CN107216874A - A kind of lead aluminium mixing perovskite blue light quantum point material and preparation method thereof, application - Google Patents
A kind of lead aluminium mixing perovskite blue light quantum point material and preparation method thereof, application Download PDFInfo
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- CN107216874A CN107216874A CN201710358656.4A CN201710358656A CN107216874A CN 107216874 A CN107216874 A CN 107216874A CN 201710358656 A CN201710358656 A CN 201710358656A CN 107216874 A CN107216874 A CN 107216874A
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- lead
- blue light
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 70
- 239000004411 aluminium Substances 0.000 title claims abstract description 67
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002156 mixing Methods 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 150000004820 halides Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000005642 Oleic acid Substances 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 20
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 19
- -1 aluminum halide Chemical class 0.000 claims description 15
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 11
- 229910052792 caesium Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006862 quantum yield reaction Methods 0.000 claims description 7
- 238000009396 hybridization Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims 2
- 239000002096 quantum dot Substances 0.000 abstract description 21
- 238000005349 anion exchange Methods 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 6
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910052794 bromium Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000165940 Houjia Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- NOSLERKXFBMFFQ-UHFFFAOYSA-N [Ti].[Ca].[Cl] Chemical compound [Ti].[Ca].[Cl] NOSLERKXFBMFFQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003752 improving hair Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001773 titanium mineral Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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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- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
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- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention discloses a kind of lead aluminium mixing perovskite blue light quantum point material and preparation method thereof, application, wherein, the material includes lead halide perovskite doped body and Al-doping presoma, partial replacement is carried out by the Pb positions in Al ion pair lead halide perovskite doped bodies, realize the regulation and control to perovskite quantum dot light emitting wavelength, and eliminate the problems such as spectral width, chromaticity are drifted about caused by quick anion exchange, the doping of lead position can also reduce the content of heavy metal element lead in material simultaneously, promote environmental protection；Further, the preparation method of lead aluminium mixing perovskite blue light quantum point material that the present invention is provided simply easily realization, low cost, low toxicity and has versatility；The lead aluminium mixing perovskite blue light quantum point material can be directly used in the fluorescence conversion layer in electroluminescent LED or WLED.
Description
Technical field
The present invention relates to blue light quantum point Material Field, more particularly to a kind of lead aluminium mixing perovskite blue light quantum point material
And preparation method thereof, application.
Background technology
Lead halogen perovskite quantum dot combines the advantage of perovskite material and the characteristic of quantum dot, and it has luminous efficiency
High, luminescence spectrum is narrow and the adjustable characteristic of emission wavelength, is the ideal chose for obtaining wide colour gamut high-quality display panel, not
Carry out great commercial value in Display Technique.
Although the preparation of perovskite quantum dot has been achieved for greater advance, still there is problems with it：1st, it is high
Quality blue light material lacks：The species of the regulation dependence halogen atom of current perovskite quantum dot light emitting wavelength, and lead chlorine calcium titanium
The usual luminous efficiency of ore deposit quantum dot blue light material is relatively low（PLQY<30%）, heat endurance it is poor, it is impossible to ensure perovskite quantum dot
The reliability of device；Although the launch wavelength of lead bromine flaky nanocrystalline can be blue shifted to blue light from green glow, the system is easy to
Orientation absorption occurs under illumination, aggregation is formed, causes blue light to occur red shift；2nd, it is fast between different lead halogen perovskite quantum dots
Fast anion exchange reaction, while being offered convenience to quantum dot energy gap adjustability, also brings spectral width, chromaticity drift
The a series of potential problems such as shifting；Although perovskite quantum dot, which is embedded in polymer or silica medium, can hinder anion
Exchange reaction, but the strategy is not particularly suited for electroluminescent device；3rd, lead halogen perovskite quantum dot contains a huge sum of money for heavier ratio
Belong to Element Lead, do not possess environment friendly, limit its following application in luminescence display field.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of lead aluminium mixing perovskite blue light amount
Point material and preparation method thereof, application, it is intended to which solving existing perovskite blue light quantum point material, to there is luminous efficiency low, thermally-stabilised
Property is poor, and spectral width and chromaticity are the problem of drift about.
Technical scheme is as follows：
A kind of lead aluminium mixing perovskite blue light quantum point material, wherein, including lead halide perovskite doped body and aluminium ion mix
Aluminium ion in miscellaneous presoma, the Al-doping presoma is to the lead ion carry out portion in lead halide perovskite doped body
Divide and replace, form the lead aluminium mixing perovskite blue light quantum point material of high-fluorescence quantum yield.
Described lead aluminium mixing perovskite blue light quantum point material, wherein, the aluminium ion is blue in lead aluminium mixing perovskite
Shared weight ratio is less than or equal to 10% in light quanta point material.
Described lead aluminium mixing perovskite blue light quantum point material, wherein, the lead halide perovskite doped body includes
Organic inorganic hybridization perovskite, inorganic metal hal ide perovskite and two-dimensional metallic halide perovskite.
Described lead aluminium mixing perovskite blue light quantum point material, wherein, the Al-doping presoma includes halogenation
The metal alkoxide and aluminium sulfocyanide of aluminium, aluminium.
As above a kind of preparation method of any described lead aluminium mixing perovskite blue light quantum point material, wherein, including step
Suddenly：
A, first lead halide perovskite doped body and Al-doping presoma added in octadecylene solvent and mixed, then added
Isometric oleyl amine and oleic acid, is heated to predetermined temperature until obtaining settled solution；
B, to the settled solution continue heat, isometric oleyl amine and oleic acid is added again, oleic acid caesium presoma is eventually adding,
React after the scheduled time, that is, the lead aluminium mixing perovskite blue light quantum point material is made.
The preparation method of described lead aluminium mixing perovskite blue light quantum point material, wherein, the lead halide perovskite is mixed
Miscellaneous main body and the mol ratio of Al-doping presoma are 1：0.01-1：10.
The preparation method of described lead aluminium mixing perovskite blue light quantum point material, wherein, the pre- constant temperature in the step A
Spend for 100-200 DEG C.
The preparation method of described lead aluminium mixing perovskite blue light quantum point material, wherein, the pre- timing in the step B
Between be 10-600s.
The preparation method of described lead aluminium mixing perovskite blue light quantum point material, wherein, also wrapped after the step B
Include:
C, reacted lead aluminium mixing perovskite blue light quantum point solution is cooled to after room temperature, sequentially passes through centrifugation, separate, carry
Lead aluminium mixing perovskite blue light quantum point powder body material is obtained after pure and mild vacuum drying.
As above a kind of application of any described lead aluminium mixing perovskite blue light quantum point material, wherein, the lead aluminium is mixed
Perovskite blue light quantum point material is closed for the fluorescence conversion layer in WLED or electroluminescent LED is directly used in.
Beneficial effect：Lead aluminium mixing perovskite blue light quantum point material quantum yield that the present invention is provided is high, stability is strong,
Partial replacement is carried out by the Pb positions in Al ion pair lead halide perovskite doped bodies, realized to perovskite quantum dot light emitting
The regulation and control of wavelength, and the problems such as spectral width, chromaticity are drifted about caused by quick anion exchange is eliminated, while lead position is mixed
It is miscellaneous to reduce the content of heavy metal element lead in material, promote environmental protection；Further, the lead aluminium mixing perovskite that the present invention is provided
The preparation method of blue light quantum point material simply easily realization, low cost, low toxicity and with versatility；The lead aluminium calcium mixture titanium
Mineral blue light quanta point material can be directly used in the fluorescence conversion layer in electroluminescent LED or WLED.
Brief description of the drawings
Fig. 1 is a kind of flow of the preparation method preferred embodiment of lead aluminium mixing perovskite blue light quantum point material of the invention
Figure；
Fig. 2 is the doped and undoped CsPbBr of Al of the present invention3Nanocrystalline absorption spectrum；
Fig. 3 is the doped and undoped CsPbBr of Al of the present invention3Nanocrystalline fluorescence spectrum；
Fig. 4 is the CsPbBr that Al of the present invention adulterates3Nanocrystalline TEM phenogram pictures；
Fig. 5 for the present invention undoped with CsPbBr3Nanocrystalline TEM phenogram pictures；
Fig. 6 is the doped and undoped CsPbBr of Al3Corresponding intensity variation in nanocrystalline thermal cycle；
Fig. 7 is the CsPbBr that blue light Al adulterates3Nanocrystalline and green glow CsPbBr3The fluorescence spectrum of the nanocrystalline mixture of perovskite；
Fig. 8 is the CsPbBr that blue light Al adulterates3Nanocrystalline and green glow CsPbBr3With the nanocrystalline mixing of feux rouges CdSe@ZnS perovskites
The photoluminescence spectra of the white light LEDs of thing composition.
Embodiment
The present invention provides a kind of lead aluminium mixing perovskite blue light quantum point material and preparation method thereof, application, to send out this
Bright purpose, technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that herein
Described specific embodiment only to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of lead aluminium mixing perovskite blue light quantum point material, wherein, including lead halide perovskite mixes
Aluminium ion in miscellaneous main body and Al-doping presoma, the Al-doping presoma is to lead halide perovskite doped body
In lead ion carry out partial replacement, formed high-fluorescence quantum yield lead aluminium mixing perovskite blue light quantum point material.
Specifically, perovskite material has abundant component diversity, and its electronic structure and the characteristics of luminescence are except that can lead to
The change to anion component and ratio is crossed outside being regulated and controled, by the doping to cation to regulate and control；It is logical
The doping to non-halogen position particle is crossed, the regulation and control to perovskite quantum dot light emitting wavelength can be achieved, and is eliminated by quick cloudy
The direct approach for the problems such as spectral width, chromaticity are drifted about caused by ion-exchange reactions；The present invention is by using the 3rd main group member
Plain Al has been prepared with high-fluorescence quantum yield and the stable blue luminescence quantum dot of performance to Pb progress partial replacements
Material.
Further, in the present invention, the lead halide perovskite doped body includes organic inorganic hybridization perovskite, inorganic
Metal halide perovskite and two-dimensional metallic halide perovskite, wherein organic inorganic hybridization perovskite can be
CH3NH3PbX3Or CH (NH2)2PbX3, the inorganic metal hal ide perovskite can be CsPbX3, the two-dimensional metallic halogenation
Thing perovskite can be (C6H5CH2CH2NH3)2PbX3, wherein X can be any one in Cl, Br, I or two kinds of combinations；Institute
Stating Al-doping presoma includes aluminum halide（For example, AlI3、AlBr3、AlCl3）, aluminium metal alkoxide and aluminium sulfocyanide.
Specifically, in the present invention, the aluminium ion prepares luminous lead aluminium mixing perovskite blue light quantum point in the present invention
Shared weight ratio is less than or equal to 10% in material, and the pattern of the lead aluminium mixing perovskite blue light quantum point material is sheet
Nanocrystalline, cubic nanometer is brilliant, spherical nanocrystalline, columnar nanometer is brilliant, wire is nanocrystalline or polyhedron it is nanocrystalline in one kind.
Further, the present invention also provides a kind of preparation method of lead aluminium mixing perovskite blue light quantum point material, such as Fig. 1
Shown, it specifically includes step：
S10, first lead halide perovskite doped body and Al-doping presoma added in octadecylene solvent and mixed, Ran Houjia
Enter isometric oleyl amine and oleic acid, be heated to predetermined temperature until obtaining settled solution；
Specifically, the CsPbBr of the invention to prepare Al doping3Perovskite blue light quantum point material exemplified by, first by PbBr2
With Al-doping presoma（AlBr3）Added in dry octadecylene solvent, isometric oleyl amine of drying is then added
With oleic acid as surfactant, 100-200 DEG C is heated to until lead bromide and AlBr3All dissolving, obtains settled solution；This
Invention is preferably heated to 120 DEG C；
Further, in the step S10, the lead halide perovskite doped body and Al-doping presoma of reactant are used as
Mol ratio be 1:0.01-1:10, preferably 1:2.
S20, to the settled solution continue heat, isometric oleyl amine and oleic acid is added again, oleic acid caesium is eventually adding
Presoma, after the reaction scheduled time, that is, is made the lead aluminium mixing perovskite blue light quantum point material.
Specifically, the preparation of oleic acid caesium presoma should be also included before the step S20, specifically can be by 0.64g's
Cs2CO3With dry oleic acid（2 mL）With dry octadecylene（24ml）It is added in 50ml three neck round bottom, Ran Houjia
Heat is to 150 °C until all Cs2CO3Oleic acid caesium presoma is generated with elaidin reaction.
Further, in the step S20, the settled solution is continued to heat, 160 °C, Ran Houzai are preferably heated to
The isometric oleyl amine of secondary addition and oleic acid make solution keep clarification, and the oleyl amine and the amount of oleic acid specifically added in step S10 with adding
The oleyl amine and the amount of oleic acid entered can be the same or different；Finally it is rapidly injected and is preheated to 140 °C of oleic acid caesium forerunner in advance
After body, reaction 10-600s, preferably 120s, you can liquid lead aluminium mixing perovskite blue light quantum point material is made.
Further, also include after the step S20：
The liquid lead aluminium mixing perovskite blue light quantum point material is transferred in the freezer of anhydrous and oxygen-free and is cooled to room
Wen Hou, obtains sediment by centrifugation step, the sediment is distributed in dry toluene and further cleaned, afterwards using second
Nitrile is further precipitated and centrifuged, and obtained sediment is dispersed again in dry toluene；Finally by rotary evaporation or vacuum
Dry after the solvent, obtain the lead aluminium mixing perovskite blue light quantum point material of powder shaped.
The heat injection that the preparation method of lead aluminium mixing perovskite blue light quantum point material proposed by the present invention belongs to after improving
Hair, its step is simply easily realized, and with versatility, is applicable not only to the doping of full-inorganic perovskite quantum dot, is equally also fitted
For mixing for organic inorganic hybridization perovskite quantum dot, three-dimensional perovskite quanta point material and two-dimentional perovskite quanta point material
Miscellaneous, the method that the present invention is provided is processed under the conditions of whole soln, with low cost, low toxicity, high color purity and high fluorescence
The features such as quantum yield.
Further, the present invention also provides a kind of method of low temperature preparation lead aluminium mixing perovskite blue light quantum point material,
It specifically includes step：
A, using lead halide and Al-doping presoma as reactant, be dissolved in dry DMF（DMF）
In, the first precursor solution that concentration range is 0.02 ~ 0.1 mol/L, wherein lead halide and Al-doping presoma is made
Mol ratio be 1：（0.01-10）；
B, with caesium halide（CsX, X=Cl, Br, Br/I mixing, Cl/Br mixing）Or halogen acid salt（CH3NH3X、CH(NH2)2X、
C6H5CH2CH2NH3X, X=Cl, Br, Br/I mixing, Cl/Br mixing）For reactant, dry DMF is dissolved in
（DMF）The second precursor solution that concentration range is 0.02 ~ 0.1 mol/L is made in solvent；
C, add in dry octadecylene solvent by surfactant of oleyl amine and oleic acid, under 40 ~ 90 DEG C of temperature conditionss, point
The first precursor solution and the second precursor solution are not injected in the octadecylene solvent, oil is made after the reaction scheduled time molten
The quantum dot presoma of property；The first precursor solution and the mol ratio of the second precursor solution wherein injected is 1:（0.3~3）,
The ratio that the volume sum of first precursor solution and the second precursor solution accounts for octadecylene solvent volume is 2-10%；
4th, after reaction different time, the toluene solution of 5-10 times of octadecylene solvent volume is injected, promotes quantum dot Precipitation, from
The lead aluminium mixing perovskite blue light quantum point material of powder shaped is obtained after heart separating-purifying, vacuum drying.
Below with prepare aluminium doping CsPbBr3To a kind of lead aluminium of the invention exemplified by perovskite quantum dot blue fluorescent material
The preparation method of mixing perovskite blue light quantum point material is further explained explanation：
Embodiment 1
1. the preparation of oleic acid caesium：With reference to quantum dot heat injection synthetic method, by Cs2CO3（0.640 g）, dry OA（2 mL）
With dry ODE（24 mL）In the three neck round bottom for being added to 50 mL, 150 °C are then heated to until all Cs2CO3With
OA reacts.140 °C are preheated to before injection.All reactions are all in the glove box full of nitrogen（0.1 ppm H2O；0.1 ppm
O2）It is middle to carry out.
The CsPbX 2. Al adulterates3Nanocrystal（X=Br, Br/I）Synthesis：Dry ODE（5 mL）, AlBr3
（0.0301 g）, PbX2, such as PbBr2（0.0690 g）Or their mixture PbBr2/PbI2（The g of 0.0367 g/0.0433,
Mol ratio 1:1）, it is fitted into 25 mL three-necked flasks.Then dry OAm is injected in 120 oC（0.5 mL）And OA（0.5 mL）.
It is being completely dissolved PbX2After salt, temperature is risen into 160 oC.It is subsequently injected into dry OAm（0.3 mL）With dry OA（0.3
mL）Solution is set to keep clarification.Then it is rapid to inject oleic acid caesium solution（0.4 mL）.After 1 minute, transfer the solution into glove box
Refrigerator in cooled down.
3. the separation and purifying of caesium base nanometer crystal：The nanocrystalline Precipitation from ODE at room temperature, and by centrifugation, incline
Supernatant liquor isolates sediment.Then solid nano crystalline product is distributed in dry toluene., will further to clean
It is nanocrystalline with acetonitrile precipitation and to centrifuge, then it is dispersed again in dry toluene.Rotary evaporation falls after solution, collects nanometer crystal powder
Body, is stored in standby in glove box.
Illustrate aluminium doping CsPbBr below by experimental data3It is nanocrystalline and undoped with CsPbBr3Property between nanocrystalline
The difference of energy and form：
Fig. 2 is the doped and undoped CsPbBr of Al3Nanocrystalline absorption spectrum, Fig. 3 is the doped and undoped CsPbBr of Al3
Nanocrystalline fluorescence spectrum, by contrast find, it is aluminum ions doping cause it is nanocrystalline in the first exciton absorption peak and fluorescence
The blue shift of emission peak, undoped with CsPbBr3It is nanocrystalline to show green emission at 515nm, and the CsPbBr of Al doping3Receive
Meter Jing shows blue emission at 456nm, and its half-peak breadth only has 16nm.
Further, by the doped and undoped CsPbBr of Al3Nanocrystalline TEM is characterized and measured, as a result such as Fig. 4
With shown in Fig. 5, Al doping CsPbBr3Nanocrystalline pattern there occurs obvious change, undoped with CsPbBr3It is nanocrystalline to be in
Existing near cubic form, and the CsPbBr after Al doping3It is nanocrystalline to be deformed into elongated bar shaped, that is to say, that after Al doping
Lattice Contraction can be caused.
The heat endurance of perovskite nanocrystal should be used to say that an important considerations for LED, in order to test
The heat endurance of perovskite nanocrystal, the present invention enters in 20-100 °C of control temperature range to perovskite nanocrystal film
The assessment of photoluminescence intensity, thermal cycle result gone as shown in fig. 6, the CsPbBr of Al doping3It is nanocrystalline not only to show more
Good stability, and solve the problems, such as mixed halide it is nanocrystalline in anion exchange；Further, as shown in fig. 7, having
Identical halogen element Br green glow CsPbBr3With blue light Al:CsPbBr3In mixed system, skew and the width of spectrum is not observed
Change.
Further, present invention also offers a kind of application of lead aluminium mixing perovskite blue light quantum point material, wherein, institute
Lead aluminium mixing perovskite blue light quantum point material is stated for the fluorescence conversion layer in WLED or electroluminescent LED is directly used in；
In order to show the CsPbBr of Al doping3Nanocrystalline that the ability for producing white light is combined with other illuminators, the present invention is by inciting somebody to action
The CsPbBr of Al doping3Nanocrystalline and a certain amount of green glow CsPbBr3The nanocrystalline and nanocrystalline mixing of feux rouges CdSe@ZnS, system
The WLED devices of surface attaching type are made；The fluorescence emission spectrum of the WLED devices is as shown in figure 8, the fluorescence of RGB three primary colours
Launch wavelength position is respectively in 615 nm, 515 nm and 456 nm.The triangle of RGB coordinates composition is that the backlight device can be realized
Gamut range, by calculating, the colour gamut of the white light parts reached 116 % in NTSC standard space.
In summary, the lead aluminium mixing perovskite blue light quantum point material quantum yield height of the invention provided, stability are strong, pass through
Pb positions in Al ion pair lead halide perovskite doped bodies carry out partial replacement, realize to perovskite quantum dot light emitting wavelength
Regulation and control, and the problems such as spectral width, chromaticity are drifted about caused by quick anion exchange is eliminated, while the doping of lead position is also
The content of heavy metal element lead in material can be reduced, promotes environmental protection；Further, the lead aluminium mixing perovskite blue light that the present invention is provided
The preparation method of quanta point material simply easily realization, low cost, low toxicity and with versatility；The lead aluminium mixing perovskite is blue
Light quanta point material can be directly used in the fluorescence conversion layer in electroluminescent LED or WLED.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
1. a kind of lead aluminium mixing perovskite blue light quantum point material, it is characterised in that including lead halide perovskite doped body and
Aluminium ion in Al-doping presoma, the Al-doping presoma to the lead in lead halide perovskite doped body from
Son carries out partial replacement, forms the lead aluminium mixing perovskite blue light quantum point material of high-fluorescence quantum yield.
2. lead aluminium mixing perovskite blue light quantum point material according to claim 1, it is characterised in that the aluminium ion exists
Shared weight ratio is less than or equal to 10% in lead aluminium mixing perovskite blue light quantum point material.
3. lead aluminium mixing perovskite blue light quantum point material according to claim 1, it is characterised in that the lead halide calcium
Titanium ore doped body includes organic inorganic hybridization perovskite, inorganic metal hal ide perovskite and two-dimensional metallic halide calcium titanium
Ore deposit.
4. lead aluminium mixing perovskite blue light quantum point material according to claim 1, it is characterised in that the aluminium ion is mixed
Miscellaneous presoma includes aluminum halide, the metal alkoxide and aluminium sulfocyanide of aluminium.
5. a kind of preparation method of lead aluminium mixing perovskite blue light quantum point material as described in claim 1-4 is any, it is special
Levy and be, including step：
A, first lead halide perovskite doped body and Al-doping presoma added in octadecylene solvent and mixed, then added
Isometric oleyl amine and oleic acid, is heated to predetermined temperature until obtaining settled solution；
B, to the settled solution continue heat, isometric oleyl amine and oleic acid is added again, oleic acid caesium presoma is eventually adding,
React after the scheduled time, that is, the lead aluminium mixing perovskite blue light quantum point material is made.
6. the preparation method of lead aluminium mixing perovskite blue light quantum point material according to claim 5, it is characterised in that institute
The mol ratio for stating lead halide perovskite doped body and Al-doping presoma is 1：0.01-1：10.
7. the preparation method of lead aluminium mixing perovskite blue light quantum point material according to claim 5, it is characterised in that institute
It is 100-200 DEG C to state the predetermined temperature in step A.
8. the preparation method of lead aluminium mixing perovskite blue light quantum point material according to claim 5, it is characterised in that institute
It is 10-600s to state the scheduled time in step B.
9. the preparation method of lead aluminium mixing perovskite blue light quantum point material according to claim 5, it is characterised in that institute
Stating also includes after step B:
C, reacted lead aluminium mixing perovskite blue light quantum point solution is cooled to after room temperature, sequentially passes through centrifugation, separate, carry
Lead aluminium mixing perovskite blue light quantum point powder is obtained after pure and mild vacuum drying.
10. a kind of application of lead aluminium mixing perovskite blue light quantum point material as described in claim 1-4 is any, its feature exists
In fluorescence conversion layer or be directly used in electroluminescent that the lead aluminium mixing perovskite blue light quantum point material is used in WLED
LED。
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| CN109962172A (en) * | 2019-03-20 | 2019-07-02 | 浙江大学 | A kind of preparation method and photoelectric device of photoelectric device |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647530A (en) * | 2016-02-01 | 2016-06-08 | 南京理工大学 | Preparation method of metal halide inorganic perovskite quantum dots |
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-
2017
- 2017-05-19 CN CN201710358656.4A patent/CN107216874B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647530A (en) * | 2016-02-01 | 2016-06-08 | 南京理工大学 | Preparation method of metal halide inorganic perovskite quantum dots |
| CN105702865A (en) * | 2016-04-05 | 2016-06-22 | 河北大学 | Metal-ion-doped perovskite thin film, preparation method and application therefor |
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