CN110437831A - A method of widening unleaded double-perovskite light emitting region - Google Patents
A method of widening unleaded double-perovskite light emitting region Download PDFInfo
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Abstract
A method of widening unleaded double-perovskite light emitting region, comprising the following steps: with the Cs of submicron-scale2AgBiBr6As sample, using diamond anvil cell press as pressurizing device, sample is put into pressure chamber, takes silicone oil as transmission medium, to being unloaded after sample persistent pressure to normal pressure to get to the Cs for having widened extent of fluorescence2AgBiBr6Perovskite.The method of the present invention is the effect by applying ambient pressure, and pressure can change the arrangement mode and electronic structure of atom, influence interatomic interaction.In the methods of the invention, due to Cs2AgBiBr6In AgBr6And BiBr6There is torsion under stress in inorganic octahedron, causes Ag-Br and Bi-Br bond distance consistent in length to be divided into two kinds respectively, increases the number of STE energy state between band gap, expands the range of fluorescent emission, Cs2AgBiBr6Material extent of fluorescence is widened to 520-1000 nm, and halfwidth is widened to 230-245 nm.
Description
Technical field
The invention belongs to perovskite luminescent material technical fields, and in particular to a kind of metal halide perovskite light emitting region
Widen method.
Background technique
As the emerging semiconductor material for obtaining extensive concern and research in recent years, perovskite since its preparation cost is low,
The absorption coefficient of light is high, and carrier diffusion length is big, a series of advantage such as photoluminescence quantum yield height, in solar battery, shines
Diode, photoelectric sensor etc. have important potential application.The wide range luminescent material of single-matrix can be to avoid instantly
Commercialization illuminates more a series of disadvantages of substrate fluorescent powder, for example the self-absorption between different materials leads to efficiency decline and color not
Stablize.Based on this purpose, researcher has been devoted to find the method for widening perovskite material light emitting region, with obtain can
The single-matrix perovskite efficient stable luminescent material for covering each different-waveband, can play important work in a series of scenes
With, such as illumination, display and infrared detection etc..There is researcher by large-sized organic cation to Pb based perovskite at present
Chemical shearing is carried out, so that Pb based perovskite structure two dimension and there is lattice distortion, to widen emission spectrum range, model
Generally 400-650 nm is enclosed, but the wherein Pb of large scale organic cation and lead element therein to water dissolvable2+Ion
There is irreversible injury to the nervous system of people, also results in stability of material reduction.And unleaded full-inorganic
Cs2AgBiBr6Perovskite light emitting region is generally 500-700 nm, there is the potential value as single-matrix wide range emissive material；
Develop the perovskite luminescent device of more application prospect, important prerequisite, which is lain also in, proposes new method, widens its emission spectrum
Range, come adjust and it is expansionary can be good, can be used for the unleaded full-inorganic perovskite of maturation of single-matrix wide range illumination.
Summary of the invention
The problem of considering background technique, finds research blank range, and the present invention provides one kind and widens unleaded double calcium
The method of titanium ore light emitting region effectively widens Cs with a kind of new method2AgBiBr6Perovskite material light emitting region.
The object of the present invention is achieved in the following manner:
A method of widening unleaded double-perovskite light emitting region, comprising the following steps: with the Cs of submicron-scale2AgBiBr6
As sample, using diamond anvil cell press as pressurizing device, sample is put into pressure chamber, silicone oil is taken to be situated between as pressure transmission
Matter, to being unloaded after sample persistent pressure to normal pressure to get to the Cs for having widened extent of fluorescence2AgBiBr6Perovskite.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, utilizes diamond anvil cell press precompressed metal
Piece, and aperture is drilled through as sample cavity, then by Cs at impression center2AgBiBr6Sample is put into sample cavity, and instills silicone oil work
For transmission medium, using ruby as pressure calibration substance, persistent pressure is unloaded and is depressed into often when pressure reaches 16-22 GPa
Pressure, has been widened the Cs of extent of fluorescence2AgBiBr6Perovskite.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, unloads when being forced into 20 GPa and is depressed into normal pressure.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, the Cs2AgBiBr6The equal crystallite dimension of perovskite
In 100-1000 nm.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, the Cs2AgBiBr6Perovskite thin film is averaged
For crystallite dimension in 200 nm, tial crystalline structure is cubic phase.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, the Cs2AgBiBr6Perovskite thin film is in pressure
Preceding launch wavelength 590-650 nm, launch wavelength 660-719 nm after pressurized treatments.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, the Cs2AgBiBr6Perovskite thin film is in pressure
Preceding emission center wavelength is 650 nm, is 719 nm after pressurized treatments.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, Cs2AgBiBr6Material extent of fluorescence widen to
520-1000 nm, halfwidth are 230-245 nm, and sample crystallite dimension is reduced to 3-12 nm after pressure treatment.
A kind of above-mentioned method for widening unleaded double-perovskite light emitting region, Cs2AgBiBr6The spectrum that material is widened is in normal pressure
Under be able to maintain.
Compared with the existing technology, it has the advantage that
The method of the present invention is the effect by applying ambient pressure, and pressure can change the arrangement mode and electronic structure of atom,
Influence interatomic interaction.In the methods of the invention, due to Cs2AgBiBr6In AgBr6And BiBr6Inorganic octahedron exists
Occur torsion under pressure, causes Ag-Br and Bi-Br bond distance consistent in length to be divided into two kinds respectively, increase STE between band gap
The number of energy state expands the range of fluorescent emission, Cs2AgBiBr6Material extent of fluorescence is widened to 520-1000 nm, halfwidth
It widens to 230-245 nm.
Beneficial effects of the present invention are listed below:
1. the mode of HIGH PRESSURE TREATMENT of the invention has widened Cs2AgBiBr6The fluorescence spectra of perovskite, halfwidth is by 145
Nm increases to 245 nm.
2. material preparation cost of the invention is cheap, step is simple.
3. the spectral region that the method for the present invention is widened can also be kept after release.
Detailed description of the invention
Fig. 1 is diamond anvil cell press schematic diagram.
Fig. 2 is Cs2AgBiBr6The scanning electron microscope and element image of perovskite thin film.
Fig. 3 is Cs2AgBiBr6The high-resolution-ration transmission electric-lens figure of perovskite.
Fig. 4 is Cs2AgBiBr6The excitation spectrum of different emission under perovskite normal pressure and absorption, fluorescence spectrum.
Fig. 5 is Cs under pressure2AgBiBr6The fluorescence spectrum change curve of perovskite.
Fig. 6 is the Cs before and after pressure treatment2AgBiBr6The correlation curve of perovskite fluorescence spectrum variation.
Fig. 7 is the light activated Cs of 488 nm under pressure2AgBiBr6Perovskite fluorescence spectrum change curve, maximum pressure 16
GPa。
Fig. 8 is the light activated Cs of 514 nm under pressure2AgBiBr6Perovskite fluorescence spectrum change curve, maximum pressure 4
GPa。
Fig. 9 is Cs2AgBiBr6High-resolution-ration transmission electric-lens figure of the perovskite after 22 GPa pressure treatments.
Specific embodiment
Embodiment 1
Using T301 stainless steel as gasket seal, first using diamond anvil cell device to its it is pre- be depressed into 50 microns of thickness, then
Precompressed position the big aperture of 120 microns of diameter of centre drill one as pressure chamber, by 60 microns of sizes of diameter
Cs2AgBiBr6Thin film perovskites sample is put into pressure chamber, and enclosed silicone oil is being generated as pressure transmission medium diamond anvil cell
Pressure carries out in-situ test while acting on, and device is as shown in Figure 1.Then persistent pressure power sheds pressure to 22 GPa completely,
Cs is tested using Raman spectrometer2AgBiBr6The fluorescence signal of perovskite.As a result as shown in figure 5, Cs2AgBiBr6Perovskite
Fluorescent peal is first blue shifted to 600 nm, then red shift to 700 nm, and extent of fluorescence is widened to from 520 nm to 1000 nm,
Halfwidth is 230 nm.Also, pressure rises to 20GPa, then after shedding pressure, sample crystallite dimension has been reduced to mean size 6
Nm, 245 nm of halfwidth, the fluorescence that light emitting region occupies 520-1000 nm have been retained.
Embodiment 2
Using with identical sample in embodiment 1 and opposed anvils packaging method.Using 488 nm laser of Raman spectrometer as
Then exciting light, persistent pressure power shed pressure to 16 GPa completely.The fluorescence signal of test sample, as a result as shown in fig. 6,
There is red shift after being blue shifted to 600 nm in the fluorescence of sample, can differentiate and a new luminous acromion occurs in long wave length direction, lead
Widening for fluorescence spectra is caused, extent of fluorescence is widened to from 520 nm to 740 nm, and halfwidth is 230 nm.Shed pressure
Afterwards, new luminous acromion is also retained, and the sample after pressure treatment remains the property of fluorescence spectrum wideization, and halfwidth is
245 nm。
Embodiment 3
Using with identical sample in embodiment 1 and opposed anvils packaging method.Made using 514.5 nm laser of Raman spectrometer
For exciting light, then persistent pressure to 4 GPa sheds pressure completely, the fluorescence signal of test sample, as a result as shown in fig. 7,
Cs2AgBiBr6There is similar blue spectral shift in perovskite sample pressure process, sheds and restores after pressure to original position, not
There is the widthization phenomenon of spectrum.
Embodiment 4
Using with identical sample in embodiment 1 and opposed anvils packaging method.Made using 514.5 nm laser of Raman spectrometer
For exciting light, then persistent pressure sheds pressure to 18 GPa completely.People etc. are existing in the experiment observed before according to the present invention
As the phenomenon that sample after pressure will retain spectral width can be shed with reasonable expectation.
Embodiment 5
Using with identical sample in embodiment 1 and opposed anvils packaging method.Made using 514.5 nm laser of Raman spectrometer
For exciting light, then persistent pressure sheds pressure to 16.5 GPa completely.People etc. are in the experiment observed before according to the present invention
Phenomenon can shed the phenomenon that sample after pressure will retain spectral width with reasonable expectation.
Embodiment 6
Using with identical sample in embodiment 1 and opposed anvils packaging method.Made using 514.5 nm laser of Raman spectrometer
For exciting light, then persistent pressure sheds pressure to 21.5 GPa completely.People etc. are in the experiment observed before according to the present invention
Phenomenon can shed the phenomenon that sample after pressure will retain spectral width with reasonable expectation.
The sheet metal of diamond anvil cell press precompressed of the invention can use any sheet metal, as long as being pressurized to 16-
It when 22 GPa, unloads and is depressed into normal pressure, just can have been widened the Cs of extent of fluorescence2AgBiBr6Perovskite.
Sample Cs of the present invention2AgBiBr6Perovskite thin film, the Cs2AgBiBr6The spin coating rate of perovskite thin film is
2000 r/min, spin-coating time are 30 seconds, and annealing temperature is 280 degree, and annealing time is 5 minutes, and average grain size is in 100-
1000 nm；Under non-plus-pressure, launch wavelength is 610-650, is become with the variation (325 nm-532 nm) of excitation wavelength
Change, this experiment is mainly the laser excitation using 514.5 nm；Cs2AgBiBr6The excitation wavelength 488- of perovskite thin film
514.5 nm when by being pressurized to 16-22 GPa, unloading and being depressed into normal pressure, just can have been widened the Cs of extent of fluorescence2AgBiBr6Calcium
Titanium ore.
The sheet metal of diamond anvil cell press precompressed in experiment is selected with a thickness of any value in 40-70 microns, metal
The diameter of steel disc centre-drilling hole is R1, raw material Cs2AgBiBr6Perovskite thin film is having a size of R2, Cs2AgBiBr6Perovskite thin film is
By Cs2AgBiBr6The micron-sized film sample of perovskite little crystal grain composition, film dimensions R2 are less than sample cavity R1.
No matter using the obtained Cs for having widened extent of fluorescence of that process conditions2AgBiBr6Perovskite passes through test
Sample fluorescence signal, extent of fluorescence are widened to 520-1000 nm, halfwidth to 230-245 nm, sample crystal grain after pressure treatment
It is reduced to 3 nm-12 nm, 6 nm of mean size.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without depart from that overall concept of the invention, several changes and improvements can also be made, these also should be considered as of the invention
Protection scope, these all will not influence the effect and patent practicability that the present invention is implemented.
Claims (9)
1. a kind of method for widening unleaded double-perovskite light emitting region, it is characterised in that: the following steps are included: with sub-micro meter ruler
Very little Cs2AgBiBr6As sample, using diamond anvil cell press as pressurizing device, sample is put into pressure chamber, is taken
Silicone oil is as transmission medium, to being unloaded after sample persistent pressure to normal pressure to get to the Cs for having widened extent of fluorescence2AgBiBr6Calcium titanium
Mine.
2. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that: utilize
Diamond anvil cell press precompressed sheet metal, and aperture is drilled through as sample cavity, then by Cs at impression center2AgBiBr6Sample
It is put into sample cavity, and instills silicone oil as transmission medium, using ruby as pressure calibration substance, when pressure reaches 16-22
It when GPa, unloads and is depressed into normal pressure, widened the Cs of extent of fluorescence2AgBiBr6Perovskite.
3. a kind of method for widening unleaded double-perovskite light emitting region according to claim 2, it is characterised in that: pressurization
It is unloaded when to 20 GPa and is depressed into normal pressure.
4. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that: described
Cs2AgBiBr6The equal crystallite dimension of perovskite is in 100-1000 nm.
5. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that: described
Cs2AgBiBr6For the average grain size of perovskite thin film in 200 nm, tial crystalline structure is cubic phase.
6. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that: described
Cs2AgBiBr6Perovskite thin film the launch wavelength 590-650 nm before pressure, the launch wavelength 660-719 after pressure treatment
nm。
7. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that: described
Cs2AgBiBr6Perovskite thin film centre of luminescence wavelength 650 nm before pressure is 719 nm after pressurized processing.
8. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that:
Cs2AgBiBr6Material extent of fluorescence is widened to 520-1000 nm, and halfwidth is 230-245 nm, sample crystal grain after pressure treatment
Size is reduced to 3-12 nm.
9. a kind of method for widening unleaded double-perovskite light emitting region according to claim 1, it is characterised in that:
Cs2AgBiBr6The spectrum that material is widened can be kept under normal pressure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862105A (en) * | 2019-11-22 | 2020-03-06 | 郑州大学 | Pyramid-shaped zinc oxide nano-particles with enhanced fluorescence intensity as well as preparation method and application thereof |
| CN111077175A (en) * | 2019-12-31 | 2020-04-28 | 四川大学 | Device and method for measuring solubility of crystal under high pressure |
-
2019
- 2019-09-05 CN CN201910838728.4A patent/CN110437831B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| FU RUIJING: "Pressure-induced structural transition and band gap evolution of double perovskite Cs2AgBiBr6 nanocrystals", 《NANOSCALE》 * |
| LI QIAN: "High-Pressure Band-Gap Engineering in Lead-Free Cs2AgBiBr6 Double Perovskite", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862105A (en) * | 2019-11-22 | 2020-03-06 | 郑州大学 | Pyramid-shaped zinc oxide nano-particles with enhanced fluorescence intensity as well as preparation method and application thereof |
| CN111077175A (en) * | 2019-12-31 | 2020-04-28 | 四川大学 | Device and method for measuring solubility of crystal under high pressure |
| CN111077175B (en) * | 2019-12-31 | 2022-04-05 | 四川大学 | Device and method for measuring solubility of crystal under high pressure |
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| CN110437831B (en) | 2022-06-17 |
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