CN110735182A - Method for preparing high-fluorescence zero-dimensional perovskite single crystal by utilizing solution self-assembly - Google Patents

Method for preparing high-fluorescence zero-dimensional perovskite single crystal by utilizing solution self-assembly Download PDF

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CN110735182A
CN110735182A CN201911044757.XA CN201911044757A CN110735182A CN 110735182 A CN110735182 A CN 110735182A CN 201911044757 A CN201911044757 A CN 201911044757A CN 110735182 A CN110735182 A CN 110735182A
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zero
dimensional perovskite
solution
single crystal
assembly
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徐伟龙
肖进
陈海悦
卞维柏
熊超
赵宇
郑敏
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Changzhou Institute of Technology
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Changzhou Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

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  • Crystallography & Structural Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a method for preparing high-fluorescence zero-dimensional perovskite single crystals by using solution self-assembly, which comprises the following steps of 1) dissolving lead bromide and cesium bromide in a dimethylformamide solution, 2) treating the solution by using top ultrasound, 3) standing after complete reaction, 4) cleaning and precipitating by using dimethyl sulfoxide to obtain zero-dimensional perovskite powder, 5) dissolving the powder in dimethyl sulfoxide, 6) dropwise adding the solution on a glass substrate, and placing in a closed atmosphere to obtain the zero-dimensional perovskite single crystals, wherein the average size of the zero-dimensional perovskite single crystals is about 100 micrometers.

Description

Method for preparing high-fluorescence zero-dimensional perovskite single crystal by utilizing solution self-assembly
Technical Field
The invention relates to methods for preparing high-fluorescence zero-dimensional perovskite single crystals by using solution self-assembly, belonging to the technical field of photoelectric materials and devices.
Background
The perovskite is type ABX3A material in the form of a film. The basic structural unit is BX6The efficiency of the photovoltaic device is over 25% at present, the perovskite nanocrystals have broad prospects in the fields of luminescence and display due to high fluorescence efficiency and adjustable band gap, however, in the thin film state, the fluorescence efficiency is reduced due to aggregation effect and surface defect induced fluorescence quenching between the nanocrystals6The octahedron is completely separated, excitons generated by illumination cannot be effectively separated, and the excitons are confined in the octahedron and finally emit light in a radiative recombination mode. There are many methods for synthesizing zero-dimensional perovskite, such as co-evaporation method, anti-solvent modulation method, thermal injection method and surfactant modulation method, and most of the products are granular or thin films, and relatively few reports are reported for large-size zero-dimensional perovskite single crystals. It is known that single crystals are less affected by surface states and defect states than thin films or particles, and therefore, the properties of the material itself can be more accurately reflected.
The current preparation of zero-dimensional perovskite single crystals has the following problems:
(1) the prior method for synthesizing the zero-dimensional perovskite has more methods, and the product is usually granular or a thin film;
(2) during the synthesis process of the zero-dimensional perovskite material, a surfactant is usually used, so that the product is not a pure-phase zero-dimensional perovskite and may contain impurities;
(3) zero-dimensional perovskite particles with impurities are adopted as crystal grains for growth, so that the properties of crystals are influenced;
(4) although zero-dimensional perovskite crystals are prepared, they are small in size.
The synthesis of the zero-dimensional perovskite single crystal is of great significance for promoting the synthesis of the zero-dimensional perovskite single crystal in the field of photoelectric devices.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly.
The invention adopts the following technical scheme:
the method for preparing the high-fluorescence zero-dimensional perovskite single crystal ore by utilizing solution self-assembly comprises the following steps:
cesium bromide (CsBr) and lead bromide (PbBr)2) Dissolving in 5 ml of dimethylformamide solution, processing the solution by a top ultrasound processing technology, wherein the power is 20 watts, the ultrasound time is 5-10 minutes, then the interval is 1-2 minutes, the process is repeated for a plurality of times, and the reaction condition is carried out under the ice bath condition. During the reaction, the color of the solution gradually changed to orange. After the reaction is completed, the solution is placed in a refrigerator, and after 24 hours, the precipitate is washed by dimethyl sulfoxide to obtain zero-dimensional perovskite powder. No surfactant is used in the reaction process, so the cleaning process is relatively simple. Dropping the zero-dimensional perovskite dissolved in the dimethyl sulfoxide solution on a glass substrate, then placing the glass substrate in a closed atmosphere, and gradually growing the crystal of the zero-dimensional perovskite along with the slow volatilization of the solvent.
Compared with other processes, the method has the following beneficial effects:
(1) cesium bromide and lead bromide react in a solution without using a surfactant, so that the cleaning process is relatively simple;
(2) in the process of synthesizing perovskite particles, the adopted method is top ultrasound, and the parameters only have power, so the method is easy to control and has good repeatability;
(3) the size of the zero-dimensional perovskite single crystal reaches 100 microns, and the zero-dimensional perovskite single crystal is larger than crystals prepared by other processes and is a regular cuboid;
(4) the invention adopts a method of assisting the self-assembly of the solution by a top ultrasonic treatment process to finally grow the perovskite crystal with a strong luminous zero-dimensional structure, and the average size of the obtained zero-dimensional perovskite single crystal is about 100 microns.
Drawings
Fig. 1 is a scanning electron microscope image of the powder.
Fig. 2 is a scanning electron microscope image of a crystal.
FIG. 3 is an X-ray diffraction spectrum of a crystal.
Fig. 4 is a photoluminescence spectrum of the crystal.
FIG. 5 is a confocal fluorescence micrograph of crystals.
FIG. 6 is a graph of fluorescence quantum efficiency test results for a crystal;
FIG. 7 is a table of results of fluorescence quantum efficiency tests on crystals.
Detailed Description
The present invention is further described in detail below with reference to the attached figures.
Example
The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by using the solution self-assembly method comprises the following steps of:
1) 1.16 g of cesium bromide (CsBr) powder, 0.5 g of lead bromide (PbBr) were weighed in2) Dissolving in dimethylformamide solution;
2) placing the mixed solution in an ice bath environment;
3) processing the solution by adopting a top ultrasonic process, wherein the power is 20 watts, the ultrasonic time is 5 minutes, and the solution turns orange;
4) after 5 minutes of sonication, 1 minute was stopped;
5) repeating the above steps for 5 times;
6) putting the solution in a refrigerator, and precipitating for 24 hours;
7) cleaning the precipitate by using a dimethyl sulfoxide solution to obtain zero-dimensional perovskite powder;
8) dissolving zero-dimensional perovskite powder in dimethyl sulfoxide, and dropwise adding the solution on a glass substrate;
9) placing the glass substrate in a closed atmosphere, and gradually growing the zero-dimensional perovskite crystal along with slow volatilization of the solvent;
10) and taking out the crystal after the solvent is completely volatilized, and testing and characterizing.
Example two
The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by using the solution self-assembly method comprises the following steps of:
1) 0.8 g of cesium bromide (CsBr) powder, 0.34 g of lead bromide (PbBr) were weighed in2) Dissolving in dimethylformamide solution;
2) placing the mixed solution in an ice bath environment;
3) processing the solution by adopting a top ultrasonic process, wherein the power is 20 watts, the ultrasonic time is 10 minutes, and the solution turns orange;
4) after 10 minutes of sonication, 2 minutes were stopped;
5) repeating the above steps for 5 times;
6) putting the solution in a refrigerator, and precipitating for 24 hours;
7) cleaning the precipitate by using a dimethyl sulfoxide solution to obtain zero-dimensional perovskite powder;
8) dissolving zero-dimensional perovskite powder in dimethyl sulfoxide, and dropwise adding the solution on a glass substrate;
9) placing the glass substrate in a closed atmosphere, and gradually growing the zero-dimensional perovskite crystal along with slow volatilization of the solvent;
10) and taking out the crystal after the solvent is completely volatilized, and testing and characterizing.
EXAMPLE III
The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by using the solution self-assembly method comprises the following steps of:
1) 1.16 g of cesium bromide (CsBr) powder, 0.5 g of lead bromide (PbBr) were weighed in2) Dissolving in dimethylformamide solution;
2) placing the mixed solution in an ice bath environment;
3) processing the solution by adopting a top ultrasonic process, wherein the power is 20 watts, the ultrasonic time is 5 minutes, and the solution turns orange;
4) after 10 minutes of sonication, 2 minutes were stopped;
5) repeating the above steps for 5 times;
6) putting the solution in a refrigerator, and precipitating for 24 hours;
7) cleaning the precipitate by using a dimethyl sulfoxide solution to obtain zero-dimensional perovskite powder;
8) dissolving zero-dimensional perovskite powder in dimethyl sulfoxide, and dropwise adding the solution on a glass substrate;
9) placing the glass substrate in a closed atmosphere, and gradually growing the zero-dimensional perovskite crystal along with slow volatilization of the solvent;
10) and taking out the crystal after the solvent is completely volatilized, and testing and characterizing.
The invention is further described in detail with reference to the figures and examples.
FIG. 1 is a scanning electron microscope image of a zero-dimensional perovskite powder having a particle average size of 1 micron and in an amorphous state;
FIG. 2 is a scanning electron microscope image of a zero-dimensional perovskite crystal having an average size of about 100 μm, a relatively regular structure, and a rectangular parallelepiped with well defined corners;
FIG. 3 is an X-ray diffraction pattern of a zero-dimensional perovskite crystal, and the comparison with the diffraction pattern in a library shows that the peak position is well corresponding to JPCDS No.73-2478, and the result shows that the crystal is a pure-phase zero-dimensional perovskite, and the chemical composition is Cs4PbBr6；
FIG. 4 is a photoluminescence spectrum of a crystal, wherein the luminescence peak position is 517nm, the full width at half maximum is 19nm, and the luminescence peak position is relatively narrow;
FIG. 5 is a confocal fluorescence microscopic image of zero-dimensional perovskite crystals, which can be seen to be luminescent throughout the crystals;
FIGS. 6-7 show the results of the fluorescence quantum efficiency test of the crystal, from which it can be seen that the fluorescence quantum yield is 32.5%.
In the embodiment, the high-fluorescence zero-dimensional perovskite single crystal is prepared by self-assembly of a solution, firstly, zero-dimensional perovskite powder is prepared by top ultrasound, and then, the powder is placed in a sealed dimethyl sulfoxide atmosphere to obtain the large-size zero-dimensional perovskite single crystal.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by utilizing solution self-assembly is characterized by comprising the following steps of:
1) dissolving lead bromide and cesium bromide in a dimethylformamide solution;
2) treating the solution by using ultrasound;
3) standing after the reaction is completed;
4) washing the precipitate by using dimethyl sulfoxide to obtain zero-dimensional perovskite powder;
5) dissolving zero-dimensional perovskite powder in dimethyl sulfoxide solution, and placing in a closed atmosphere to grow crystals.
2. The method for preparing a high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly as claimed in claim 1, wherein in the step 1), cesium bromide powder is 0.8-1.16 g, and lead bromide powder is 0.34-0.5 g.
3. The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly according to claim 1, wherein the ultrasonic mode in the step 2) is top ultrasonic.
4. The method for preparing a high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly as claimed in claim 1, wherein the step 2) ultrasonic time is 5-10 minutes, the interval time is 1-2 minutes, and the process is repeated several times.
5. The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly according to claim 1, wherein the step 2) ultrasonic process is performed under ice bath conditions.
6. The method for preparing a high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly as claimed in claim 1, wherein the standing process of step 3) is standing in a refrigerator.
7. The method for preparing a high-fluorescence zero-dimensional perovskite single crystal by using solution self-assembly as claimed in claim 1, wherein the step 4) is performed with several times of cleaning.
8. The method for preparing the high-fluorescence zero-dimensional perovskite single crystal by using the solution self-assembly as claimed in claim 1, wherein the substrate material in the step 5) is a glass substrate, and the time is long until the solvent is completely volatilized.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944525A (en) * 2020-08-25 2020-11-17 深圳大学 Zero-dimensional cesium-lead-bromine inorganic perovskite material and preparation method thereof
CN113479927A (en) * 2021-07-01 2021-10-08 东南大学 Synthesis of yellow light-emitting halogen perovskite CsCu in water2I3Method for producing powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944525A (en) * 2020-08-25 2020-11-17 深圳大学 Zero-dimensional cesium-lead-bromine inorganic perovskite material and preparation method thereof
CN111944525B (en) * 2020-08-25 2022-05-10 深圳大学 Zero-dimensional cesium-lead-bromine inorganic perovskite material and preparation method thereof
CN113479927A (en) * 2021-07-01 2021-10-08 东南大学 Synthesis of yellow light-emitting halogen perovskite CsCu in water2I3Method for producing powder

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