CN110144217A - A kind of CsPbBr3/Cs4PbBr6Composite perofskite material and preparation method thereof - Google Patents
A kind of CsPbBr3/Cs4PbBr6Composite perofskite material and preparation method thereof Download PDFInfo
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- CN110144217A CN110144217A CN201910511311.7A CN201910511311A CN110144217A CN 110144217 A CN110144217 A CN 110144217A CN 201910511311 A CN201910511311 A CN 201910511311A CN 110144217 A CN110144217 A CN 110144217A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
Abstract
The invention discloses a kind of CsPbBr3/Cs4PbBr6Composite perofskite material and preparation method thereof, the preparation method of the material is the following steps are included: take PbBr2It is dissolved in n,N-Dimethylformamide with CsBr, quickly then cetyl trimethylammonium bromide is added thereto under fast stirring to being completely dissolved and is prepared into precursor solution by stirring；Precursor solution is added in toluene, is stirred to react, after reaction centrifugal treating, collect precipitating, drying to get.Compared with the existing technology, the present invention provides a kind of new synthesis process, it is unique ligand in reaction with cetyl trimethylammonium bromide, controllably synthesizes monodispersed CsPbBr3/Cs4PbBr6Rodlike composite perofskite material, wherein CsPbBr3It is evenly embedded into rodlike Cs4PbBr6In matrix.Sandwich prepared by the present invention can effectively prevent the CsPbBr of solid powder3Fluorescent quenching.And raw materials are simple, utilization rate is high, at low cost, controllability is good.
Description
Technical field
The invention belongs to composite perofskite field of material technology, and in particular to a kind of CsPbBr3/Cs4PbBr6Composite calcium titanium
Pit wood material and preparation method thereof.
Background technique
Since synthesis technology is simple, high luminescence generated by light, caesium lead halide perovskite nanocrystal is in the photoelectric device such as sun
Energy battery, light emitting diode and field of lasers cause more and more to pay close attention to.However, commonly used organic ligand oleic acid
And oleyl amine, the proton translocation between them can cause serious ligand loss.On the other hand, work as CsPbX3It is transferred to solid powder
When for photoelectric device, the loss of organic capping ligand will lead to the aggregation of nanocrystal and the damage of subsequent quantum confinement
It loses, so that quantum yield, which is seriously reduced to, is approximately less than 0.1%.
In Cs4PbBr6CsPbBr is embedded in matrix3Nanocrystal, the strategy for forming composite construction are successfully proved
It is able to solve the loss due to quantum confinement and under solids accumulation state perovskite nanocrystal fluorescent quenching.It is unfortunate
, the controlledly synthesis of the dispersed nano level composite material with bright burn is still one and huge chooses in the solid state
War.
Summary of the invention
Goal of the invention: in view of the above technical problems, the present invention provides a kind of CsPbBr3/Cs4PbBr6Composite perofskite material
Material, it is intended to solve to assemble under existing perovskite organic ligand loss and solid powder state, lead to perovskite material stability
The problem of difference, fluorescent quenching.
Another object of the present invention is to provide the CsPbBr3/Cs4PbBr6The preparation method of composite perofskite material,
Its raw material is simple, utilization rate is high, at low cost, controllability is good.
Technical solution: in order to achieve the above object of the invention, the technical solution adopted in the present invention is as follows:
A kind of CsPbBr3/Cs4PbBr6The preparation method of composite perofskite material, comprising the following steps:
Take PbBr2It is dissolved in n,N-Dimethylformamide with CsBr, quickly then stirring is quickly being stirred to being completely dissolved
Lower be added thereto cetyl trimethylammonium bromide is prepared into precursor solution；Precursor solution is added in toluene, is stirred
Mix reaction, after reaction centrifugal treating, collect precipitating, drying to get.
As preferred:
The PbBr2Molar ratio with CsBr is (0.8~2): 4.
The cetyl trimethylammonium bromide is unique ligand in reaction.
The molar ratio of the CsBr and cetyl trimethylammonium bromide is 4:(1~6).
The quick mixing speed is 400rpm or more.
The time being stirred to react is 3-5h, and reaction temperature is 22-28 DEG C.
The centrifugal rotational speed is 5000rpm or more.
CsPbBr obtained by above-mentioned preparation method3/Cs4PbBr6Composite perofskite material.
The material includes rodlike Cs4PbBr6, and it is coated on rodlike Cs4PbBr6Interior several CsPbBr3Quantum dot
Particle.
The CsPbBr3/Cs4PbBr6The partial size of composite perofskite material is 0.2~1 μm.
Technical effect: compared with the existing technology, the present invention provides a kind of new synthesis processes, with cetyl trimethyl
Ammonium bromide is unique ligand in reaction, controllably synthesizes monodispersed CsPbBr3/Cs4PbBr6Rodlike composite perofskite material
Expect, wherein CsPbBr3It is evenly embedded into rodlike Cs4PbBr6In matrix.Sandwich prepared by the present invention can effectively be prevented
The only CsPbBr of solid powder3Fluorescent quenching.And raw materials are simple, utilization rate is high, at low cost, controllability is good.
Detailed description of the invention
Fig. 1 is CsPbBr prepared by the embodiment of the present invention 13/Cs4PbBr6The survey of the XRD of rodlike composite perofskite material
Attempt；
Fig. 2 is CsPbBr prepared by the embodiment of the present invention 13/Cs4PbBr6The Ultraluminescence of rodlike composite perofskite material
Scheme with PLE；
Fig. 3 is CsPbBr prepared by the embodiment of the present invention 13/Cs4PbBr6The TEM of rodlike composite perofskite material is tested
Figure；
Fig. 4 is CsPbBr prepared by the embodiment of the present invention 23/Cs4PbBr6The TEM of rodlike composite perofskite material is tested
Figure；
Fig. 5 is CsPbBr prepared by the embodiment of the present invention 43/Cs4PbBr6The TEM of rodlike composite perofskite material is tested
Figure；
Fig. 6 is CsPbBr prepared by the embodiment of the present invention 33/Cs4PbBr6Rodlike composite perofskite material and pure
CsPbBr3The solid fluorescence decay pattern of perovskite；
Specific embodiment
With reference to the accompanying drawing and specific embodiment the invention will be further described.
Embodiment 1
A kind of CsPbBr3/Cs4PbBr6The preparation method of composite perofskite material includes the following steps: to weigh respectively
0.08mmol PbBr2It is dissolved in 10ml n,N-Dimethylformamide with 0.4mmol CsBr, 400rpm or more speed is quickly stirred
It mixes to being completely dissolved, then adds under fast stirring using 0.4mmol cetyl trimethylammonium bromide as unique organic ligand
Enter and is wherein prepared into precursor solution；1ml precursor solution is added in 10ml toluene, 4h is stirred to react, reaction temperature is
25℃；Centrifugal treating under conditions of revolving speed is greater than 5000rpm collects precipitating drying.
Embodiment 2
A kind of CsPbBr3/Cs4PbBr6The preparation method of composite perofskite material includes the following steps: to weigh respectively
0.12mmol PbBr2It is dissolved in 10ml n,N-Dimethylformamide with 0.4mmol CsBr, 400rpm or more speed is quickly stirred
It mixes to being completely dissolved, then adds under fast stirring using 0.4mmol cetyl trimethylammonium bromide as unique organic ligand
Enter and is wherein prepared into precursor solution；1ml precursor solution is added in 10ml toluene, 4h is stirred to react, reaction temperature is
25℃；Centrifugal treating under conditions of revolving speed is greater than 5000rpm collects precipitating drying.
Embodiment 3
A kind of CsPbBr3/Cs4PbBr6The preparation method of composite perofskite material includes the following steps: to weigh respectively
0.16mmol PbBr2It is dissolved in 10ml n,N-Dimethylformamide with 0.4mmol CsBr, 400rpm or more speed is quickly stirred
It mixes to being completely dissolved, then adds under fast stirring using 0.6mmol cetyl trimethylammonium bromide as unique organic ligand
Enter and is wherein prepared into precursor solution；1ml precursor solution is added in 10ml toluene, 4h is stirred to react, reaction temperature is
25℃；Centrifugal treating under conditions of revolving speed is greater than 5000rpm collects precipitating drying.
Embodiment 4
A kind of CsPbBr3/Cs4PbBr6The preparation method of composite perofskite material includes the following steps: to weigh respectively
0.2mmol PbBr2It is dissolved in 10ml n,N-Dimethylformamide with 0.4mmol CsBr, 400rpm or more speed quickly stirs
To being completely dissolved, then it is added under fast stirring using 0.1mmol cetyl trimethylammonium bromide as unique organic ligand
Wherein it is prepared into precursor solution；1ml precursor solution is added in 10ml toluene, 4h, reaction temperature 25 are stirred to react
℃；Centrifugal treating under conditions of revolving speed is greater than 5000rpm collects precipitating drying.
Test example
(1) to the CsPbBr prepared in embodiment 13/Cs4PbBr6The solid powder of rodlike composite perofskite material is penetrated
The test of line diffraction, and by test result and CsPbBr3Perovskite material and Cs4PbBr6The standard card PDF# of perovskite material
54-0750 and PDF#73-2478, result are as shown in Figure 1, wherein topmost is to prepare in embodiment 1 in figure
CsPbBr3/Cs4PbBr6The XRD diagram of rodlike composite perofskite material, middle part CsPbBr3The XRD standard card of perovskite material
Piece, lowest part are Cs4PbBr6The standard card of perovskite material.
Interpretation of result: it can be seen that the CsPbBr of discovery synthesis from the result of figure3/Cs4PbBr6Perovskite composite material
There are a large amount of Cs in solid powder4PbBr6Material and a small amount of CsPbBr3Perovskite material.
(2) CsPbBr that will be prepared in embodiment 13/Cs4PbBr6It is molten that the solid powder of perovskite composite material is dissolved in toluene
Liquid is tested with UV detector and Fluorescence spectrophotometer, and test results are shown in figure 2, obtains CsPbBr3/
Cs4PbBr6UV, PLE and PL spectrum of perovskite composite material.
Interpretation of result: such as Fig. 2, the absorption peak at the place 495nm or so and the excitation with 450nm wavelength in ultra-violet absorption spectrum
The fluorescence emission peak Yu typical CsPbBr at the place 530nm or so in light activated fluorescence emission spectrum3Perovskite material it is ultraviolet
Photoluminescent property matches；Paddy peak and Cs in PLE spectrum, at the position 315nm4PbBr6Perovskite material matches.
(3) CsPbBr that will be prepared in embodiment 13/Cs4PbBr6Perovskite composite material is seen under transmission electron microscope
It surveys, obtained TEM figure, such as Fig. 3, the upper left corner is partial enlarged view.
Interpretation of result: it can be seen from the figure that nanometer rods have the size of about 50nm, it can be obvious in partial enlarged view
It is seen that there is a small amount of CsPbBr3Perovskite material is evenly distributed on Cs4PbBr6In material.
(4) CsPbBr that will be prepared in embodiment 23/Cs4PbBr6Perovskite composite material is seen under transmission electron microscope
It surveys, obtained TEM figure, such as Fig. 4.
Interpretation of result: it can be seen from the figure that nanometer rods have the size of about 200nm.
(5) CsPbBr that will be prepared in embodiment 43/Cs4PbBr6Perovskite composite material is seen under transmission electron microscope
It surveys, obtained TEM figure, such as Fig. 5.
Interpretation of result: it can be seen from the figure that nanometer rods have about 1 μm of size.
(6) CsPbBr that will be prepared in embodiment 13/Cs4PbBr6The solid powder of perovskite composite material and normal
CsPbBr3Film is made in perovskite solid powder, and being placed in temperature is 25 DEG C, in the temperature and humidity case that relative humidity (RH) is 60%.
The fluorescence decay of the two is monitored, obtained fluorescence decay curve such as Fig. 6.
Interpretation of result: can as seen from the figure, due to CsPbBr3Nanocrystal is dispersed in Cs4PbBr6It is blunt in matrix
Change their surface, CsPbBr3/Cs4PbBr6The air stability of composite nano materials is significantly improved, compared to pure
CsPbBr3Perovskite just falls below 50% hereinafter, CsPbBr in 30 days relative fluorescence quantum yields3/Cs4PbBr6Composite Nano material
Material still maintains 70% or more relative fluorescence quantum yield after 60 days.
Claims (10)
1. a kind of preparation method of composite perofskite material, which comprises the following steps:
Take PbBr2It is dissolved in n,N-Dimethylformamide with CsBr, quickly then stirring under fast stirring will to being completely dissolved
Cetyl trimethylammonium bromide, which is added thereto, is prepared into precursor solution；Precursor solution is added in toluene, stirring is anti-
Answer, after reaction centrifugal treating, collect precipitating, drying to get.
2. the preparation method of composite perofskite material according to claim 1, which is characterized in that the PbBr2With CsBr's
Molar ratio is (0.8~2): 4.
3. the preparation method of composite perofskite material according to claim 1, which is characterized in that the cetyl front three
Base ammonium bromide is unique ligand in reaction.
4. the preparation method of composite perofskite material according to claim 1, which is characterized in that the CsBr and hexadecane
The molar ratio of base trimethylammonium bromide is 4:(1~6).
5. the preparation method of composite perofskite material according to claim 1, which is characterized in that the quick mixing speed
For 400rpm or more.
6. the preparation method of composite perofskite material according to claim 1, which is characterized in that it is described be stirred to react when
Between be 3-5h, reaction temperature be 22-28 DEG C.
7. the preparation method of composite perofskite material according to claim 1, which is characterized in that the centrifugal rotational speed is
5000rpm or more.
8. composite perofskite material obtained by any one of claim 1-7 preparation method.
9. composite perofskite material according to claim 8, which is characterized in that the material includes rodlike Cs4PbBr6, with
And it is coated on rodlike Cs4PbBr6Interior several CsPbBr3Quantum dot particle.
10. composite perofskite material according to claim 8, which is characterized in that the CsPbBr3/Cs4PbBr6Composite calcium
The partial size of titanium ore material is 0.2~1 μm.
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Cited By (6)
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| CN110846715A (en) * | 2019-11-01 | 2020-02-28 | 南京航空航天大学 | Large size zero dimension Cs4PbBr6/CsPbBr3Perovskite scintillation crystal and preparation method thereof |
| WO2020081696A1 (en) * | 2018-10-16 | 2020-04-23 | Wake Forest University | Perovskite lighting systems |
| CN112345113A (en) * | 2020-10-15 | 2021-02-09 | 天津理工大学 | Small quantum dot temperature sensor |
| CN113244935A (en) * | 2021-05-17 | 2021-08-13 | 电子科技大学长三角研究院(湖州) | In-situ generated perovskite heterojunction photocatalyst and preparation method thereof |
| CN113462387A (en) * | 2021-07-01 | 2021-10-01 | 齐鲁工业大学 | Zero-dimensional perovskite nanocrystalline material with tunable light-emitting wavelength, preparation method thereof and light-emitting wavelength regulating method |
| CN113845908A (en) * | 2021-09-22 | 2021-12-28 | 天津理工大学 | Cs (volatile organic Compounds)4PbX6/CsPbX3Preparation method of composite microcrystal |
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| CN113244935A (en) * | 2021-05-17 | 2021-08-13 | 电子科技大学长三角研究院(湖州) | In-situ generated perovskite heterojunction photocatalyst and preparation method thereof |
| CN113462387A (en) * | 2021-07-01 | 2021-10-01 | 齐鲁工业大学 | Zero-dimensional perovskite nanocrystalline material with tunable light-emitting wavelength, preparation method thereof and light-emitting wavelength regulating method |
| CN113462387B (en) * | 2021-07-01 | 2023-08-25 | 齐鲁工业大学 | Zero-dimensional perovskite nanocrystalline material with tunable luminous wavelength, preparation method thereof and luminous wavelength regulation and control method |
| CN113845908A (en) * | 2021-09-22 | 2021-12-28 | 天津理工大学 | Cs (volatile organic Compounds)4PbX6/CsPbX3Preparation method of composite microcrystal |
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Application publication date: 20190820 |