution was added to the dispersion.
9. The method of claim 8, wherein the heating comprises: under the vacuum condition, firstly heating to 100-150 ℃, then preserving heat for 10-60 minutes, and then heating to 150-200 ℃.
10. The method of claim 1, wherein the in-situ reaction is performed under a nitrogen atmosphere and with stirring;
the temperature of the in-situ reaction is 150-200 ℃, and the time of the in-situ reaction is 5-10 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316944A (en) * | 2021-12-07 | 2022-04-12 | 西安交通大学 | Method for preparing high-stability zirconium oxide coated quantum dots |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106701070A (en) * | 2016-11-16 | 2017-05-24 | 华南理工大学 | Blue, yellow and orange light calcium titanium mining quantum dot and molecular sieve composite luminescent material and preparing method and application thereof |
| CN107118769A (en) * | 2017-05-27 | 2017-09-01 | 华南理工大学 | A kind of additive Mn perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application |
| CN107384387A (en) * | 2017-08-30 | 2017-11-24 | 华南理工大学 | A kind of additive Mn CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application |
| CN109266344A (en) * | 2018-11-21 | 2019-01-25 | 南京邮电大学 | The preparation method of one type halogen perovskite quanta point material |
| CN110041915A (en) * | 2019-04-24 | 2019-07-23 | 深圳大学 | The preparation method of perovskite quantum dot and metal organic frame composite luminescent material |
| CN110635012A (en) * | 2019-09-12 | 2019-12-31 | 南昌航空大学 | Preparation of high-stability perovskite quantum dot white light-emitting diode based on manganese ion doped lead-cesium chloride embedded in zeolite |
-
2020
- 2020-03-31 CN CN202010243667.XA patent/CN111534301A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106701070A (en) * | 2016-11-16 | 2017-05-24 | 华南理工大学 | Blue, yellow and orange light calcium titanium mining quantum dot and molecular sieve composite luminescent material and preparing method and application thereof |
| CN107118769A (en) * | 2017-05-27 | 2017-09-01 | 华南理工大学 | A kind of additive Mn perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application |
| CN107384387A (en) * | 2017-08-30 | 2017-11-24 | 华南理工大学 | A kind of additive Mn CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application |
| CN109266344A (en) * | 2018-11-21 | 2019-01-25 | 南京邮电大学 | The preparation method of one type halogen perovskite quanta point material |
| CN110041915A (en) * | 2019-04-24 | 2019-07-23 | 深圳大学 | The preparation method of perovskite quantum dot and metal organic frame composite luminescent material |
| CN110635012A (en) * | 2019-09-12 | 2019-12-31 | 南昌航空大学 | Preparation of high-stability perovskite quantum dot white light-emitting diode based on manganese ion doped lead-cesium chloride embedded in zeolite |
Non-Patent Citations (5)
| Title |
|---|
| JIA-YI SUN ET AL.: "Facile Two-Step Synthesis of All-Inorganic Perovskite CsPbX3 (X = Cl, Br, and I) Zeolite-Y Composite Phosphors for Potential Backlight Display Application", 《ADV. FUNCT. MATER.》 * |
| VICTOR MALGRAS ET AL.: "Stable Blue Luminescent CsPbBr3 Perovskite Nanocrystals Confined in Mesoporous Thin Films", 《ANGEW. CHEM.》 * |
| ZHEN LI ET AL.: "Strongly quantum-confined Mn2+-doped CsPbBr3 nanocrystals in MCM-41 with pure blue emission", 《NEW J. CHEM.》 * |
| 孙佳奕: "钙钛矿量子点与分子筛复合材料的制备与性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 杜晓燕: "钛硅酸钠无机离子交换材料的制备及对艳的吸附效果研究", 《中国优秀硕士论文全文数据库工程科技II辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316944A (en) * | 2021-12-07 | 2022-04-12 | 西安交通大学 | Method for preparing high-stability zirconium oxide coated quantum dots |
| CN114316944B (en) * | 2021-12-07 | 2023-11-21 | 西安交通大学 | Method for preparing high-stability zirconia coated quantum dot |
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