CN108502927B - A kind of preparation method of caesium bismuth bromine perovskite nanometer sheet - Google Patents
A kind of preparation method of caesium bismuth bromine perovskite nanometer sheet Download PDFInfo
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- CN108502927B CN108502927B CN201810535204.3A CN201810535204A CN108502927B CN 108502927 B CN108502927 B CN 108502927B CN 201810535204 A CN201810535204 A CN 201810535204A CN 108502927 B CN108502927 B CN 108502927B
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- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of preparation methods of caesium bismuth bromine perovskite nanometer sheet, it is characterized in that, the following steps are included: bismuth bromide and oleic acid, oleyl amine, 1- octadecylene are mixed to form mixture by (1), then, under conditions of persistently vacuumizing, the mixture is heated to 100-120 DEG C, and maintains 60-120min, obtains the mixed solution containing bismuth bromide；(2) mixed solution of Xiang Hanyou bismuth bromide is filled with nitrogen, and temperature is risen to 170-180 DEG C, is then injected into oleic acid caesium solution, and the reaction time maintains 5-60s, can be obtained including Cs3Bi2Br9Reaction product including perovskite nanometer sheet.The present invention is improved by the process flow setting to preparation method entirety, key parameter condition, it can effectively solve the problem that a nanometer piece preparation method complexity, problem at high cost, it is the method for completely new solwution method technique, low cost preparation nanometer sheet, and the nanometer sheet being prepared has the characteristics that highly crystalline, fabulous stability, good optical characteristics.
Description
Technical field
The invention belongs to perovskite technical field of nanometer material preparation, receive more particularly, to a kind of caesium bismuth bromine perovskite
The preparation method of rice piece.
Background technique
Nanocrystalline perovskite is a kind of semiconductor nano material with excellent optical property, when particle size enters nanometer
When magnitude, size confinement will cause quantum size effect, quantum confined effect, macro quanta tunnel effect and skin effect, from
And the low-dimensional physical property that nanometer system is different from meta system and microsystem is derived, it shows many different from macroscopic body material
Physicochemical properties.
Cs3Bi2Br9Perovskite nanometer sheet as a kind of novel lead-free perovskite photoelectric material, both with two-dimensional material can
The features such as solution processing, flexibility, wearable property, carrier mobility height, exciton confinement high but also with perovskite material crystallinity
Can the characteristics such as big and absorption coefficient of light height, have become the hot spot in investigation of materials field and receive significant attention.Traditional lead system calcium
Titanium ore nano material has many important features, such as half-peak width, emission wavelength are adjustable, quantum yield is high.However, having
The unleaded perovskite nanometer sheet of two-dimensional structure is but rarely reported.The performance of two-dimension nano materials and its thickness often have close pass
System, by taking laminated perovskite nanometer sheet as an example, when thickness is smaller, which will have extremely strong optical coupling effect, crystal structure
The phenomena such as relaxation and fluorescence spectrum displacement.There are still many to ask for the preparation method of conventional two-dimensional perovskite nano material
Topic, such as nanometer sheet is prepared using template, it needs to be divided into two steps, PbX is prepared by vapor deposition or solution methods first2(X
=Cl/Br/I) nanometer chip architecture, then, by further chemically reacting, by pre-prepared PbX2(X=Cl/Br/I) it receives
Rice structure is changed into perovskite nanometer sheet, and such template preparation process is complex, and needing two-step reaction just can obtain finally
Product, and substrate and expensive chemical vapor deposition instrument are used in first step reaction, preparation cost is higher, operating process
Complexity is unfavorable for large scale preparation；Common self-assembled growth strategy, it is still desirable to which two-step method is prepared by microemulsion first
Technology obtains monodispersed perovskite nano particle, then prepares two-dimentional perovskite from prefabricated perovskite nano particle
Nanometer sheet, wherein after nano particle is made in the first step, it is also necessary to it is further purified, the preparation of next step could be used for,
Its operating process is complicated, is not easy largely to prepare, and the shortcomings that for both the above common method, the present invention can just make up above-mentioned
Disadvantage, operation of the present invention process is simple, and one-step method can prepare nanometer sheet, does not need expensive apparatus for preparation, to experiment item
Part is of less demanding, at low cost, and can be suitable for industrialized production with large scale preparation, be provided one for the preparation of nanometer sheet
Plant simply and easily preparation method.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of caesium bismuth bromine perovskites
The preparation method of nanometer sheet, wherein (as former in reacted by the process flow setting to preparation method entirety, key parameter condition
The type and proportion of material, atmospheric condition, treatment temperature and time locating for various processing etc.) it improves, it is received with tradition preparation
The technology of rice piece is compared, and is effectively solved the problems, such as that nanometer piece preparation method is complicated, at high cost, is provided a kind of completely new solwution method work
Skill, the method for low cost preparation nanometer sheet；The nanometer sheet that the present invention is prepared have highly crystalline, fabulous stability,
The features such as good optical characteristics, is especially advantageous for playing Cs3Bi2Br9The various good characteristics of perovskite nanometer sheet；Also, this hair
It is bright to adjust the size of nanometer chip size by controlling reaction time length.
To achieve the above object, it is proposed, according to the invention, a kind of preparation method of caesium bismuth bromine perovskite nanometer sheet is provided, it is special
Sign is, comprising the following steps:
(1) bismuth bromide and oleic acid, oleyl amine, 1- octadecylene are mixed to form mixture, wherein the bismuth bromide is at this
Concentration in mixture is 0.025-0.035mol/L；Then, under conditions of persistently vacuumizing, which is heated to
100-120 DEG C, and 60-120min is maintained, make bismuth bromide dissolution to obtain the mixed solution containing bismuth bromide；
(2) mixed solution containing bismuth bromide that Xiang Suoshu step (1) obtains is filled with nitrogen or argon gas, and will be warm
Degree rises to 170-180 DEG C, and then oleic acid caesium solution is injected into the mixed solution, and the reaction time maintains 5-60s, can be obtained
Including Cs3Bi2Br9Reaction product including perovskite nanometer sheet.
It is described when being preferably 5s in the reaction time in the step (2) as present invention further optimization
Cs3Bi2Br9The size of perovskite nanometer sheet is 17-21nm；When being preferably 30s in the reaction time, the Cs3Bi2Br9Calcium
The size of titanium ore nanometer sheet is 47-53nm；When being preferably 60s in the reaction time, the Cs3Bi2Br9Perovskite nanometer sheet
Size be 120-160nm.
As present invention further optimization, the preparation method of the caesium bismuth bromine perovskite nanometer sheet, further includes following step
It is rapid:
(3) reaction product obtained to the step (2) cools down；Then reaction product after cooling is carried out
Centrifugal treating is precipitated, and n-hexane is then added into the obtained precipitating and makes its dispersion, then carries out centrifugation point again
From supernatant is obtained, then into the supernatant, addition acetone is centrifuged Cs can be obtained again3Bi2Br9Perovskite nanometer sheet.
As present invention further optimization, in the step (1), in the mixture, every 0.15-0.21mmol substance
The bismuth bromide of amount to correspond to the liquid volume of the oleic acid be 0.5ml, the liquid volume of the corresponding oleyl amine is 0.5ml,
The liquid volume of the corresponding 1- octadecylene is 5ml.
As present invention further optimization, in the step (2), oleic acid contained in the oleic acid caesium solution of injection
The molar ratio of both bismuth bromides used in caesium and the step (1) is 0.76-1.07；Preferably, the oleic acid caesium solution
Concentration be 0.4mol/L.
Contemplated above technical scheme through the invention, compared with prior art, be first by bismuth bromide be dissolved in oleic acid,
Oleyl amine, 1- octadecylene three are mixed to form in solution, formed the mixed solution containing bismuth bromide, then by control ambiance and
Temperature simultaneously injects oleic acid caesium solution thereto, and caesium bismuth bromine perovskite nanometer sheet (i.e. Cs can finally be prepared3Bi2Br9Perovskite
Nanometer sheet)；The preparation method has the advantages that on the whole
(1) operating process is simple, and preparation process is not high to environmental requirement, required equipment and raw material cost is low.
(2) various sizes of nanometer sheet can be prepared.
(3) it is suitable for a large amount of preparation nanometer sheets.
(4) the gained aerial stability of nanometer sheet is very good.
The present invention can obtain the Cs of different sizes by adjusting different reaction time length3Bi2Br9Perovskite
Nanometer sheet, the growth kinetics of nanometer sheet are the increase with the reaction time, and the size of nanometer sheet is gradually increased.For example,
When being 5s between when reacted, Cs3Bi2Br9Perovskite nanometer sheet is preferably dimensioned to be 17-21nm；When being 30s between when reacted,
Cs3Bi2Br9Perovskite nanometer sheet is preferably dimensioned to be 47-53nm；When being 60s between when reacted, Cs3Bi2Br9Perovskite nanometer
Piece is preferably dimensioned to be 120-160nm.Therefore the nanometer of different sizes can be obtained by the length in control reaction time
Piece.
The present invention is explored by the reaction condition etc. to crucial preparation method principle and each step reaction, preferably
Control concentration of the bismuth bromide in bismuth bromide, oleic acid, oleyl amine, 1- octadecylene mixture be 0.025-0.035mol/L (such as
0.03mol/L), the heating temperature for controlling the mixture is 100-120 DEG C, heating time 60-120min, and passes through control
Reaction temperature is 170-180 DEG C, and the reaction time maintains 5-60s, can obtain the Cs that dimensional parameters are 17-160nm3Bi2Br9Calcium
Titanium ore nanometer sheet.Preparation method principle of the invention is molten to be rapidly injected oleic acid caesium into the mixed solution of bismuth bromide at high temperature
Liquid can be nucleated immediately at this time, the small sized caesium bismuth bromine perovskite nanometer sheet of shape, then as the extension in reaction time, small ruler
Very little nanometer sheet can gradually grow up, and the mechanism grown up is carried out with Ostwald ripening, i.e., in the growth of nanometer sheet
In the process, the nanometer sheet of small size is decomposed into monomer, with the growth for large-sized nanometer sheet, therefore the nanometer of small size
Piece is decomposed into monomer, and large-sized nanometer sheet endlessly consumes monomer with the growth for itself, with this growth mechanism
Obtain caesium bismuth bromine perovskite nanometer sheet to the end.The dissolving step that the present invention dissolves bismuth bromide is persistently to vacuumize lower progress
, the purpose persistently vacuumized is to remove water and oxygen, so that by oxygen and water in oleic acid, oleyl amine and 1- octadecylene liquid
Divide and excludes completely, so as to obtain the good caesium bismuth bromine nanometer sheet of stability.In addition, the injection temperature control of oleic acid caesium is existed
170-180 DEG C is best section, and when injection temperature is higher, after the injection of oleic acid caesium, nucleation rate is accelerated, and growth rate can also add
Fastly；When injection temperature is lower, after the injection of oleic acid caesium, nucleation rate slows down, and growth rate can also slow down.
The present invention selects bismuth bromide substitution lead bromide as bismuth source, the caesium lead bromine system being generally studied in the prior art,
It is unfavorable to ecological environment and human health since lead element is a kind of toxic heavy-metal elements, and the present invention is used
Bismuth element just can solve this problem；In addition, what the prior art mainly studied is lead-based perovskite nanometer sheet, for nothing
Lead perovskite also has been reported that, but its pattern all concentrates on torispherical, and unleaded perovskite nanometer sheet is but rarely reported, and this hair
It is bright, a kind of preparation method of unleaded perovskite nanometer sheet well is provided, this technological gap has been filled up.
The absorption peak for the nanometer sheet that the present invention obtains is very symmetrical, and also very sharp, the halfwidth of absorption peak only has 22nm, table
Very strong exciton absorption characteristic is revealed.Having benefited from control of the present invention to injection temperature and growth temperature, (present invention will inject
Temperature and growth temperature control are 170-180 DEG C) so that the nanometer sheet synthesized using preparation method of the present invention its first swash
Sub- absorption peak strongly, shows excellent optical characteristics, and compared to traditional body phase material, absorption peak occurs apparent
Blue shift shows this perovskite nanometer sheet with very strong quantum confined effect.
Perovskite nanometer sheet that the present invention is prepared while there is good stability, has benefited from preparing and contain bismuth bromide
Mixed solution used by persistently vacuumize this operation under high temperature (present invention be the mixed solution by bismuth bromide in 100-
120 DEG C persistently vacuumize 60-120min), oleic acid, oleyl amine and moisture and oxygen content in 1- octadecylene can be removed, it can be with
More thoroughly in solution water content and oxygen content exclude it is clean, exactly under these conditions, so that the present invention is prepared into
The nanometer sheet defect arrived is seldom, in air, excellent stability is also shown under laser irradiation, with traditional lead base calcium titanium
Mine nanometer sheet is compared, and stability is greatly improved.
It is also a critical issue in preparation method that how separating-purifying, which goes out nanometer sheet, after Product formation.Present invention synthesis
Reacting in obtained stoste both includes nanometer sheet, also includes the product of torispherical.The separating-purifying of conventional nano piece is often
It is after stoste after synthesizing directly is centrifuged, to take its supernatant, gives up precipitating, and the present invention attempts to utilize this conventional separation
Method of purification does not obtain spawn but by transmission electron microscope phenetic analysis；Also, it is obtained due to synthetic reaction of the present invention
The stoste product containing nanometer sheet and torispherical simultaneously, how the separation of the product of nanometer sheet and torispherical, obtain pure receive
Rice piece is also crucial.For solve the problems, such as nanometer sheet separating-purifying this, the present invention is preferably by selective precipitation technology, that is, will
The stoste that synthetic reaction obtains takes its precipitating after being directly centrifuged, into precipitating be added n-hexane make its dispersion (can by stirring or
The modes such as ultrasonic treatment, which make to precipitate, to be become dispersing discrete state in the solution from stacking states), and be centrifuged to obtain again
Supernatant, then conventional acetone centrifugal treating is carried out to the supernatant and has just finally obtained Cs3Bi2Br9Perovskite nanometer sheet.Just
It is the processing mode preferably by this selective precipitation, smoothly the product of nanometer sheet and torispherical can be separated, finally
Obtain pure nanometer sheet.
To sum up, the present invention can synthesize Cs by simple and economic mode3Bi2Br9Perovskite nanometer sheet passes through optimization
The injection temperature and reaction time length of predecessor, to the Cs being prepared3Bi2Br9Perovskite nanometer sheet is centrifuged,
It can ensure the Cs that the present invention is prepared3Bi2Br9Perovskite nanometer sheet is with stability in highly crystalline, fabulous air
The features such as with good optical characteristics, can effectively push the application of nanometer sheet.The nanometer sheet prepared using this method is highly stable,
This method is at low cost, easy to operate, not stringent to environmental requirement and be suitable for large scale preparation.
Detailed description of the invention
Fig. 1 is the Cs obtained through the invention3Bi2Br9The absorption spectra and emission spectra of perovskite nanometer sheet.
Fig. 2 is the Cs obtained through the invention3Bi2Br9The X-ray diffractogram of perovskite nanometer sheet.
Fig. 3 is the Cs obtained through the invention3Bi2Br9The TEM of perovskite nanometer sheet schemes.
Fig. 4 is the Cs obtained through the invention3Bi2Br9Perovskite nanometer sheet various sizes of TEM figure, (a) in Fig. 4,
(b), (c) corresponding reaction time is respectively 5s, 30s and 60s, and the scale in (a), (b), (c) is 100nm.
Fig. 5 is the Cs obtained through the invention3Bi2Br9The stability map of perovskite nanometer sheet.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
The present invention is and the bismuth bromide using previously prepared oleic acid caesium as caesium source, oleic acid, oleyl amine and 1- octadecylene it is mixed
Object is closed as bismuth bromide source, prepares Cs using the method for heat injection3Bi2Br9Perovskite nanometer sheet specifically may include following step
It is rapid:
(1) 0.084g bismuth bromide is weighed in three-neck flask, measures 0.5ml oleic acid, 0.5ml oleyl amine, 5ml 1- octadecylene
Mixture is vacuumized.
(2) 120 DEG C of maintenance 60min are heated the mixture under vacuum-pumping conditions, are filled with nitrogen later, it then will mixing
Object is warming up to 180 DEG C, be rapidly injected 0.4ml oleic acid caesium solution (concentration of the oleic acid caesium solution be 0.4mol/L；It is used
Solvent can be the mixed solution of oleic acid and 1- octadecylene), and 60s is reacted, during the reaction every certain time interval
A small amount of reaction solution is taken immediately, a small amount of reaction solution is taken in 5s, 30s, 60s respectively, by selective precipitation technology (at selective precipitation
The concrete operations of reason can be found in following steps 3), its pattern and size, pattern and size are measured under transmission electron microscope
Respectively as (a), (b), (c) in Fig. 4 are shown.
(3) 30 DEG C are cooled the temperature to after reaction, and centrifugation is directly carried out to the reaction product after cooling, is connect
, be added into the obtained precipitating n-hexane make precipitating dispersion (can by stir or be ultrasonically treated etc. modes make precipitating by
Stacking states become dispersing discrete state in the solution), and be centrifuged to obtain supernatant again, above-mentioned centrifugal process turns
Speed can be 7000 revs/min, and centrifugation time is 3 minutes, and acetone is then added into the supernatant and is centrifuged again
Obtain Cs3Bi2Br9Perovskite nanometer sheet.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption in Fluorescence Spectrometer, measures in spectrophotometric
Its fixed fluorescence emission spectrum, as shown in Figure 1.
Cs is measured on X-ray diffractometer3Bi2Br9Perovskite nanometer sheet diffracting spectrum, as shown in Figure 2.
Take Cs3Bi2Br9Perovskite nanometer sheet solution drop spontaneously dries, at transmission electron microscope (TEM) on copper mesh
Imaging, as shown in Figure 3.
The Cs for taking differential responses time sampling to obtain3Bi2Br9Perovskite nanometer sheet solution drop is spontaneously dried on copper mesh,
It is imaged at transmission electron microscope (TEM), as shown in Figure 4.
The Cs that will be obtained3Bi2Br9Perovskite nanometer sheet maintains 120h under laser irradiation, places 20 days in air, surveys
Its absorption spectrum is measured, as shown in Figure 5.The Cs obtained by this method3Bi2Br9Perovskite nanometer sheet maintains under laser irradiation
120h, its first exciton absorption peak shows to utilize this method preparation substantially without any variation after placing 20 days in air
Nanometer sheet is highly stable, and this method is at low cost, easy to operate, not stringent to environmental requirement and be suitable for large scale preparation.
Embodiment 2
The present embodiment the following steps are included:
(1) 0.084g bismuth bromide is weighed in three-neck flask, measures 0.5ml oleic acid, 0.5ml oleyl amine, 5ml 1- octadecylene
Mixture is vacuumized.
(2) 120 DEG C of maintenance 60min are heated the mixture under vacuum-pumping conditions, are filled with nitrogen later, it then will mixing
Object is warming up to 180 DEG C, is rapidly injected the oleic acid caesium (concentration 0.4mol/L) of 0.4ml, and reacts 5s, by selective precipitation skill
Art measures its pattern and size under transmission electron microscope, and pattern and size are respectively as (a) in Fig. 4 is shown.
(3) 30 DEG C are cooled the temperature to after reaction, and centrifugation is directly carried out to the reaction product after cooling, is connect
, n-hexane is added into the obtained precipitating makes its dispersion (precipitating can be made by heap by the modes such as stirring or being ultrasonically treated
Cumuliformis state becomes dispersing discrete state in the solution), and be centrifuged to obtain supernatant, the revolving speed of above-mentioned centrifugal process again
It is 7000 revs/min, centrifugation time is 3 minutes, and acetone is then added into the supernatant and is centrifuged can be obtained again
Cs3Bi2Br9Perovskite nanometer sheet.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Take Cs3Bi2Br9Perovskite nanometer sheet solution drop spontaneously dries, at transmission electron microscope (TEM) on copper mesh
Imaging, as shown in (a) in Fig. 4, it is not difficult to find that Cs3Bi2Br9The size of perovskite nanometer sheet is 17-21nm.
Embodiment 3
The present embodiment the following steps are included:
(1) 0.084g bismuth bromide is weighed in three-neck flask, measures 0.5ml oleic acid, 0.5ml oleyl amine, 5ml 1- octadecylene
Mixture is vacuumized.
(2) 120 DEG C of maintenance 60min are heated the mixture under vacuum-pumping conditions, are filled with nitrogen later, it then will mixing
Object is warming up to 180 DEG C, is rapidly injected the oleic acid caesium (concentration 0.4mol/L) of 0.4ml, and reacts 30s, by selective precipitation
Technology measures its pattern and size under transmission electron microscope, and pattern and size are respectively as (b) in Fig. 4 is shown.
(3) 30 DEG C are cooled the temperature to after reaction, and centrifugation is directly carried out to the reaction product after cooling, is connect
, n-hexane is added into the obtained precipitating makes its dispersion (precipitating can be made by heap by the modes such as stirring or being ultrasonically treated
Cumuliformis state becomes dispersing discrete state in the solution), and be centrifuged to obtain supernatant, the revolving speed of above-mentioned centrifugal process again
It is 7000 revs/min, centrifugation time is 3 minutes, and acetone is then added into the supernatant and is centrifuged can be obtained again
Cs3Bi2Br9Perovskite nanometer sheet.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Take Cs3Bi2Br9Perovskite nanometer sheet solution drop spontaneously dries, at transmission electron microscope (TEM) on copper mesh
Imaging, as shown in (b) in Fig. 4, it is not difficult to find that Cs3Bi2Br9The size of perovskite nanometer sheet is 47-53nm.
Embodiment 4
The present embodiment the following steps are included:
(1) 0.084g bismuth bromide is weighed in three-neck flask, measures 0.5ml oleic acid, 0.5ml oleyl amine, 5ml 1- octadecylene
Mixture is vacuumized.
(2) 120 DEG C of maintenance 60min are heated the mixture under vacuum-pumping conditions, are filled with nitrogen later, it then will mixing
Object is warming up to 180 DEG C, is rapidly injected the oleic acid caesium (concentration 0.4mol/L) of 0.4ml, and reacts 60s, by selective precipitation
Technology measures its pattern and size under transmission electron microscope, and pattern and size are respectively as (c) in Fig. 4 is shown.
(3) 30 DEG C are cooled the temperature to after reaction, and centrifugation is directly carried out to the reaction product after cooling, is connect
, n-hexane is added into the obtained precipitating makes its dispersion (precipitating can be made by heap by the modes such as stirring or being ultrasonically treated
Cumuliformis state becomes dispersing discrete state in the solution), and be centrifuged to obtain supernatant, the revolving speed of above-mentioned centrifugal process again
It is 7000 revs/min, centrifugation time is 3 minutes, and acetone is then added into the supernatant and is centrifuged can be obtained again
Cs3Bi2Br9Perovskite nanometer sheet.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, as shown in Figure 1.
Take Cs3Bi2Br9Perovskite nanometer sheet solution drop spontaneously dries, at transmission electron microscope (TEM) on copper mesh
Imaging, as shown in (c) in Fig. 4, it is not difficult to find that Cs3Bi2Br9The size of perovskite nanometer sheet is 120-160nm；And pass through
The discrete nanometer sheet of measurement portion can measure and obtain it with a thickness of 8-10nm.
Embodiment 5
The present embodiment the following steps are included:
(1) 0.067g bismuth bromide is weighed in three-neck flask, measures 0.5ml oleic acid, 0.5ml oleyl amine, 5ml 1- octadecylene
Mixture is vacuumized.
(2) 120 DEG C of maintenance 60min are heated the mixture under vacuum-pumping conditions, are filled with nitrogen later, it then will mixing
Object is warming up to 180 DEG C, is rapidly injected the oleic acid caesium (concentration 0.4mol/L) of 0.4ml, and reacts 60s.
(3) 30 DEG C are cooled the temperature to after reaction, and centrifugation is directly carried out to the reaction product after cooling, is connect
, n-hexane is added into the obtained precipitating makes its dispersion (precipitating can be made by heap by the modes such as stirring or being ultrasonically treated
Cumuliformis state becomes dispersing discrete state in the solution), and be centrifuged to obtain supernatant, the revolving speed of above-mentioned centrifugal process again
It is 7000 revs/min, centrifugation time is 3 minutes, and acetone is then added into the supernatant and is centrifuged can be obtained again
Cs3Bi2Br9Perovskite nanometer sheet.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Cs is measured on X-ray diffractometer3Bi2Br9Perovskite nanometer sheet diffracting spectrum, it is similar to Fig. 2.
Embodiment 6
The embodiment is substantially the same manner as Example 5, and distinctive points are: the quality that bismuth bromide is weighed in three-neck flask is
0.094g。
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Cs is measured on X-ray diffractometer3Bi2Br9Perovskite nanometer sheet diffracting spectrum, it is similar to Fig. 2.
Embodiment 7
The embodiment is substantially the same manner as Example 4, and distinctive points are: heating the mixture to 110 under vacuum-pumping conditions
DEG C maintain 60min.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Cs is measured on X-ray diffractometer3Bi2Br9Perovskite nanometer sheet diffracting spectrum, it is similar to Fig. 2.
Embodiment 8
The embodiment is substantially the same manner as Example 4, and distinctive points are: heating the mixture to 120 under vacuum-pumping conditions
DEG C maintain 120min.
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Cs is measured on X-ray diffractometer3Bi2Br9Perovskite nanometer sheet diffracting spectrum, it is similar to Fig. 2.
Embodiment 9
The embodiment is substantially the same manner as Example 4, and distinctive points are: heating the mixture to 120 under vacuum-pumping conditions
DEG C maintain 60min, be filled with nitrogen later, mixture be then warming up to 170 DEG C,
Gained Cs3Bi2Br9The performance characterization of perovskite nanometer sheet are as follows:
Take Cs3Bi2Br9Perovskite nanometer sheet solution measures its optical absorption spectra in Fluorescence Spectrometer, in spectrophotometer
Its fluorescence emission spectrum is measured, it is similar to Fig. 1.
Cs is measured on X-ray diffractometer3Bi2Br9Perovskite nanometer sheet diffracting spectrum, it is similar to Fig. 2.
Oleic acid caesium employed in above-described embodiment is voluntarily obtained by reacting synthesis, and specific synthetic method can refer to
Using correlation technique in the prior art (e.g., Nano Lett 2015,15,5635-5640.).Additionally, due at 20-30 DEG C
When, oleic acid caesium solution can be frozen into solid, therefore before using oleic acid caesium, need first to be heated to 120-130 DEG C, and tie up
10-20min is held, makes oleic acid caesium by Solid State Transformation liquid, is used in order to extract.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of caesium bismuth bromine perovskite nanometer sheet, which comprises the following steps:
(1) bismuth bromide and oleic acid, oleyl amine, 1- octadecylene are mixed to form mixture, wherein the bismuth bromide is in the mixing
Concentration in object is 0.025-0.035mol/L；Then, under conditions of persistently vacuumizing, which is heated to 100-
120 DEG C, and 60-120min is maintained, make bismuth bromide dissolution to obtain the mixed solution containing bismuth bromide；
(2) mixed solution containing bismuth bromide that Xiang Suoshu step (1) obtains is filled with nitrogen or argon gas, and by temperature liter
To 170-180 DEG C, then oleic acid caesium solution is injected into the mixed solution, the reaction time maintain 5-60s, can be obtained including
Cs3Bi2Br9Reaction product including perovskite nanometer sheet, Cs3Bi2Br9The size of perovskite nanometer sheet can 17-160nm it
Between adjust.
2. the preparation method of caesium bismuth bromine perovskite nanometer sheet as described in claim 1, which is characterized in that in the step (2), when
When the reaction time is 5s, the Cs3Bi2Br9The size of perovskite nanometer sheet is 17-21nm；It is when the reaction time
When 30s, the Cs3Bi2Br9The size of perovskite nanometer sheet is 47-53nm；It is described when the reaction time is 60s
Cs3Bi2Br9The size of perovskite nanometer sheet is 120-160nm.
3. the preparation method of caesium bismuth bromine perovskite nanometer sheet as described in claim 1, which is characterized in that the caesium bismuth bromine perovskite
The preparation method of nanometer sheet, further comprising the steps of:
(3) reaction product obtained to the step (2) cools down；Then reaction product after cooling is centrifuged
Processing is precipitated, and n-hexane is then added into the obtained precipitating and makes its dispersion, is then centrifuged again
To supernatant, then into the supernatant, addition acetone is centrifuged Cs can be obtained again3Bi2Br9Perovskite nanometer sheet.
4. the preparation method of caesium bismuth bromine perovskite nanometer sheet as described in claim 1, which is characterized in that in the step (1), institute
It states in mixture, the liquid volume that the bismuth bromide of the amount of every 0.15-0.21mmol substance corresponds to the oleic acid is 0.5ml,
The liquid volume of the corresponding oleyl amine is 0.5ml, and the liquid volume of the corresponding 1- octadecylene is 5ml.
5. the preparation method of caesium bismuth bromine perovskite nanometer sheet as described in claim 1, which is characterized in that in the step (2), note
Oleic acid caesium contained in the oleic acid caesium solution entered and the molar ratio of both bismuth bromides used in the step (1) are
0.76-1.07。
6. the preparation method of caesium bismuth bromine perovskite nanometer sheet as claimed in claim 5, which is characterized in that in the step (2), institute
The concentration for stating oleic acid caesium solution is 0.4mol/L.
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| CN109928426A (en) * | 2019-05-10 | 2019-06-25 | 江南大学 | A kind of nanocrystalline Rb of novel rubidium bismuth chlorine perovskite7Bi3Cl16And preparation method thereof |
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