CN115465884B - Yellow light all-inorganic perovskite quantum dot and preparation method and application thereof - Google Patents
Yellow light all-inorganic perovskite quantum dot and preparation method and application thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 28
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 27
- 239000011630 iodine Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- -1 iodide ions Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 35
- 238000005119 centrifugation Methods 0.000 description 18
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 14
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 10
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0232—Optical elements or arrangements associated with the device
- H01L31/02322—Optical elements or arrangements associated with the device comprising luminescent members, e.g. fluorescent sheets upon the device
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention relates to a perovskite quantum dot material, in particular to a yellow light full-inorganic perovskite quantum dot materialThe preparation method and application of the dot comprise the following steps: s1: csX is dissolved in cesium source solvent to prepare cesium source; pbBr is prepared 2 Mixing with tetra-n-octyl ammonium bromide, dissolving in a lead source solvent, and preparing a lead source; dissolving MI in an iodine source solvent to prepare an iodine source; s2: adding a silane solution into the lead source prepared in the step S1, sequentially adding a cesium source and an iodine source, and mixing and stirring to obtain a solution containing CsPbBr x I 3‑x A solution of quantum dots; s3: the CsPbBr obtained in the step S2 is contained x I 3‑x Centrifugal washing of the solution of the quantum dots to obtain CsPbBr x I 3‑x Quantum dots. Compared with the prior art, the invention realizes the yellow all-inorganic perovskite quantum dot CsPbBr with good quantum dot stability and crystallinity x I 3‑x Is prepared by the following steps.
Description
Technical Field
The invention relates to a perovskite quantum dot material, in particular to a yellow light full-inorganic perovskite quantum dot, and a preparation method and application thereof.
Background
Conventional II-VI quantum dots, such as CdSe, inP, inAs, etc., have a strong dependence on quantum confinement effect, and the luminescence position changes with the change of the size of the quantum dot, which generally results in a broad emission spectrum, low reproducibility, and difficulty in obtaining products with the same size distribution (luminescence position), and the luminescence position also changes with the change of temperature. In recent years, perovskite quantum dots have received a great deal of attention as an emerging photoelectric material. The light-emitting diode has excellent photoelectric properties, such as narrower full width at half maximum (FWHM), adjustable light-emitting wavelength, higher quantum efficiency and the like, and can be applied to the fields of solar batteries, photodetectors, lasers, light-emitting diodes, illumination, biomedicine and the like.
Perovskite quantum dots are roughly divided into organic-inorganic hybrid perovskite quantum dots and all-inorganic perovskite quantum dots, the hybrid perovskite quantum dots are sensitive to temperature, humidity and oxygen relative to all-inorganic perovskite quantum dots, and the quantum dots are affected by the hybrid perovskite quantum dots to undergo phase change, agglomeration and the like, so that the damaged fluorescence performance of the quantum dots is weakened or even quenched; the all-nothing perovskite quantum dot is a nano material with high yield, high monodispersity, wide emission spectrum range, adjustable emission spectrum, short fluorescence lifetime and low preparation cost.
At present, methods for preparing perovskite quantum dots include a thermal injection method, a microwave auxiliary method, a chemical vapor deposition method and the like, but the thermal injection method needs to control the heating temperature, introduce inert gas for protection and control the speed of thermal injection, and the microwave auxiliary method also needs inert gas for protection and high-temperature heating, which increases the complexity of the preparation process and is not beneficial to large-scale production.
In summary, the existing perovskite quantum dot preparation methods are complicated, require precise control of temperature, speed and other conditions, and are not suitable for mass production, so that a convenient preparation method is required to prepare perovskite quantum dots with good quantum dot stability and crystallinity.
Disclosure of Invention
The invention aims to solve at least one of the problems and provide a yellow all-inorganic perovskite quantum dot, a preparation method and application thereof, which solve the problems of complicated traditional preparation process and the need of accurate control conditions and realize the yellow all-inorganic perovskite quantum dot CsPbBr with good quantum dot stability and crystallinity x I 3-x Is prepared by the following steps.
The aim of the invention is achieved by the following technical scheme:
the first aspect of the invention discloses a yellow light all-inorganic perovskite quantum dot, the chemical formula of which is CsPbBr x I 3-x Wherein x=1.5-2.4.
The second aspect of the invention discloses a method for preparing the yellow light all-inorganic perovskite quantum dot, which comprises the following steps:
s1: csX is dissolved in cesium source solvent to prepare cesium source; pbBr is prepared 2 Mixing with tetra-n-octyl ammonium bromide, dissolving in a lead source solvent, and preparing a lead source; dissolving MI in iodine source solventAn iodine source is configured;
s2: adding silane solution into the lead source prepared in the step S1, adding cesium source at intervals of 5-30S, then adding iodine source at intervals of 5-40S, mixing and stirring to obtain a solution containing CsPbBr x I 3-x A solution of quantum dots;
s3: to step S2, csPbBr is contained x I 3-x Adding a washing solution into the solution of the quantum dots, and centrifugally washing to obtain CsPbBr x I 3-x Quantum dots.
Preferably, csX described in step S1 comprises Cs 2 CO 3 CsBr and CH 3 One or more of COOCs; the cesium source solvent comprises one or two of n-octanoic acid and oleic acid.
Preferably, the PbBr is as described in step S1 2 And tetra-n-octylammonium bromide in a molar ratio of 1:2; the lead source solvent comprises toluene. The tetra-n-octyl ammonium bromide is adopted as a ligand and a cationic active agent, so that the dissolution of lead bromide and the reaction in the subsequent process can be effectively promoted. Toluene as a matrix solution of the entire reaction system can promote the dissolution of lead bromide.
Preferably, the MI described in step S1 comprises ZnI 2 One or more of NaI, liI, and KI; the iodine source solvent comprises isopropanol.
Preferably, the silane solution described in step S2 comprises one or more of 3-aminopropyl triethoxysilane, didodecyl dimethyl ammonium bromide and tetramethoxysilane. The silane is adopted as a ligand, so that the quantum dot can be coated to prevent the quantum dot from being oversized, the size effect of the quantum dot is kept, and further the quantum dot with good crystallinity can be obtained.
Preferably, the volume ratio of the silane solution, the lead source, the cesium source and the iodine source in step S2 is 0.2-0.4:2.5-3.5:0.1-0.2:1.5-1.7; the concentration of Cs in the cesium source is 0.1-0.3mmol/mL; the concentration of Pb in the lead source is 0.3-0.4mmol/mL; the concentration of I in the iodine source is 2-3mmol/mL.
The addition at intervals in step S2 is to enable the added solution to be mixed with the original solution well.
Preferably, the centrifugal washing described in step S3 is performed 2 to 3 times, each centrifugal washing being performed after adding the washing liquid, at a rotation speed of 5000 to 6000rpm for 5 to 6 minutes.
Preferably, the washing liquid comprises n-hexane and/or isopropanol, and the volume ratio of the washing liquid to the silane solution is 5-10:0.2-0.4; the wash solution is added after the iodine source is added for 10-40 s. The n-hexane and/or isopropanol is used as a washing liquid to wash the reaction product, and meanwhile, the dispersion of the product can be assisted, so that the obtained product has better performance.
The supernatant liquid is required to be discharged before centrifugal washing, washing liquid is added again and then centrifugal washing is carried out, and the washing is repeated for 3 to 4 times, so that attachments on the surface of the quantum dots can be sufficiently removed, and CsPbBr capable of emitting yellow light under the excitation of ultraviolet light (395 nm) can be obtained x I 3-x Perovskite quantum dots.
The third aspect of the invention discloses application of the yellow-light all-inorganic perovskite quantum dot in the fields of illumination and photoelectricity.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a yellow light all-inorganic perovskite quantum dot CsPbBr x I 3-x The preparation method has the advantages that the flow operation is simple in the preparation process, the whole process can be carried out at normal temperature and normal pressure, and the production cost is low; in addition, the quantum dot prepared in the room temperature environment has good stability; meanwhile, tetra-n-octyl ammonium bromide is adopted as a ligand and a cationic active agent, so that the dissolution and subsequent reaction of lead bromide (lead source) can be promoted, the quantum dots are coated by using silane as the ligand, the oversized quantum dots can be prevented, the quantum dot size effect can be kept, and further the quantum dots with good crystallinity can be obtained.
2. The invention realizes the preparation research of quantum dots based on the principle of supersaturation crystallization, in particular to the preparation of CsPbBr by means of halogen element anion substitution x I 3-x Perovskite quantum dots, wherein, cesium sources are added into lead sources for reaction, and then iodine sources are rapidly injected at intervals of 5-40s, so that the full intersection of bromide ions and iodide ions can be further realizedChanging, and obtaining CsPbBr x I 3-x The quantum dots can be coated with silane without oversizing.
3. In the centrifugal washing in the preparation process, the attachments on the surface of the quantum dots can be sufficiently removed by repeated centrifugal washing and washing liquid replacement before each centrifugal washing, so that pure CsPbBr can be obtained x I 3-x Perovskite quantum dots.
4. CsPbBr of the present invention x I 3-x The perovskite quantum dot can be prepared in an air environment by being completely exposed, so that the perovskite quantum dot has good stability in the air and feasibility of practical application, and in addition, the cost in the preparation process is low, the material consumption is low, the large-scale production is easy, and the prepared CsPbBr is easy to realize x I 3-x The perovskite quantum dot has wide application range and good benefit.
Drawings
FIG. 1 is a graph of the all-inorganic perovskite quantum dots CsPbBr prepared in example 1 x I 3-x Is a photoluminescence spectrum of (3);
FIG. 2 is a graph of the all-inorganic perovskite quantum dots CsPbBr prepared in example 1 x I 3-x Is a transmission electron microscope image;
FIG. 3 is a graph of the all-inorganic perovskite quantum dots CsPbBr prepared in example 1 x I 3-x Fluorescent lifetime map of (2);
FIG. 4 shows the all-inorganic perovskite quantum dots CsPbBr prepared in example 1 and comparative example x I 3-x Is a photoluminescence spectrum of (3).
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The reagents used, not specifically illustrated in the examples below, may be commercially available products that can be routinely obtained by those skilled in the art; the methods employed may employ conventional means known to those skilled in the art.
Example 1
Yellow light all-inorganic perovskite quantum dot CsPbBr x I 3-x Is prepared by the following stepsThe method comprises the following steps:
(1) A preparation step of a quantum dot solution, namely placing 1mmol of cesium carbonate in a No. 1 beaker, placing 1mmol of lead bromide and 2mmol of tetra-n-octylammonium bromide in a No. two beaker, respectively taking 5mL of n-octanoic acid to be added into the No. 1 beaker, taking 3mL of toluene to be added into the No. two beaker, placing the No. two beaker on a stirrer for magnetic stirring, manually stirring the No. one beaker for 3min, standing for standby, stirring the No. two beaker for about 15min, clarifying a mixed solution, 2g of zinc iodide is placed in a third beaker, 5mL of isopropanol is added, the zinc iodide is stirred manually until the zinc iodide is completely dissolved, then 0.3mL of APTES (3-aminopropyl triethoxysilane) solution is added into the second beaker by using a pipetting gun with a measuring range of 100 mu L, the injection speed is moderate, then 100 mu L of cesium source is taken by changing the pipetting gun head, the cesium source is added into the second beaker after a period of 10 seconds, 1.6mL of iodine source solution is added rapidly after a period of about 15 seconds, and perovskite quantum dots CsPbBr are generated by reaction x I 3-x 。
(2) Adding iodine source solution for about 15s in the step (1), and adding the quantum dot CsPbBr containing reaction product x I 3-x Pouring the solution into a centrifuge tube, rapidly adding 5mL of n-hexane for centrifugation, setting the centrifugation rotation speed to 5000rpm, setting the time to 5min, pouring out the supernatant after centrifugation, adding n-hexane for standing for 4min, pouring out the supernatant, adding isopropanol for centrifugal washing, and alternately adding n-hexane and isopropanol for centrifugation for 2-3 times in the way to obtain a final centrifugal precipitate.
The measurement shows that the yellow light all-inorganic perovskite quantum dot obtained in the embodiment is CsPbBr 1.5 I 1.5 。
From FIG. 1, it can be seen that CsPbBr obtained by the present invention x I 3-x The light-emitting center wavelength of the perovskite quantum dot is positioned near 572nm, and belongs to the yellow light range.
The appearance of the quantum dots is observed by a transmission electron microscope as shown in fig. 2, so that the quantum dots can be uniformly distributed, and the silane solution added in the preparation process can be used for coating the quantum dots, so that the quantum dots are gathered together.
CsPbBr obtained by the invention x I 3-x As shown in FIG. 3, the fluorescence lifetime of the perovskite quantum dot is shown as tau, and the short lifetime and the long lifetime obtained by fitting the fluorescence lifetime spectrum of the quantum dot by a double exponential decay function are respectively 1 Is 3.41ns, τ 2 At 11.47ns, the two lifetimes are weighted 59.6% and 40.4%, respectively.
Example 2
Yellow light all-inorganic perovskite quantum dot CsPbBr x I 3-x The preparation method of (2), the method comprises the following steps:
(1) Preparing a quantum dot solution, namely placing 1mmol of cesium carbonate in a No. 1 beaker, placing 1mmol of lead bromide and 2mmol of tetra-n-octylammonium bromide in a No. two beaker, adding 5mL of n-octanoic acid into the No. 1 beaker, adding 3mL of toluene into the No. two beaker, wherein the volume ratio of the two is 5:3, placing the No. two beaker on a stirrer for magnetic stirring, manually stirring the No. one beaker for 3min, standing for standby, stirring the No. two beaker for about 15min, adding 2g of zinc iodide into the No. three beaker until a mixed solution is clear, manually stirring until the zinc iodide is completely dissolved, then adding 0.3mL of DDAB (didodecyl dimethyl ammonium bromide) solution into the No. two beaker by using a liquid-transferring gun with a measuring range of 100 mu L, then replacing the liquid-transferring gun head with a cesium source with a volume ratio of 100 mu L, adding the cesium source into the No. two beaker after a interval of 10s, adding the cesium source into the No. two beaker with a space of 15 mu.L, and adding the 3 mu.L of zinc iodide into the No. three beaker for a fast reaction to obtain a Pb3 quantum dot solution, wherein the PbR is prepared by a fast reaction of 1.6mL of the calcium-doped quantum dot solution x I 3-x 。
(2) Adding iodine source solution for about 15s in the step (1), and adding the quantum dot CsPbBr containing reaction product x I 3-x Pouring into a centrifuge tube, rapidly adding 5mL of n-hexane for centrifugation, setting the centrifugation speed at 5000rpm for 5min, pouring out the supernatant after centrifugation, and then alternately adding n-hexane and isopropanol for centrifugation 2-3 times as described in example 1 to obtain a final centrifugation precipitate.
Example 3
The method comprises the following steps ofYellow light full-inorganic perovskite quantum dot CsPbBr x I 3-x The preparation method of (2), the method comprises the following steps:
(1) Preparing a quantum dot solution, namely placing 1mmol of cesium bromide in a No. 1 beaker, placing 1mmol of lead bromide and 2mmol of tetra-n-octylammonium bromide in a No. two beaker, adding 5mL of oleic acid into the No. 1 beaker, adding 3mL of toluene into the No. two beaker, wherein the volume ratio of the two is 5:3, placing the No. two beaker on a stirrer, magnetically stirring the No. one beaker for 3min, standing for standby, stirring the No. two beaker for about 15min, until the mixed solution is clear, basically no obvious solid substance is at the bottom of the cup, placing 2g of potassium iodide in the No. three beaker, adding 5mL of isopropanol, manually stirring until the potassium iodide is completely dissolved, then adding 0.4mL of TMS (tetramethoxysilane) solution into the No. two beaker by using a pipette with a measuring range of 100 mu L, pouring speed moderate, then changing the pipette head to take 200 mu L of cesium source, adding the cesium source into the No. two beaker after adding TMS solution for 30s, adding the No. 5s of solid substance at intervals, placing 2g of potassium iodide in the No. three beaker, adding 2g of cesium source into the No. three beaker, and adding the No. 5s of PbO quantum dot solution, and rapidly obtaining the quantum dot solution, namely, and generating the quantum dot solution, namely, br x I 3-x 。
(2) Adding iodine source solution into the step (1) for about 10s, and adding the quantum dot CsPbBr containing the reaction product x I 3-x Pouring into a centrifuge tube, rapidly adding 8mL of n-hexane for centrifugation, setting the centrifugation speed at 6000rpm for 5min, pouring out the supernatant after centrifugation, and then alternately adding n-hexane and isopropanol for centrifugation 2-3 times as described in example 1 to obtain a final centrifugation precipitate.
Comparative example
(1) Preparing a quantum dot solution, namely placing 1mmol of cesium carbonate in a first beaker, placing 1mmol of lead bromide and 2mmol of tetra-n-octylammonium bromide in a second beaker, adding 5mL of n-octanoic acid into the first beaker, adding 3mL of toluene into the second beaker, placing the second beaker on a stirrer for magnetic stirring according to the volume ratio of 5:3, manually stirring the first beaker for 3min, then standing for later use, stirring the second beaker for about 15min, clarifying the mixed solution until no obvious solid substance is basically found at the bottom of the cup, and taking 2g of iodinePutting zinc oxide in a third beaker, adding 5mL of isopropanol, manually stirring until the zinc iodide is completely dissolved, then adding 0.3mL of APTES (3-aminopropyl triethoxysilane) solution into a second beaker by using a pipette with a measuring range of 100 mu L, injecting at moderate speed, then changing the pipette head to take 100 mu L of cesium source, adding into the second beaker, adding 1.6mL of iodine source solution at intervals of about 60 seconds, and reacting to generate perovskite quantum dots CsPbBr x I 3-x 。
(2) Adding iodine source solution for about 15s in the step (1), and adding the quantum dot CsPbBr containing reaction product x I 3-x Pouring the solution into a centrifuge tube, rapidly adding 5mL of normal hexane for centrifugation, setting the centrifugation speed to 5000rpm, setting the time to 5min, pouring out supernatant after centrifugation, and then alternately adding normal hexane and isopropanol for centrifugation for 2-3 times to obtain a final centrifugal precipitate.
As shown in FIG. 4, perovskite quantum dots CsPbBr prepared in example 1 and comparative example x I 3-x The main difference between the two is the different addition time intervals of cesium source and iodine source, and the result shows that the perovskite quantum dots CsPbBr of example 1 are between 550 and 600nm x I 3-x Is far greater than the perovskite quantum dot CsPbBr of the comparative example x I 3-x To control the addition time interval of cesium source and iodine source for perovskite quantum dots CsPbBr x I 3-x The photoluminescent performance of (2) is greatly affected.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (6)
1. Preparation of yellow light full-inorganic perovskite quantum dotThe method is characterized in that the chemical formula of the all-inorganic perovskite quantum dot is CsPbBr x I 3-x Wherein x=1.5-2.4;
the all-inorganic perovskite quantum dot is prepared through the following steps:
s1: csX is dissolved in cesium source solvent to prepare cesium source; pbBr is prepared 2 Mixing with tetra-n-octyl ammonium bromide, dissolving in a lead source solvent, and preparing a lead source; dissolving MI in an iodine source solvent to prepare an iodine source;
s2: adding silane solution into the lead source prepared in the step S1, adding cesium source at intervals of 5-30S, then adding iodine source at intervals of 5-40S, mixing and stirring to obtain a solution containing CsPbBr x I 3-x A solution of quantum dots;
s3: the CsPbBr obtained in the step S2 is contained x I 3-x Centrifugal washing of the solution of the quantum dots to obtain CsPbBr x I 3-x A quantum dot;
MI in the step S1 is ZnI 2 One or more of NaI, liI, and KI; the iodine source solvent is isopropanol;
the silane solution in the step S2 is one or two of 3-aminopropyl triethoxysilane and tetramethoxysilane;
in the step S2, adding a lead source into the cesium source for reaction, then adding an iodine source at intervals of 5-40S to fully exchange bromide ions and iodide ions, thereby obtaining CsPbBr x I 3-x The quantum dots are coated with silane.
2. The method for preparing yellow light fully inorganic perovskite quantum dots according to claim 1, wherein CsX in the step S1 comprises Cs 2 CO 3 CsBr and CH 3 One or more of COOCs; the cesium source solvent comprises one or two of n-octanoic acid and oleic acid.
3. The method for preparing yellow light full inorganic perovskite quantum dots according to claim 1, wherein the PbBr in the step S1 is as follows 2 And tetra-n-octylammonium bromide in a molar ratio of 1:2; the lead source solvent comprises toluene。
4. The method for preparing the yellow light full inorganic perovskite quantum dot according to claim 1, wherein the volume ratio of the silane solution, the lead source, the cesium source and the iodine source in the step S2 is 0.2-0.4:2.5-3.5:0.1-0.2:1.5-1.7; the concentration of Cs in the cesium source is 0.1-0.3mmol/mL; the concentration of Pb in the lead source is 0.3-0.4mmol/mL; the concentration of I in the iodine source is 2-3mmol/mL.
5. The method for preparing the yellow light full inorganic perovskite quantum dot according to claim 1, wherein the centrifugal washing in the step S3 is carried out 2-3 times, and each centrifugal washing is carried out at a rotation speed of 5000-6000rpm for 5-6min after the washing liquid is added.
6. The method for preparing the yellow light full inorganic perovskite quantum dot according to claim 5, wherein the washing liquid comprises n-hexane and/or isopropanol, and the volume ratio of the washing liquid to the silane solution is 5-10:0.2-0.4; the wash solution is added after the iodine source is added for 10-40 s.
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| CN109337674A (en) * | 2018-08-29 | 2019-02-15 | 湖北大学 | A kind of preparation method of the ligand modified perovskite CsPbX3 quantum dot of binary |
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