CN106010518B - A kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material and preparation method and purposes - Google Patents
A kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material and preparation method and purposes Download PDFInfo
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- CN106010518B CN106010518B CN201610383953.XA CN201610383953A CN106010518B CN 106010518 B CN106010518 B CN 106010518B CN 201610383953 A CN201610383953 A CN 201610383953A CN 106010518 B CN106010518 B CN 106010518B
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000005253 cladding Methods 0.000 title claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 17
- 150000002367 halogens Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- -1 octadecylene Chemical group 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 17
- 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
- 238000005119 centrifugation Methods 0.000 claims description 10
- 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
- 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
- 229910052792 caesium Inorganic materials 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 210000004209 hair Anatomy 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 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical class [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 7
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000001507 sample dispersion Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity 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
- 238000007689 inspection Methods 0.000 description 1
- 238000004020 luminiscence type 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
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 230000001105 regulatory effect Effects 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
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization 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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- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- 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 method and purposes, the skeleton symbol of the material is CsPb1‑xCuxBr3：Between ranging from the 01 of X, obtained material is faint yellow or yellow powder, which is cubic phase, and space group is.By the way that dissolving is repeatedly washed with n-hexane or toluene equal solvent to the reaction that further occurs, purifies and obtain Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, size is between 10 30 nm, by testing its UV, visible light in organic solvent under high temperature（350 700 nm of wave-length coverage）And fluorescence spectrum（Excitation wavelength is 360nm）, which also occurs Red Shift Phenomena with the increase absorbing wavelength and corresponding fluorescence emission wavelengths of Copper-cladding Aluminum Bar amount, while fluorescence quantum yield also changes.Preparation method of the present invention is simple, environmentally protective, has good application potential in preparing 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 after incandescent lamp, fluorescent lamp,
The 4th generation light source after high-intensity gas discharge lamp.LED is a kind of light source by made by semiconductor technology, is sent out
The wavelength of light covers infrared light, it is seen that light and ultraviolet light.Since LED is that a kind of emerging illumination being different from conventional light source is set
It is standby, directly it can become collection crowd families with maturation and the breakthrough of manufacturing technology for the light emitting diode (LED) of luminous energy by converting electrical energy
The luminescence component of advantage, but also LED becomes 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, as organic molecule shines material
Material, high-molecular luminous material and organic coordination compound luminescent material；And metal semiconductor is nanocrystalline or nano-cluster.And we are usually
The carbon material for the macroscopic view said lacks suitable band gap, therefore itself is difficult to be developed into a kind of ideal luminescent material.Currently,
Fluorescent conversion type white light LEDs are still faced with many problems and challenge, be mainly shown as improve luminous efficiency, promoted luminous mass,
Improve radiator structure.Therefore, developing inexpensive, preparing simple, excellent fluorescent material is white-light illuminating display neck
The important topic in domain.
In recent years, perovskite solar cell is latent by good light absorptive, charge transport rate and huge exploitation
Power is known as " new hope of photovoltaic art ".About the photovoltaic device of hybrid inorganic-organic its electricity conversion recently
More than 20%, and another similar full-inorganic perovskite material is because of its good photoelectricity quality, and narrow excitation band energy is excellent
Different thermal stability, suitable photoelectricity transmission time, in high energy photovoltaic cell, light excitation diode (LED), laser, laser inspection
The application for surveying device causes the extensive research 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 compound), in the structure, cation A is located at cube
Body vertex position, metal B atoms are located at cubic cell body-centered, and halogen X atoms are located at the cube center of area, compared to total rib,
The structure of coplanar fashion connection, perovskite structure are more stablized, and are more advantageous to the diffusive migration of defect, therefore can effectively improve material
The photovoltaic performance of material.
CsPbX3Perovskite material before a century just advantageously, it has been found that about its synthesis, crystal structure and its
Light guide behavior is also reported for work before half a century, however about the nanocrystalline until ability in 2015 is by for the first time of its collosol and gel state
Report.Since its preparation time is short, stablize relatively in environment, fluorescence quantum yield is up to 90%, it is therefore expected that it is in phosphor
There is potential application in terms of material.CsPbBr3Relative to other halogen perovskite materials have be easily-synthesized, excellent charge transmission
The perovskite structure of property and stabilization, therefore it is used to the research of fluorescent material at first.At present to the study on the modification of the material
Mainly around the replacement in anion, such as I ions or Cl ions are replaced Br, the replacement of both ions can widen this
Levy the absorbing wavelength of material.But it is difficult then to carry out for the replacement of its cation, to find out its cause, main, there are two aspects, work as portion
Segregant cannot meet when being replaced B ions octoploids structure and replacement after material whether can still keep its perovskite knot
Structure.Relative to other inorganic metal ions, Cu ions can meet Hund1/2 as a potential magnetic particle, electronic structure
Free principle, while the metallic element of copper and metal oxide do not have ferromagnetism.Based on this, we are quasi- will using Cu ions
CsPbBr3In part Pb ions be replaced, with the photoluminescent property of this further research material.
Invention content
The object of the present invention is to provide a kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material and preparation methods and use
On the way, the skeleton symbol of the material is CsPb1-xCuxBr3, between the ranging from 0-1 of x, obtained material is faint yellow or yellow
Powder, the material are cubic phase, and space group isBy under high temperature in organic solvent dissolving to further occur
Reaction is washed with n-hexane or toluene equal solvent, purifies and obtain Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, and size is
Between 10-30nm, by testing its UV, visible light (wave-length coverage 350-700nm) 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, while fluorescence also occur for the material
Quantum yield also changes.Preparation method of the present invention is simple, environmentally protective, and material has good application latent in terms of LED
Energy.
A kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material of the present invention, the material structure skeleton symbol are：
CsPb1-XCuxBr3, wherein x is between 0-1, which is faint yellow or yellow powder, and cubic phase, space group is
The preparation method of the Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material can realize suction by regulating and controlling copper content
Wavelength is received to follow these steps to carry out from blue to the red shift of green, concrete operations：
A, it is 10-18 by volume by oleic acid, oleyl amine and octadecylene:1:1 be respectively put into equipped with mass ratio be 1:0-1:1
Lead bromide is sealed with rubber plug with the quartz reactor of bromination copper powders, is placed in magnetic agitation electric jacket, vacuumizes, slowly
It is warming up to 100-120 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 130-180 DEG C, after temperature is stablized, is continued
Constant temperature 30 minutes；
C, the octadecylene solution containing a concentration of 0.1-0.8M cesium ions is rapidly injected in step b systems, reacts 5-
10 seconds, entire quartz reactor is placed in ice-water bath 5-10 minutes rapidly；
D, by the solution in step c, 8000-12000 turns lower centrifugation 15 minutes in supercentrifuge；
E, by step d centrifugation product toluene or n-hexane solvent wash 3-5 times, then in the vacuum drying of 80 DEG C of temperature
Obtain CsPb1-xCuxBr3Fluorescent material.
Cesium ion in step c is cesium acetate or cesium carbonate, and cesium ion is x with the mass ratio of copper bromide and lead bromide:1-
x:1.2, wherein x is between 0-1.
The Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material is preparing the purposes in LED shines.
The preparation method of the Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material of the present invention is solvent heat
Inorganic reaction object is dissolved under nitrogen atmosphere high temperature in organic solvent, the chemical reaction further occurred by method.It is involved
To reactant and solvent commercially available raw material all can be used.
Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material of the present invention purposes in preparing LED and shining.
Description of the drawings
Fig. 1 is the powder diffraction XRD spectrum that Copper-cladding Aluminum Bar amount of the present invention is X=0.1.
Fig. 2 be Copper-cladding Aluminum Bar amount of the present invention be X=0.1 sample dispersion in n-hexane, a concentration of 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 X=0.1 sample dispersion in n-hexane, a concentration of 10-5The fluorescent emission of M
Collection of illustrative plates, excitation wavelength 360nm.
Fig. 4 is the scanning electron microscope (SEM) photograph for the sample that Copper-cladding Aluminum Bar amount of the present invention is X=0.1.
Specific implementation mode
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 bromides (CuBr2) powder be placed in 30mL quartz it is anti-
It answers in device, the octadecylene of 5mL is added, be then added the oleic acid of 0.3mL and 0.3mL oleyl amines, sealed with rubber plug, be placed in magnetic force and stir
It mixes in electric jacket, vacuumizes, be to slowly warm up to 100 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 170 DEG C, is filled with nitrogen, and temperature is stablized
Afterwards, continue constant temperature 30 minutes,
C, the 0.4mL octadecylene solution for containing a concentration of 0.8M cesium ions is rapidly injected in step b systems, reaction 5
Second, entire quartz reactor is placed in ice-water bath 5 minutes rapidly；
D, the solution in step c is centrifuged 15 minutes in supercentrifuge under 9000 turns,
E, the centrifugation product in step d is washed 3 times with toluene solvant, is dried in vacuo and obtains at 80 DEG C of temperature
CsPb0.95Cu0.05Br3Fluorescent material.
Obtained fluorescent material is placed in n-hexane, make its a concentration of 10-5M, with ultraviolet-visual spectrometer and fluorescence light
Spectrometer tests its UV absorption range and fluorescence emission spectrum, it is seen that spectral region 300-511nm, maximum fluorescence emission spectrum
For 503.6nm, it is 72.3% that its fluorescence quantum yield is calculated on the basis of rhodamine B.
Embodiment 2
A, by the lead bromide (PbBr of 0.16mmoL2) and 0.04mmoL copper bromides (CuBr2) powder be placed in 30mL quartz it is anti-
It answers in device, the octadecylene of 5mL is added, be then added the oleic acid of 0.4mL and 0.4mL oleyl amines, sealed with rubber plug, be placed in magnetic force and stir
It mixes in electric jacket, vacuumizes, be to slowly warm up to 105 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 160 DEG C, is filled with nitrogen, and temperature is stablized
Afterwards, continue constant temperature 30 minutes；
C, the 0.3mL octadecylene solution for containing a concentration of 0.1M cesium ions is rapidly injected in step b systems, reaction 7
Second, entire quartz reactor is placed in ice-water bath 6 minutes rapidly,
D, the solution in step c is centrifuged 15 minutes in supercentrifuge under 8000 turns；
E, the centrifugation product in step d is washed 4 times with n-hexane solvent, is dried in vacuo and obtains at 80 DEG C of temperature
CsPb0.8Cu0.2Br3Fluorescent material.
By detection method in embodiment 1, the uv-vis spectra ranging from 300-517nm of the material, maximum fluorescence emission
Spectrum is 508.6nm, fluorescence quantum yield 81.2%.
Embodiment 3
A, by the lead bromide (PbBr of 0.12mmoL2) and 0.08mmoL copper bromides (CuBr2) powder be placed in 30mL quartz it is anti-
It answers in device, the octadecylene of 5mL is added, be then added the oleic acid of 0.5mL and 0.5mL oleyl amines, sealed with rubber plug, be placed in magnetic force and stir
It mixes in electric jacket, vacuumizes, be to slowly warm up to 110 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 170 DEG C, is filled with nitrogen, and temperature is stablized
Afterwards, continue constant temperature 30 minutes；
C, the 0.4mL octadecylene solution for containing a concentration of 0.5M cesium ions is rapidly injected in step b systems, reaction 8
Second, entire quartz reactor is placed in ice-water bath 10 minutes rapidly；
D, the solution in step c is centrifuged 15 minutes in supercentrifuge under 10000 turns；
E, the centrifugation product in step d is washed 4 times with n-hexane solvent, is dried in vacuo and obtains at 80 DEG C of temperature
CsPb0.6Cu0.4Br3Fluorescent material.
By detection method in embodiment 1, the uv-vis spectra ranging from 300-522nm of the material, maximum fluorescence emission
Spectrum is 513.4nm, fluorescence quantum yield 74.6%.
Embodiment 4
A, by the lead bromide (PbBr of 0.17mmoL2) and 0.03mmoL copper bromides (CuBr2) powder be placed in 30mL quartz it is anti-
It answers in device, the octadecylene of 5mL is added, be then added the oleic acid of 0.4mL and 0.4mL oleyl amines, sealed with rubber plug, be placed in magnetic force and stir
It mixes in electric jacket, vacuumizes, be to slowly warm up to 120 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 160 DEG C, is filled with nitrogen, and temperature is stablized
Afterwards, continue constant temperature 30 minutes；
C, the 0.5mL octadecylene solution for containing a concentration of 0.8M cesium ions is rapidly injected in step b systems, reaction 6
Second, entire quartz reactor is placed in ice-water bath 5 minutes rapidly；
D, the solution in step c is centrifuged 15 minutes in supercentrifuge under 11000 turns；
E, the centrifugation product in step d is washed 5 times with n-hexane solvent, is dried in vacuo and obtains at 80 DEG C of temperature
CsPb0.85Cu0.15Br3Fluorescent material.
By detection method in embodiment 1, between the uv-vis spectra ranging from 300-514nm of the material, maximum fluorescence
Emission spectrum is 509nm, fluorescence quantum yield 69.3%.
Embodiment 5
A, by the lead bromide (PbBr of 0.15mmoL2) and 0.05mmoL copper bromides (CuBr2) powder be placed in 30mL quartz it is anti-
It answers in device, the octadecylene of 5mL is added, be then added the oleic acid of 0.6mL and 0.6mL oleyl amines, sealed with rubber plug, be placed in magnetic force and stir
It mixes in electric jacket, vacuumizes, be to slowly warm up to 120 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 170 DEG C, is filled with nitrogen, and temperature is stablized
Afterwards, continue constant temperature 30 minutes；
C, the 0.6mL octadecylene solution for containing a concentration of 0.6M cesium ions is rapidly injected in step b systems, reaction 8
Second, entire quartz reactor is placed in ice-water bath 10 minutes rapidly；
D, the solution in step c is centrifuged 15 minutes in supercentrifuge under 12000 turns；
E, the centrifugation product in step d is washed 5 times with n-hexane solvent, is dried in vacuo and obtains at 80 DEG C of temperature
CsPb0.75Cu0.25Br3Fluorescent material；
By detection method in embodiment 1, between the uv-vis spectra ranging from 300-519nm of the material, maximum fluorescence
Emission spectrum is 510nm, fluorescence quantum yield 66.6%.
Embodiment 6
A, by the lead bromide (PbBr of 0.1mmoL2) and 0.1mmoL copper bromides (CuBr2) powder is placed in the quartz reaction of 30mL
In device, the octadecylene of 5mL is added, is then added the oleic acid of 0.6mL and 0.6mL oleyl amines, is sealed with rubber plug, be placed in magnetic agitation
It in electric jacket, vacuumizes, is to slowly warm up to 120 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 180 DEG C, is filled with nitrogen, and temperature is stablized
Afterwards, continue constant temperature 30 minutes；
C, the 0.6mL octadecylene solution for containing a concentration of 0.8M cesium ions is rapidly injected in step b systems, reaction 8
Second, entire quartz reactor is placed in ice-water bath 10 minutes rapidly；
D, the solution in step c is centrifuged 15 minutes in supercentrifuge under 8000 turns；
E, the centrifugation product in step d is washed 5 times with n-hexane solvent, is dried in vacuo and obtains at 80 DEG C of temperature
CsPb0.5Cu0.5Br3Fluorescent material.
By detection method in embodiment 1, between the uv-vis spectra ranging from 300-526nm of the material, maximum fluorescence
Emission spectrum is 518nm, fluorescence quantum yield 62.6%.
Claims (2)
1. a kind of Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material, it is characterised in that the material structure skeleton symbol is：CsPb1- XCuxBr3, wherein x is 0.01,0.04,0.08,0.03,0.05,0.1, which is faint yellow or yellow powder, and cubic phase is empty
Between group be, concrete operations follow these steps to carry out：
A, it is 10-18 by volume by oleic acid, oleyl amine and octadecylene:1:1 be respectively put into equipped with mass ratio be 1:0-1:1 bromination
Lead is sealed with rubber plug with the quartz reactor of bromination copper powders, is placed in magnetic agitation electric jacket, vacuumizes, and is slowly heated up
To 100-120 DEG C；
B, constant temperature is filled with nitrogen after 30 minutes, and reaction system is to slowly warm up to 130-180 DEG C, after temperature is stablized, continues constant temperature
30 minutes；
C, the octadecylene solution containing a concentration of 0.1-0.8M cesium ions is rapidly injected in step b systems, is reacted 5-10 seconds
Entire quartz reactor is placed in ice-water bath 5-10 minutes, the wherein quality of cesium ion and copper bromide and lead bromide by clock rapidly
Than for x:1-x:1.2, wherein x are 0.01,0.04,0.08,0.03,0.05,0.1；
D, by the solution in step c, 8000-12000 turns lower centrifugation 15 minutes in supercentrifuge；
E, by step d centrifugation product toluene or n-hexane solvent wash 3-5 times, then obtained in 80 DEG C of vacuum drying of temperature
CsPb1-xCuxBr3Fluorescent material.
2. the Copper-cladding Aluminum Bar full-inorganic halogen perovskite fluorescent material that method obtains according to claim 1 is being prepared in LED hairs
Purposes in light.
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| CN110408378A (en) * | 2018-04-28 | 2019-11-05 | Tcl集团股份有限公司 | Core-shell quanta dots material and preparation method thereof |
| CN109065738B (en) * | 2018-08-13 | 2022-05-06 | 许昌学院 | Method for in-situ synthesis of high-crystallinity copper-doped perovskite thin film |
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| CN109728111B (en) * | 2018-12-21 | 2020-12-29 | 苏州大学 | Method for preparing high-performance all-inorganic perovskite solar cell based on copper bromide |
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| CN109957395B (en) * | 2019-04-10 | 2022-03-22 | 济宁学院 | Temperature-sensitive light-emitting semiconductor material and preparation method and application thereof |
| CN110394194B (en) * | 2019-08-07 | 2021-12-17 | 浙江师范大学 | Controllable preparation method of novel photocatalyst based on inorganic ligand modification |
| CN111661867B (en) * | 2020-06-30 | 2022-04-29 | 重庆大学 | Preparation method of lead-free cesium copper chloride nanocrystalline and product and application thereof |
| CN112520781B (en) * | 2020-12-03 | 2022-02-11 | 吉林大学 | Copper-doped ternary metal halide and preparation method thereof |
| CN114605996A (en) * | 2022-04-12 | 2022-06-10 | 重庆邮电大学 | Preparation method of sodium and copper co-doped cesium lead bromine perovskite quantum dot, product and application thereof |
| CN115261020A (en) * | 2022-06-13 | 2022-11-01 | 广东墨睿科技有限公司 | Graphene-loaded copper ion-doped blue-light perovskite nanocrystalline dispersion |
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