CN106010518A - Copper-doped all-inorganic halogen perovskite fluorescent material and preparation method and application thereof - Google Patents
Copper-doped all-inorganic halogen perovskite fluorescent material and preparation method and application thereof Download PDFInfo
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- CN106010518A CN106010518A CN201610383953.XA CN201610383953A CN106010518A CN 106010518 A CN106010518 A CN 106010518A CN 201610383953 A CN201610383953 A CN 201610383953A CN 106010518 A CN106010518 A CN 106010518A
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 19
- 150000002367 halogens Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005253 cladding Methods 0.000 claims abstract description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 16
- -1 octadecylene Chemical group 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 12
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 230000006641 stabilisation Effects 0.000 claims description 8
- 238000011105 stabilization Methods 0.000 claims description 8
- 238000004020 luminiscence type Methods 0.000 claims description 5
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 9
- 238000006862 quantum yield reaction Methods 0.000 abstract description 9
- 230000005284 excitation Effects 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001507 sample dispersion Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming 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
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
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Abstract
The present invention relates to a kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material and preparation methods and purposes, the range that the skeleton symbol of the material is CsPb1-xCuxBr3:X is between 0-1, obtained material is faint yellow or yellow powder, which is cubic phase, and space group is
By the way that the reaction to further occurrence is dissolved under high temperature in organic solvent, it repeatedly washed with n-hexane or toluene equal solvent, purify and obtain Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, it is having a size of between 10-30 nm, by testing its UV, visible light (wave-length coverage 350-700 nm) and fluorescence spectrum (excitation wavelength 360nm), with the increase absorbing wavelength and corresponding fluorescence emission wavelengths of Copper-cladding Aluminum Bar amount Red Shift Phenomena also occurs for the material, while fluorescence quantum yield also changes. Preparation method of the present invention is simple, environmentally protective, has good application potential in preparation LED.
Description
Technical field
The present invention relates to a kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite method of manufacturing fluorescent material and purposes.
Background technology
LED (Light Emitting Diode) is acknowledged as the new light sources of 21 century, be continue electric filament lamp, fluorescent lamp,
The 4th generation light source after high-intensity gas discharge lamp.LED is a kind of by the light source made by semiconductor technology, and it is sent
The wavelength of light covers infrared light, it is seen that light and ultraviolet light.Owing to LED is that a kind of emerging illumination being different from conventional light source sets
Standby, can converting electrical energy be directly the light emitting diode (LED) of luminous energy, along with maturation and the breakthrough of manufacturing technology, become the many families of collection
Advantage luminescence component, also makes LED become the rising star of 21 century lighting source.LED is by phosphor
Material generally comprises inorganic fluorescent material, such as alkaline-earth metal and rare earth element；Organic fluorescence materials, such as organic little mulecular luminescence material
Material, high-molecular luminous material and organic coordination compound luminescent material；And metal semiconductor is nanocrystalline or nano-cluster.And we are usual
The material with carbon element of the macroscopic view said lacks suitable band gap, therefore itself is difficult to be developed into a kind of preferably luminescent material.At present,
Fluorescent conversion type white light LEDs is still faced with a lot of problem and challenge, mainly show as improving luminous efficiency, promote luminous mass,
Improve radiator structure.Therefore, develop that inexpensive, preparation be simple, the fluorescent material of excellent is white-light illuminating display neck
The important topic in territory.
In recent years, perovskite solaode is by good light absorptive, charge transport rate, and huge exploitation is dived
Power, is described as " the new hope of photovoltaic art ".Nearest its electricity conversion of photovoltaic device about hybrid inorganic-organic is
More than 20%, and another full-inorganic perovskite material similarly is because of its good light electricity quality, narrow excitation band energy, excellent
Different heat stability, the suitable photoelectricity transmission time, at high energy photovoltaic cell, light excitation diode (LED), laser, laser is examined
The application surveying device causes the widely studied of people.The general structure of full-inorganic halogen perovskite material is ABX3(wherein A=Rb+,Cs+；B=Ge2+,Sn2+,Pb2+；X=F-,Cl-,Br-,I-, or their complex), in this structure, cation A is positioned at cube
Body vertex position, metal B atom is positioned at cubic cell body-centered, and halogen X atom is positioned at the cube center of area, compared to common rib,
The structure that coplanar fashion connects, perovskite structure is more stable, is more beneficial for the diffusive migration of defect, therefore can be effectively improved material
The photovoltaic performance of material.
CsPbX3Perovskite material before a century just advantageously, it has been found that about it synthesis, crystal structure and
Photoconduction behavior was also reported for work before half a century, but about the nanocrystalline of its collosol and gel state until 2015 just by first
Report.Owing to its preparation time is short, the most stable in environment, fluorescence quantum yield is up to 90%, it is therefore expected that it is at phosphor
Material aspect has potential application.CsPbBr3Have relative to other halogen perovskite material be easily-synthesized, the transmission of excellent electric charge
Character and stable perovskite structure, be used to the research of fluorescent material the most at first.Study on the modification to this material at present
Mainly around the replacement in anion, as I ion or Cl ion replaced by Br, the replacement of both ions can widen this
Levy the absorbing wavelength of material.But the replacement for its cation is then difficult to carry out, and traces it to its cause, mainly has two aspects, work as portion
Can not meet when segregant is replaced B ion octoploids structure and replace after material whether can still keep its perovskite to tie
Structure.Relative to other inorganic metal ion, Cu ion can meet Hund1/2 as a potential magnetic particle, its electronic structure
Free principle, metallic element and the metal-oxide of copper does not the most possess ferromagnetism simultaneously.Based on this, we intend employing Cu ion will
CsPbBr3In part Pb ion be replaced, with the photoluminescent property of this further research material.
Summary of the invention
It is an object of the invention to, it is provided that a kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material and preparation method and use
On the way, the skeleton symbol of this material is CsPb1-xCuxBr3, between x is in the range of 0-1, obtained material is faint yellow or yellow
Powder, this material is Emission in Cubic, and space group isOccur further by dissolving in organic solvent under high temperature
Reaction, with normal hexane or toluene equal solvent wash, purification obtains Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, it is a size of
Between 10-30nm, by testing its UV, visible light (wave-length coverage 350-700nm) and fluorescence spectrum (excitation wavelength is 360nm),
Also Red Shift Phenomena, simultaneously fluorescence is there is in this material along with increase absorbing wavelength and the corresponding fluorescence emission wavelengths of Copper-cladding Aluminum Bar amount
Quantum yield also changes.Preparation method of the present invention is simple, environmental protection, and material has good application in terms of LED and dives
Energy.
Described a kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material of the present invention, this material structure skeleton symbol is:
CsPb1-XCuxBr3, wherein x is between 0-1, and this material is faint yellow or yellow powder, Emission in Cubic, and space group is
The preparation method of described Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, can realize inhaling by regulation and control copper content
Receiving wavelength from blueness to green red shift, concrete operations follow these steps to carry out:
A, oleic acid, oleyl amine and octadecylene to be respectively put into equipped with mass ratio for 10-18:1:1 by volume be 1:0-1:1's
Lead bromide, with the quartz reactor of copper bromide powder, seals with plug, is placed in magnetic agitation electric jacket, evacuation, slowly
It is warming up to 100-120 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 130-180 DEG C, after temperature stabilization, continue
Constant temperature 30 minutes；
C, will be rapidly injected in step b system containing the octadecylene solution that concentration is 0.1-0.8M cesium ion, react 5-
10 seconds, rapidly whole quartz reactor is placed in ice-water bath 5-10 minute；
D, the 8000-12000 in high speed centrifuge of the solution in step c is turned lower centrifugal 15 minutes；
E, the centrifugal product toluene in step d or normal hexane solvent are washed 3-5 time, then in temperature 80 DEG C vacuum drying
Obtain CsPb1-xCuxBr3Fluorescent material.
Cesium ion in step c is cesium acetate or cesium carbonate, and cesium ion is x:1-with the mass ratio of copper bromide and lead bromide
X:1.2, wherein x is between 0-1.
The purposes in LED luminescence prepared by described Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material.
The preparation method of described Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material of the present invention, for solvent thermal
Method, will be dissolved in organic solvent by inorganic reaction thing under nitrogen atmosphere high temperature, the chemical reaction occurred further.Involved
To reactant and solvent all can use commercially available raw material.
Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material of the present invention is purposes in preparation LED luminescence.
Accompanying drawing explanation
Fig. 1 be Copper-cladding Aluminum Bar amount of the present invention be X=0.1 powder diffraction XRD figure spectrum.
Fig. 2 be Copper-cladding Aluminum Bar amount of the present invention be the sample dispersion of X=0.1 in normal hexane, concentration is 10-5The UV, visible light of M
Absorb collection of illustrative plates.
Fig. 3 be Copper-cladding Aluminum Bar amount of the present invention be the sample dispersion of X=0.1 in normal hexane, concentration is 10-5The fluorescent emission of M
Collection of illustrative plates, excitation wavelength is 360nm.
Fig. 4 be Copper-cladding Aluminum Bar amount of the present invention be the scanning electron microscope (SEM) photograph of the sample of X=0.1.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1
A, by the lead bromide (PbBr of 0.19mmoL2) and 0.01mmoL copper bromide (CuBr2) to be placed in the quartz of 30mL anti-for powder
Answer in device, add the octadecylene of 5mL, be subsequently adding the oleic acid of 0.3mL and 0.3mL oleyl amine, seal with plug, be placed in magnetic force and stir
Mix in electric jacket, evacuation, it is to slowly warm up to 100 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 170 DEG C, be filled with nitrogen, temperature stabilization
After, continue constant temperature 30 minutes,
C, 0.4mL is contained the octadecylene solution that concentration is 0.8M cesium ion it is rapidly injected in step b system, react 5
Second, rapidly whole quartz reactor is placed in ice-water bath 5 minutes；
D, by the solution in step c in high speed centrifuge under 9000 turns centrifugal 15 minutes,
E, the centrifugal product toluene solvant in step d is washed 3 times, be vacuum dried at temperature 80 DEG C and obtain
CsPb0.95Cu0.05Br3Fluorescent material.
The fluorescent material obtained is placed in normal hexane so that it is concentration is 10-5M, with ultraviolet-visual spectrometer and fluorescence light
Its uv absorption scope and fluorescence emission spectrum tested by spectrometer, it is seen that spectral region is 300-511nm, maximum fluorescence emission spectrum
For 503.6nm, calculating its fluorescence quantum yield on the basis of rhodamine B is 72.3%.
Embodiment 2
A, by the lead bromide (PbBr of 0.16mmoL2) and 0.04mmoL copper bromide (CuBr2) to be placed in the quartz of 30mL anti-for powder
Answer in device, add the octadecylene of 5mL, be subsequently adding the oleic acid of 0.4mL and 0.4mL oleyl amine, seal with plug, be placed in magnetic force and stir
Mix in electric jacket, evacuation, it is to slowly warm up to 105 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 160 DEG C, be filled with nitrogen, temperature stabilization
After, continue constant temperature 30 minutes；
C, 0.3mL is contained the octadecylene solution that concentration is 0.1M cesium ion it is rapidly injected in step b system, react 7
Second, rapidly whole quartz reactor is placed in ice-water bath 6 minutes,
D, by the solution in step c in high speed centrifuge under 8000 turns centrifugal 15 minutes；
E, the centrifugal product normal hexane solvent in step d is washed 4 times, be vacuum dried at temperature 80 DEG C and obtain
CsPb0.8Cu0.2Br3Fluorescent material.
By detection method in embodiment 1, the ultraviolet-visible spectral limit of this material is 300-517nm, maximum fluorescence emission
Spectrum is 508.6nm, and fluorescence quantum yield is 81.2%.
Embodiment 3
A, by the lead bromide (PbBr of 0.12mmoL2) and 0.08mmoL copper bromide (CuBr2) to be placed in the quartz of 30mL anti-for powder
Answer in device, add the octadecylene of 5mL, be subsequently adding the oleic acid of 0.5mL and 0.5mL oleyl amine, seal with plug, be placed in magnetic force and stir
Mix in electric jacket, evacuation, it is to slowly warm up to 110 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 170 DEG C, be filled with nitrogen, temperature stabilization
After, continue constant temperature 30 minutes；
C, 0.4mL is contained the octadecylene solution that concentration is 0.5M cesium ion it is rapidly injected in step b system, react 8
Second, rapidly whole quartz reactor is placed in ice-water bath 10 minutes；
D, by the solution in step c in high speed centrifuge under 10000 turns centrifugal 15 minutes；
E, the centrifugal product normal hexane solvent in step d is washed 4 times, be vacuum dried at temperature 80 DEG C and obtain
CsPb0.6Cu0.4Br3Fluorescent material.
By detection method in embodiment 1, the ultraviolet-visible spectral limit of this material is 300-522nm, maximum fluorescence emission
Spectrum is 513.4nm, and fluorescence quantum yield is 74.6%.
Embodiment 4
A, by the lead bromide (PbBr of 0.17mmoL2) and 0.03mmoL copper bromide (CuBr2) to be placed in the quartz of 30mL anti-for powder
Answer in device, add the octadecylene of 5mL, be subsequently adding the oleic acid of 0.4mL and 0.4mL oleyl amine, seal with plug, be placed in magnetic force and stir
Mix in electric jacket, evacuation, it is to slowly warm up to 120 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 160 DEG C, be filled with nitrogen, temperature stabilization
After, continue constant temperature 30 minutes；
C, 0.5mL is contained the octadecylene solution that concentration is 0.8M cesium ion it is rapidly injected in step b system, react 6
Second, rapidly whole quartz reactor is placed in ice-water bath 5 minutes；
D, by the solution in step c in high speed centrifuge under 11000 turns centrifugal 15 minutes；
E, the centrifugal product normal hexane solvent in step d is washed 5 times, be vacuum dried at temperature 80 DEG C and obtain
CsPb0.85Cu0.15Br3Fluorescent material.
By detection method in embodiment 1, the ultraviolet-visible spectral limit of this material is between 300-514nm, maximum fluorescence
Emission spectrum is 509nm, and fluorescence quantum yield is 69.3%.
Embodiment 5
A, by the lead bromide (PbBr of 0.15mmoL2) and 0.05mmoL copper bromide (CuBr2) to be placed in the quartz of 30mL anti-for powder
Answer in device, add the octadecylene of 5mL, be subsequently adding the oleic acid of 0.6mL and 0.6mL oleyl amine, seal with plug, be placed in magnetic force and stir
Mix in electric jacket, evacuation, it is to slowly warm up to 120 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 170 DEG C, be filled with nitrogen, temperature stabilization
After, continue constant temperature 30 minutes；
C, 0.6mL is contained the octadecylene solution that concentration is 0.6M cesium ion it is rapidly injected in step b system, react 8
Second, rapidly whole quartz reactor is placed in ice-water bath 10 minutes；
D, by the solution in step c in high speed centrifuge under 12000 turns centrifugal 15 minutes；
E, the centrifugal product normal hexane solvent in step d is washed 5 times, be vacuum dried at temperature 80 DEG C and obtain
CsPb0.75Cu0.25Br3Fluorescent material；
By detection method in embodiment 1, the ultraviolet-visible spectral limit of this material is between 300-519nm, maximum fluorescence
Emission spectrum is 510nm, and fluorescence quantum yield is 66.6%.
Embodiment 6
A, by the lead bromide (PbBr of 0.1mmoL2) and 0.1mmoL copper bromide (CuBr2) powder is placed in the quartz reaction of 30mL
In device, add the octadecylene of 5mL, be subsequently adding the oleic acid of 0.6mL and 0.6mL oleyl amine, seal with plug, be placed in magnetic agitation
In electric jacket, evacuation, it is to slowly warm up to 120 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 180 DEG C, be filled with nitrogen, temperature stabilization
After, continue constant temperature 30 minutes；
C, 0.6mL is contained the octadecylene solution that concentration is 0.8M cesium ion it is rapidly injected in step b system, react 8
Second, rapidly whole quartz reactor is placed in ice-water bath 10 minutes；
D, by the solution in step c in high speed centrifuge under 8000 turns centrifugal 15 minutes；
E, the centrifugal product normal hexane solvent in step d is washed 5 times, be vacuum dried at temperature 80 DEG C and obtain
CsPb0.5Cu0.5Br3Fluorescent material.
By detection method in embodiment 1, the ultraviolet-visible spectral limit of this material is between 300-526nm, maximum fluorescence
Emission spectrum is 518nm, and fluorescence quantum yield is 62.6%.
Claims (4)
1. a Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, it is characterised in that this material structure skeleton symbol is: CsPb1- XCuxBr3, wherein x is between 0-1, and this material is faint yellow or yellow powder, Emission in Cubic, and space group is。
The preparation method of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material the most according to claim 1, it is characterised in that
Can realize absorbing wavelength from blueness to green red shift by regulation and control copper content, concrete operations follow these steps to carry out:
A, oleic acid, oleyl amine and octadecylene to be respectively put into equipped with mass ratio for 10-18:1:1 by volume be the bromination of 1:0-1:1
Lead, with the quartz reactor of copper bromide powder, seals with plug, is placed in magnetic agitation electric jacket, evacuation, slowly heats up
To 100-120 DEG C；
B, constant temperature, after 30 minutes, are filled with nitrogen, reaction system are to slowly warm up to 130-180 DEG C, after temperature stabilization, continue constant temperature
30 minutes；
C, will be rapidly injected in step b system containing the octadecylene solution that concentration is 0.1-0.8M cesium ion, react the 5-10 second
Clock, is placed in whole quartz reactor rapidly in ice-water bath 5-10 minute；
D, the 8000-12000 in high speed centrifuge of the solution in step c is turned lower centrifugal 15 minutes；
E, the centrifugal product toluene in step d or normal hexane solvent are washed 3-5 time, then obtain in 80 DEG C of vacuum drying of temperature
CsPb1-xCuxBr3Fluorescent material.
The preparation method of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material the most according to claim 1, it is characterised in that
Cesium ion in step c is cesium acetate or cesium carbonate, and cesium ion is x:1-x:1.2 with the mass ratio of copper bromide and lead bromide, its
Middle x is between 0-1.
The use in LED luminescence prepared by Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material the most according to claim 1
On the way.
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| CN109065738A (en) * | 2018-08-13 | 2018-12-21 | 许昌学院 | Method based on Pot metal in-situ one-step synthesis high-crystallinity Copper-cladding Aluminum Bar perovskite thin film |
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