CN116925742A - Preparation method of ligand self-coated perovskite quantum dot - Google Patents
Preparation method of ligand self-coated perovskite quantum dot Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 70
- 239000003446 ligand Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 41
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 28
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 28
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 26
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 26
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005642 Oleic acid Substances 0.000 claims abstract description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000005253 cladding Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 19
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical group [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229940046892 lead acetate Drugs 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical group [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 8
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- 239000000243 solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical group [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 239000012454 non-polar solvent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000033830 Hot Flashes Diseases 0.000 description 1
- 206010060800 Hot flush Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- -1 heat Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical compound Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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Abstract
The invention discloses a preparation method of ligand self-cladding perovskite quantum dots, and belongs to the field of perovskite quantum dot preparation. The preparation method of the ligand self-cladding perovskite quantum dot comprises the following steps: dissolving a cesium source, a lead source and oleic acid in a solvent to prepare a cesium source and a lead source precursor; adding a bromine source and oleic acid into a solvent for dissolution to prepare a bromine source precursor; and mixing cesium source with lead source precursor and bromine source precursor, and reacting to form the ligand self-coated perovskite quantum dot. The preparation method disclosed by the invention is simple to operate, complex post-treatment on the synthesized quantum dots is not needed, and ligand coating can be realized while perovskite quantum dots are formed in situ. The perovskite quantum dot has high stability thanks to efficient coating of the ligand.
Description
Technical Field
The invention relates to the field of perovskite quantum dot preparation, in particular to a preparation method of ligand self-cladding perovskite quantum dots.
Background
In recent years, perovskite quantum dots have the advantages of high carrier mobility, long carrier service life, high absorption coefficient and the like, so that great research interests of vast scientific researchers are brought up, and research hot flashes are raised. At present, perovskite materials have been widely used in the photoelectric fields of solar cells, light emitting diodes, photodetectors, field effect transistors, and the like. Generally, compared with the traditional inorganic quantum dot material which is formed by stronger covalent bond connection, the perovskite quantum dot has the characteristics of ionic compounds, and the ionic bond energy among the components is lower and is easy to generate phase change, so that the perovskite quantum dot has weak tolerance to water, heat, oxygen and light and poor stability, and further application in the field of photoelectricity is limited. Therefore, how to improve the stability of perovskite materials has become a precondition for achieving large-scale applications thereof.
At present, the most effective method for improving the stability of perovskite quantum dots is to coat a layer of oxide or organic polymer on the surface of the perovskite quantum dots to isolate external water and oxygen (ACS Nano 2019, 13, 5366-5374;ACS Nano 2018, 12, 8579-8587), and most of the methods are a two-step method, namely, firstly synthesizing the perovskite quantum dots and then coating the surface of the perovskite quantum dots. However, this method is generally complicated, and because perovskite quantum dots are relatively sensitive, certain damage is often caused to the surface of the perovskite quantum dots in the second step of coating process, and the optical performance is reduced. Therefore, how to improve the stability of perovskite quantum dots and maintain the excellent optical properties thereof is one of the important preconditions for practical applications.
Disclosure of Invention
The invention aims to provide a preparation method of one-step in-situ ligand self-cladding perovskite quantum dots. In particular, the method is simple to operate, does not need to carry out post-treatment such as coating oxide or organic polymer on the synthesized quantum dots, can realize the coating of the quaternary ammonium salt ligand while forming the perovskite quantum dots in situ, and has high stability due to the coating of rich ligands.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: the preparation method of the ligand self-coated perovskite quantum dot comprises the following steps:
dissolving a cesium source, a lead source and oleic acid in a solvent to prepare a cesium source and a lead source precursor;
adding a bromine source and oleic acid into a solvent for dissolution to prepare a bromine source precursor;
mixing cesium source with lead source precursor and bromine source precursor, and reacting to form the ligand self-cladding perovskite quantum dot;
the bromine source is Dioctadecyl Dimethyl Ammonium Bromide (DDAB).
Preferably, the solvent of the cesium source and lead source precursors is octadecene; the solvent of the bromine source precursor is 1-octadecene.
Preferably, the cesium source is cesium carbonate; the lead source is lead oxide or lead acetate; the molar ratio of the cesium source to the lead source to the bromine source is 0.125-0.5:1:3.
Preferably, the reaction time is 10 to 30 seconds and the temperature is 160 to 250 ℃.
Preferably, after the reaction is completed, a rapid cooling step is further included.
More preferably, the rapid cooling method is cooling with an ice water ice bath; after the ice bath is cooled, the method further comprises a dispersing step, wherein the dispersing step comprises the following steps: blending nonpolar solvent and quantum dots, centrifuging, dispersing in nonpolar solvent, and preserving; the nonpolar solvent in the blending step is ethyl acetate, and the nonpolar solvent in the dispersing step is toluene.
Ethyl acetate was used in the blending step for analytical washing, and toluene was finally used as a solvent because toluene was a good solvent for dispersion.
The addition of oleic acid is important for quaternary ammonium salt, can play a good role in promoting dissolution, and the 1-octadecene alone can not dissolve DDAB. In the past, it has been reported that the perovskite quantum dot is synthesized by dissolving another quaternary ammonium salt (tetraoctylammonium bromide) with toluene to realize heat injection, but in the process of dissolving with toluene, the boiling point of toluene is low, so that the heating condition cannot exceed the boiling point of toluene (110.6 ℃), and if the boiling point of toluene is high, the preparation cannot be realized because of the flash evaporation of toluene, which severely limits the upper limit of the synthesis temperature. According to the invention, the DDAB is dissolved by combining oleic acid with 1-octadecene, and the dissolution mode has good solubility, so that the optimal synthesis condition of perovskite can be explored in a higher temperature area in the process of designing a scheme.
The invention prepares the high boiling point bromine source precursor by using oleic acid to help dissolve dioctadecyl dimethyl ammonium bromide, so that the product can obtain the quantum dot with excellent crystallinity at higher temperature. Meanwhile, since dioctadecyl dimethyl ammonium bromide in the scheme of the invention is added in an excessive form, br is provided in addition - In addition to participating in quantum dot synthesis reactions, there are also a number of DDAs + Ligand residue; and DDAB melting point is high and is crystalline solid at normal temperature, so a large amount of quaternary ammonium salt ligand is quickly condensed and attached to the periphery of the perovskite quantum dot in the ice bath cooling process, a coated ligand layer is formed in situ, and the synthetic perovskite quantum dot has excellent stability due to the fact that the rich ligand is coated to form a film.
The second technical scheme of the invention is as follows: the ligand self-cladding perovskite quantum dot obtained by the preparation method is provided.
The third technical scheme of the invention: the ligand self-cladding perovskite quantum dot is applied to the field of luminous illumination.
The beneficial technical effects of the invention are as follows:
the invention designs a method for preparing perovskite quantum dots by self-cladding of in-situ ligands by a one-step method for the first time; in the coating process, the quaternary ammonium salt ligand cannot damage the surface of the quantum dot to reduce the optical performance, so that the synthesized perovskite quantum dot is ensured to have excellent stability.
The preparation method disclosed by the invention is simple to operate, complex post-treatment on the synthesized quantum dots is not needed, and the compact ligand film type coating can be realized while the perovskite quantum dots are formed in situ. The perovskite quantum dot has high stability thanks to efficient coating of the ligand.
Drawings
FIG. 1 is a TEM image of the product of example 1 at different scales; wherein, (a) is a TEM image at 200nm, and (b) is a TEM image at 100 nm.
FIG. 2 is a graph showing the UV-visible absorption spectrum and fluorescence spectrum of the product of example 1.
FIG. 3 is a TEM image of the product of comparative example 1.
FIG. 4 is a graph comparing the stability of the products of example 1 and comparative example 2.
Fig. 5 is a TEM image of the product of comparative example 2.
FIG. 6 is a TEM image of the product of comparative example 3.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
The terms "comprising," "including," "having," "containing," and the like as used herein are open-ended terms, meaning including, but not limited to.
The raw materials used in the following examples and comparative examples of the present invention are all commercially available products.
Example 1
Preparing ligand self-coating perovskite quantum dots:
(1) Preparing cesium source and lead source precursors: taking 0.025mmol Cs 2 CO 3 With 0.1mmol PbO in a flask, 0.3mL of oleic acid and 4mL of 1-Octadecene (ODE) were added to be sufficiently dissolved under heating at 70 ℃, then heated to 100 ℃ and repeatedly evacuated by a vacuum pump until the vacuum gauge reading was below 0.3Torr and filled with nitrogen, which process took 2 hours, then heated to 160 ℃ at a heating rate of 5 ℃/min, to prepare cesium source and lead source precursors.
(2) Preparing a bromine source precursor: 1.2mmol of Dioctadecyl Dimethyl Ammonium Bromide (DDAB) is taken, 1mL of oleic acid and 3mL of 1-octadecene are added for dissolution, the temperature is raised to 100 ℃, the vacuum is repeatedly pumped by a vacuum pump until the reading of a vacuum meter is below 0.3Torr, the vacuum meter is filled with nitrogen for 2 hours, and then the temperature is raised to 160 ℃ at a heating rate of 5 ℃/min, so that a bromine source precursor is prepared.
(3) Preparing quantum dots: at 160 ℃, 1mL of bromine source precursor is rapidly injected into the cesium source and the lead source precursor which are in a stirring state, the stirring is stopped for 10 seconds, the reaction is immediately stopped by ice water ice bath, equal volume of ethyl acetate is added into the cooled solution, the mixture is uniformly mixed, and then the mixture is centrifuged for 10 minutes at 8000r/min, and the precipitate is taken and dispersed in toluene to obtain the ligand self-coated perovskite quantum dot (CsPbBr) 3 )。
TEM analysis was performed on the perovskite quantum dots in example 1, and the results are shown in FIG. 1. As can be seen from fig. 1, the synthesized quantum dots have uniform size, a layer of film is obviously arranged at the outermost periphery of the quantum dots, the quantum dots are embedded in the film, the quantum dots are not distributed in the outer area of the film, and most of the quantum dots are protected by the film.
FIG. 2 is a graph showing the UV-visible absorption spectrum and fluorescence spectrum of the product of example 1. As can be seen from FIG. 2, the quantum dot has an obvious absorption peak at-510 nm, and the fluorescence emission position is 520nm, and has a narrower half-peak width of about 18nm.
Example 2
Preparing ligand self-coating perovskite quantum dots:
(1) Preparing cesium source and lead source precursors: taking 0.05mmol Cs 2 CO 3 With 0.1mmol of lead acetate in a flask, 0.3mL of oleic acid and 4mL of 1-Octadecene (ODE) were added to be sufficiently dissolved under heating at 70℃and then heated to 100℃and repeatedly evacuated with a vacuum pump until the vacuum gauge reading was below 0.3Torr and filled with nitrogen gas for 2 hours, followed by heating to 180℃at a heating rate of 5℃per minute, to obtain cesium source and lead source precursors.
(2) Preparing a bromine source precursor: taking 1.2mmolThe dioctadecyl dimethyl ammonium bromide is added with 1mL of oleic acid and 3mL of 1-octadecene to be dissolved, then the temperature is raised to 100 ℃, the vacuum pump is repeatedly used for vacuumizing until the reading of a vacuum meter is below 0.3Torr, nitrogen is filled for 2 hours, and then the temperature is raised to 180 ℃ at the heating rate of 5 ℃/min, so that the bromine source precursor is prepared.
(3) Preparing quantum dots: at 180 ℃, 1mL of bromine source precursor is rapidly injected into the cesium source and the lead source precursor which are in a stirring state, the stirring is stopped for 30 seconds, the reaction is immediately stopped by ice water ice bath, equal volume of ethyl acetate is added into the cooled solution, the mixture is uniformly mixed, and then the mixture is centrifuged for 10 minutes at 8000r/min, and the precipitate is taken and dispersed in toluene to obtain the ligand self-coated perovskite quantum dot (CsPbBr) 3 )。
Comparative example 1 (final Synthesis temperature of two precursors and temperature for preparation of Quantum dots were set to 100 ℃ C.)
(1) Preparing cesium source and lead source precursors: taking 0.025mmol Cs 2 CO 3 With 0.1mmol PbO in a flask, adding 0.3mL oleic acid and 4mL 1-Octadecene (ODE) to dissolve thoroughly under 70deg.C heating, heating to 100deg.C and repeatedly evacuating with vacuum pump to vacuum gauge readingThis process takes 2 hours to produce cesium and lead source precursors at below 0.3Torr and filled with nitrogen.
(2) Preparing a bromine source precursor: 1.2mmol of Dioctadecyl Dimethyl Ammonium Bromide (DDAB) is taken, 1mL of oleic acid and 3mL of 1-octadecene are added for dissolution, the temperature is raised to 100 ℃, the vacuum is repeatedly pumped by a vacuum pump until the reading of a vacuum meter is below 0.3Torr, and nitrogen is filled for 2 hours, so that a bromine source precursor is prepared.
(3) Preparing quantum dots: at 100 ℃, 1mL of bromine source precursor is rapidly injected into the cesium source and the lead source precursor which are in a stirring state, the stirring is stopped for 10 seconds, the ice water ice bath is immediately used for stopping the reaction, the equal volume of ethyl acetate is added into the cooled solution, the mixture is uniformly mixed, and the mixture is centrifuged at 8000r/min for 10min, so that the precipitate is dispersed in toluene.
The TEM of the obtained product is shown in FIG. 3, and compared with the example 1, the product obtained in the comparative example 1 is largely aggregated, has a random morphology and is non-fluorescent; it is demonstrated that DDAB is detrimental to the formation of luminescent perovskite at low temperature conditions when used as a bromine source, and luminescent perovskite needs to be produced at higher temperature conditions.
Comparative example 2
The only difference from example 1 is that the addition of DDAB was omitted and an equimolar amount of n-octylammonium bromide (TOAB) was made up.
Fig. 5 is a TEM image of the product of comparative example 2. As shown in fig. 5, the quantum dot size of the product of comparative example 2 was greatly different, and the film was not seen to wrap around the quantum dot.
Comparative example 3 (final synthesis temperature of two precursors and temperature for preparation of Quantum dot were set to 280 ℃ C.)
(1) Preparing cesium source and lead source precursors: taking 0.025mmol Cs 2 CO 3 With 0.1mmol PbO in a flask, 0.3mL oleic acid and 4mL 1-Octadecene (ODE) were added to dissolve thoroughly under heating at 70 ℃, then warmed to 100℃and repeatedly evacuated with a vacuum pump until the vacuum gauge reading was below 0.3Torr and filled with nitrogen, which process took 2 hours, then warmed to 280℃to produce cesium source and lead source precursors.
(2) Preparing a bromine source precursor: 1.2mmol of Dioctadecyl Dimethyl Ammonium Bromide (DDAB) is taken, 1mL of oleic acid and 3mL of 1-octadecene are added for dissolution, the temperature is raised to 100 ℃, the vacuum is repeatedly pumped by a vacuum pump until the reading of a vacuum meter is below 0.3Torr, and the vacuum meter is filled with nitrogen for 2 hours, and then the temperature is raised to 280 ℃ to prepare the bromine source precursor.
(3) Preparing quantum dots: at 280 ℃, 1mL of bromine source precursor is rapidly injected into the cesium source and the lead source precursor which are in a stirring state, the stirring is stopped for 10 seconds, the ice water ice bath is immediately used for stopping the reaction, the equal volume of ethyl acetate is added into the cooled solution, the mixture is uniformly mixed, and the mixture is centrifuged at 8000r/min for 10min, so that the precipitate is dispersed in toluene.
The TEM of the obtained product is shown in fig. 6, and the product of comparative example 3 is square and similar to that of example 1, but the ligand coating is not found around it, which may be due to decomposition of the surface ligand caused by the influence of high temperature, and the coating layer cannot be formed.
Effect verification
(1) The products of example 1 and comparative example 2 were tested for stability. The specific test method comprises the following steps: and taking the prepared quantum dots, measuring the fluorescence intensity of the quantum dots by using a fluorescence spectrophotometer, and measuring the fluorescence intensity for three times in parallel each time. The test results are shown in fig. 4.
FIG. 4 is a graph comparing the stability of the products of example 1 and comparative example 2. As shown in fig. 4, in example 1, the fluorescence intensity is not significantly reduced after the quantum dots are stored for one week, and it is seen that the quantum dots have good stability due to the protection of the film; the quantum dots synthesized in comparative example 2 have large size differences, and the thin film is not coated around the quantum dots, which is mainly due to the lack of protection of surface ligands, so that the stability is poor, and thus the fluorescence intensity is rapidly reduced.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. The preparation method of the ligand self-coated perovskite quantum dot is characterized by comprising the following steps of:
dissolving a cesium source, a lead source and oleic acid in a solvent to prepare a cesium source and a lead source precursor;
adding a bromine source and oleic acid into a solvent for dissolution to prepare a bromine source precursor;
mixing cesium source with lead source precursor and bromine source precursor, and reacting to form the ligand self-cladding perovskite quantum dot;
the bromine source is dioctadecyl dimethyl ammonium bromide.
2. The method of claim 1, wherein the cesium source is cesium carbonate; the lead source is lead oxide or lead acetate; the molar ratio of the cesium source to the lead source to the bromine source is 0.125-0.5:1:3.
3. The preparation method according to claim 1, wherein the reaction time is 10 to 30 seconds and the temperature is 160 to 250 ℃.
4. The method of claim 1, further comprising a rapid cooling step after the reaction is completed.
5. A ligand self-coated perovskite quantum dot obtainable by the method of any one of claims 1 to 4.
6. Use of the ligand self-coated perovskite quantum dot according to claim 5 in the field of luminescent lighting.
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