CN110437831B - Method for widening light-emitting range of lead-free double perovskite - Google Patents

Method for widening light-emitting range of lead-free double perovskite Download PDF

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CN110437831B
CN110437831B CN201910838728.4A CN201910838728A CN110437831B CN 110437831 B CN110437831 B CN 110437831B CN 201910838728 A CN201910838728 A CN 201910838728A CN 110437831 B CN110437831 B CN 110437831B
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CN110437831A (en
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杨西贵
吕超凡
单崇新
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Zhengzhou University
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Abstract

A method for broadening the luminescent range of lead-free double perovskites, comprising the steps of: cs in submicron size2AgBiBr6Using a diamond anvil cell press as a pressurizing device as a sample, putting the sample into a pressure cavity, adopting silicon oil as a pressure transmission medium, continuously pressurizing the sample, and unloading to normal pressure to obtain the Cs with widened fluorescence range2AgBiBr6Perovskite. The method of the invention is that the pressure can change the arrangement mode and the electronic structure of atoms by applying the action of the external pressure, and the interaction among the atoms is influenced. In the method of the present invention, since Cs2AgBiBr6AgBr in (1)6And BiBr6The inorganic octahedron is twisted under pressure to separate Ag-Br and Bi-Br bond lengths with the same length into two types, so that the number of STE energy states between band gaps is increased, the fluorescence emission range is expanded, and the Cs2AgBiBr6The fluorescence range of the material is widened to 520-1000 nm, and the half-height width is widened to 230-245 nm.

Description

Method for widening light-emitting range of lead-free double perovskite
Technical Field
The invention belongs to the technical field of perovskite luminescent materials, and particularly relates to a method for widening the luminescent range of metal halide perovskite.
Background
Perovskite, which is an emerging semiconductor material that has been widely focused and studied in recent years, has important potential applications in solar cells, light emitting diodes, photosensors and the like due to a series of advantages such as low production cost, high optical absorption coefficient, large carrier diffusion length, high light emission quantum yield, and the like. The single-matrix wide-spectrum luminescent material can avoid a series of defects of the current commercial lighting multi-matrix fluorescent powder, such as efficiency reduction and color instability caused by self-absorption among different materials. Based on the purpose, researchers are constantly dedicated to searching for a method for widening the light-emitting range of the perovskite material so as to obtain a single-matrix perovskite high-efficiency stable light-emitting material capable of covering various different wave bands, and the perovskite high-efficiency stable light-emitting material can play an important role in a series of scenes, such as illumination, display, infrared detection and the like. At present, researchers carry out chemical shearing on Pb-based perovskite through large-size organic cations to ensure that the Pb-based perovskite structure is two-dimensional and has lattice distortion, thereby widening the emission spectrum range, wherein the range is generally 400-650 nm, but the large size hasOrganic cation and water-soluble Pb of lead element therein2+Ions can cause irreversible damage to the human nervous system and can also lead to reduced material stability. And lead-free all-inorganic Cs2AgBiBr6The perovskite luminescence range is generally 500-700 nm, and the perovskite has potential value as a single-substrate wide-spectrum emission material; in order to develop perovskite luminescent devices with more application prospects, a new method is provided on the important premise of widening the emission spectrum range of the perovskite luminescent devices to adjust and develop mature lead-free all-inorganic perovskite which has good performance and can be used for single-substrate wide-spectrum illumination.
Disclosure of Invention
The invention provides a method for widening the luminescence range of lead-free double perovskite by taking the problems in the background technology into consideration and finding out the blank range of research, and the Cs is effectively widened by using a novel method2AgBiBr6The luminescent range of perovskite materials.
The object of the invention is achieved in the following way:
a method for broadening the luminescent range of lead-free double perovskites, comprising the steps of: cs in submicron size2AgBiBr6As a sample, a diamond anvil cell press is used as a pressurizing device, the sample is put into a pressure cavity, silicon oil is used as a pressure transmission medium, the sample is continuously pressurized and then is unloaded to the normal pressure, and the Cs with the expanded fluorescence range is obtained2AgBiBr6Perovskite.
The method for widening the light-emitting range of the lead-free double perovskite comprises the steps of prepressing a metal sheet by using a diamond anvil cell press, drilling a small hole in the center of an indentation to serve as a sample cavity, and then using Cs2AgBiBr6Putting a sample into a sample cavity, dripping silicone oil as a pressure transmission medium, using ruby as a pressure calibration substance, continuously pressurizing, and when the pressure reaches 16-22 GPa, releasing the pressure to normal pressure to obtain Cs with widened fluorescence range2AgBiBr6Perovskite.
The method for widening the light-emitting range of the lead-free double perovskite is used for relieving the pressure to normal pressure when the pressure is increased to 20 GPa.
The Cs is used for widening the luminescence range of the lead-free double perovskite2AgBiBr6The perovskite average grain size is 100-1000 nm.
The Cs is used for widening the luminescence range of the lead-free double perovskite2AgBiBr6The perovskite thin film has an average grain size of 200 nm and an initial crystal structure of cubic phase.
The method for widening the luminescence range of the lead-free double perovskite, the Cs2AgBiBr6The perovskite thin film emits light with the wavelength of 590-650 nm before pressure treatment and emits light with the wavelength of 660-719 nm after pressure treatment.
The Cs is used for widening the luminescence range of the lead-free double perovskite2AgBiBr6The emission center wavelength of the perovskite thin film before pressure is 650 nm, and after pressure treatment, the emission center wavelength is 719 nm.
The method for broadening the luminescent range of lead-free double perovskite, Cs2AgBiBr6The fluorescence range of the material is widened to 520-1000 nm, the half-height width is 230-245 nm, and the grain size of the sample is reduced to 3-12 nm after pressure treatment.
A method for widening the luminescent range of the lead-free double perovskite, Cs2AgBiBr6The broadened spectrum of the material can be maintained under normal pressure.
Compared with the prior art, the method has the following advantages:
the method of the invention is that the pressure can change the arrangement mode and the electronic structure of atoms by applying the action of the external pressure, and the interaction among the atoms is influenced. In the method of the present invention, since Cs2AgBiBr6AgBr in (1)6And BiBr6The inorganic octahedron is twisted under pressure to lead the bond lengths of Ag-Br and Bi-Br with the same length to be respectively differentiated into two types, thereby increasing the number of STE energy states between band gaps, expanding the range of fluorescence emission and obtaining Cs2AgBiBr6The fluorescence range of the material is widened to 520-1000 nm, and the half-height width is widened to 230-245 nm.
The beneficial effects of the invention are listed as follows:
1. the invention widens Cs by high-pressure treatment2AgBiBr6The fluorescence spectrum range of the perovskite is increased from 145 nm to 245 nmnm。
2. The material of the invention has low preparation cost and simple steps.
3. The spectral range broadened by the process of the invention is also maintained after pressure relief.
Drawings
Figure 1 is a schematic diagram of a diamond anvil press.
FIG. 2 shows Cs2AgBiBr6Scanning electron microscope and element imaging of the perovskite thin film.
FIG. 3 shows Cs2AgBiBr6High resolution transmission electron microscopy images of perovskites.
FIG. 4 shows Cs2AgBiBr6Excitation spectrum and absorption and fluorescence spectrum of different emission wavelengths of perovskite under normal pressure.
FIG. 5 is Cs under pressure2AgBiBr6The fluorescence spectrum change curve of perovskite.
FIG. 6 shows Cs before and after the pressure treatment2AgBiBr6Comparison curve of perovskite fluorescence spectrum change.
FIG. 7 is 488 nm photoexcited Cs under pressure2AgBiBr6The perovskite fluorescence spectrum change curve has the maximum pressure of 16 GPa.
FIG. 8 shows 514 nm light excited Cs under pressure2AgBiBr6The perovskite fluorescence spectrum change curve has the maximum pressure of 4 GPa.
FIG. 9 shows Cs2AgBiBr6And (3) performing 22 GPa pressure treatment on the perovskite to obtain a high-resolution transmission electron microscope image.
Detailed Description
Example 1
T301 stainless steel is used as a sealing gasket, a diamond anvil cell device is pre-pressed to be 50 microns thick, then a small hole with the diameter of 120 microns is drilled in the center of the pre-pressing position to serve as a pressure cavity, and Cs with the diameter of 60 microns is used2AgBiBr6The film perovskite sample is put into a pressure cavity, silicon oil is sealed in the pressure cavity to serve as a pressure transmission medium, and the diamond carries out in-situ test on the anvil while generating pressure, and the device is shown in figure 1. Continuously pressurizing to 22 GPa and then completely removing the pressure, and using Raman spectroscopyTesting of Cs2AgBiBr6Fluorescence signal of perovskite. The results are shown in FIG. 5, Cs2AgBiBr6The fluorescence peak of the perovskite is first blue-shifted to 600 nm and then red-shifted to 700 nm, and the fluorescence range is broadened to from 520 to 1000 nm with a full width at half maximum of 230 nm. And the pressure is increased to 20GPa, and then the pressure is removed, the grain size of the sample is reduced to 6 nm in average size and 245 nm in full width at half maximum, and the fluorescence with the luminescence range of 520-1000 nm is reserved.
Example 2
The same sample and counter anvil encapsulation method as in example 1 was used. The pressure was continuously applied to 16 GPa using the 488 nm laser of a Raman spectrometer as excitation light, and then the pressure was completely removed. The fluorescence signal of the sample is tested, and as a result, as shown in fig. 6, the fluorescence blue of the sample is red-shifted after being shifted to 600 nm, and a new luminescence shoulder peak in the long wavelength direction can be distinguished, so that the fluorescence spectrum range is widened, wherein the fluorescence range is widened from 520 nm to 740 nm, and the half-height width is 230 nm. After the pressure is removed, a new luminous shoulder is also reserved, and the sample after pressure treatment reserves the property of broadening of a fluorescence spectrum, and the full width at half maximum is 245 nm.
Example 3
The same sample and counter anvil encapsulation method as in example 1 was used. The fluorescence signal of the sample was measured using 514.5 nm laser from a Raman spectrometer as excitation light, continuously pressurizing to 4 GPa, then completely depressurizing, and the result is shown in FIG. 7, where Cs is2AgBiBr6Similar spectrum blue shift occurs in the pressurizing process of the perovskite sample, the perovskite sample is restored to the original position after pressure is removed, and the phenomenon of spectrum broadening does not occur.
Example 4
The same sample and counter anvil encapsulation method as in example 1 was used. The pressure was continuously increased to 18 GPa using 514.5 nm laser of a Raman spectrometer as excitation light, and then the pressure was completely removed. According to the experimental phenomenon observed by the inventor and the like, the phenomenon that the sample will keep the spectrum broadening after the pressure is removed can be reasonably presumed.
Example 5
The same sample and counter anvil encapsulation method as in example 1 was used. The pressure was continuously increased to 16.5 GPa using 514.5 nm laser of a Raman spectrometer as excitation light, and then completely released. According to the experimental phenomenon observed by the inventor and the like, the phenomenon that the sample will keep the spectrum broadening after the pressure is removed can be reasonably presumed.
Example 6
The same sample and counter anvil encapsulation method as in example 1 was used. The pressure was continuously increased to 21.5 GPa using 514.5 nm laser of a Raman spectrometer as excitation light, and then the pressure was completely removed. According to the experimental phenomenon observed by the inventor and the like before, the phenomenon that the sample keeps the spectrum broadening after the pressure is removed can be reasonably presumed.
The metal sheet prepressed by the diamond anvil cell press can adopt any metal sheet, and the Cs with widened fluorescence range can be obtained by releasing pressure to normal pressure when the pressure is increased to 16-22 GPa2AgBiBr6A perovskite.
Sample Cs of the invention2AgBiBr6Perovskite thin film, said Cs2AgBiBr6The spin coating speed of the perovskite film is 2000 r/min, the spin coating time is 30 seconds, the annealing temperature is 280 ℃, the annealing time is 5 minutes, and the average grain size is 100-1000 nm; under the condition of no pressure, the emission wavelength is 610-650, which changes along with the change of the wavelength of the excitation light (325 nm-532 nm), and the experiment mainly uses the laser excitation of 514.5 nm; cs2AgBiBr6The exciting light wavelength of the perovskite film is 488-514.5 nm, and the Cs with widened fluorescence range can be obtained by relieving the pressure to normal pressure when the perovskite film is pressurized to 16-22 GPa2AgBiBr6Perovskite.
In the experiment, the metal sheet pre-pressed by the diamond anvil cell pressing machine is selected to have any value of 40-70 microns in thickness, the diameter of the central drilling hole of the metal steel sheet is R1, and the raw material Cs is2AgBiBr6The size of the perovskite thin film is R2, Cs2AgBiBr6The perovskite thin film is formed by Cs2AgBiBr6The film size R2 of the micron-sized film sample consisting of the perovskite small grains is smaller than that of the sample cavity R1.
Whether by usingThe process conditions give Cs with broadened fluorescence range2AgBiBr6The perovskite has the fluorescence range widened to 520-1000 nm and the half-height width to 230-245 nm through testing the fluorescence signal of the sample, the crystal grain of the sample is reduced to 3-12 nm after pressure treatment, and the average size is 6 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the overall concept of the invention, and these should be considered as the protection scope of the present invention, which will not affect the effect of the implementation of the present invention and the practicability of the patent.

Claims (7)

1. A method for widening the luminescence range of lead-free double perovskite is characterized by comprising the following steps: the method comprises the following steps: cs in submicron size2AgBiBr6As a sample, a diamond anvil cell press is used as a pressurizing device, the sample is put into a pressure cavity, silicon oil is used as a pressure transmission medium, the sample is continuously pressurized and then is unloaded to the normal pressure, and the Cs with the expanded fluorescence range is obtained2AgBiBr6A perovskite;
the specific method for continuously pressurizing the sample is as follows: prepressing a metal sheet by using a diamond anvil cell press, drilling a small hole at the center of an indentation to serve as a sample cavity, and then carrying out Cs treatment on the sample cavity2AgBiBr6Putting a sample into a sample cavity, dripping silicone oil as a pressure transmission medium, using ruby as a pressure calibration substance, and releasing pressure to normal pressure when the pressure reaches 16-22 GPa;
the Cs2AgBiBr6The fluorescence range of the material is widened to 520-1000 nm, the half-height width is 230-245 nm, and the grain size of the sample after pressure treatment is reduced to 3-12 nm.
2. The method for broadening the luminescence range of lead-free double perovskites as claimed in claim 1 wherein: when the pressure is increased to 20GPa, the pressure is relieved to normal pressure.
3. The method for broadening the luminescence range of lead-free double perovskite as defined in claim 1Is characterized in that: the Cs2AgBiBr6The average grain size of the perovskite before pressure is 100-1000 nm.
4. The method for broadening the luminescence range of lead-free double perovskites as claimed in claim 1 wherein: the Cs2AgBiBr6The perovskite has an average grain size of 200 nm before stress and an initial crystal structure of cubic phase.
5. The method for broadening the luminescence range of lead-free double perovskites as claimed in claim 1 wherein: the Cs2AgBiBr6The perovskite has an emission wavelength of 590-650 nm before pressure and has an emission wavelength of 660-719 nm after pressure treatment.
6. The method for broadening the luminescence range of lead-free double perovskites as claimed in claim 1 wherein: the Cs2AgBiBr6The perovskite luminescence center wavelength is 650 nm before pressure, and 719 nm after pressure treatment.
7. The method for broadening the luminescence range of lead-free double perovskites as claimed in claim 1, wherein: cs2AgBiBr6The broadened spectrum of the material can be maintained at normal pressure.
CN201910838728.4A 2019-09-05 2019-09-05 Method for widening light-emitting range of lead-free double perovskite Active CN110437831B (en)

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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
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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
High-Pressure Band-Gap Engineering in Lead-Free Cs2AgBiBr6 Double Perovskite;Li Qian;《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》;20171115;第56卷(第50期);"Supporting Information"S2页第2段,第15970页左栏倒数第1段-右栏第1段，图2 *
Pressure-induced structural transition and band gap evolution of double perovskite Cs2AgBiBr6 nanocrystals;Fu Ruijing;《Nanoscale》;20190816;第11卷(第36期);"Supplementary Information"实验部分，图S3，图2 *

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