CN106085432B - Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application - Google Patents
Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application Download PDFInfo
- Publication number
- CN106085432B CN106085432B CN201610420314.6A CN201610420314A CN106085432B CN 106085432 B CN106085432 B CN 106085432B CN 201610420314 A CN201610420314 A CN 201610420314A CN 106085432 B CN106085432 B CN 106085432B
- Authority
- CN
- China
- Prior art keywords
- organic
- inorganic hybrid
- powder
- lanthanum fluoride
- doped lanthanum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000843 powder Substances 0.000 title claims abstract description 44
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 229910052777 Praseodymium Inorganic materials 0.000 title claims abstract description 40
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000004094 surface-active agent Substances 0.000 claims abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000011858 nanopowder Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000004140 cleaning Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910002319 LaF3 Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- -1 rare earth nitrate Chemical class 0.000 abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009396 hybridization Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application.The chemical formula composition of nano-powder is La1‑xPrxF3, 10 in chemical formula‑3≤x≤10‑1, and La1‑xPrxF3In fluorine be connected with the carbon in surfactant with C F chemical bonds and form organic-inorganic hybrid material, material is the powder of 20~70nm of particle diameter；Method is first according to La1‑ xPrxF3Component than by the lanthana of respective amount and praseodymium oxide and aqueous solution of nitric acid be configured to stirring total rare earth (TRE) ion concentration be 0.1~0.5mol/L rare earth nitrate aqueous solution, aqueous surfactant solution and ammonium fluoride are added in rare earth nitrate aqueous solution respectively successively again and stirred, obtain precursor solution, afterwards, first precursor solution is placed under air-tight state and is reacted, obtain reaction solution, separation of solid and liquid, washing and the processing of drying are carried out successively to the reaction solution cooled again, purpose product is made.It is directly sent white light by ultraviolet excitation, and pole is beneficial to widely illumination of the commercial applications in LED indoors.
Description
Technical field
The present invention relates to a kind of organic-inorganic hybrid nanometer powder and preparation method and purposes, especially a kind of praseodymium doped fluorine
Change organic-inorganic hybrid nanometer powder of lanthanum and its preparation method and application.
Background technology
The technological break-through and industrialization of the light emitting diode nineties in last century (LED) and ultraviolet LED have greatly promoted half
The development of conductor illumination.Since white LED light source has the advantages that long lifespan, small, energy conservation and environmental protection, rapid proliferation should
The every field such as daily life, industrial production are used.At present, realize the main path of white light LEDs such as entitled " White-
Light-Emitting Single Phosphors via Triply Doped LaF3Nanoparticles ",
J.Phys.Chem.C, 2013,117,12229-12238 (" pass through three heavy doping LaF3The white emitting fluorescent powder of nano-particle ",《Thing
Physicochemical C is printed》2013 volume 117 page 12229~12238) article described in, one of them is in indium gallium nitride
(InGaN) fluorescent powder of three primary colours or multiple color, the near ultraviolet sent using the chip (360~410nm) are applied on chip
Light carrys out excitated fluorescent powder and realizes white light emission.Though this approach can obtain white light, but also there is shortcoming, first, energy
The loss of energy is larger in amount transfer process, and obtained RGB light energy is relatively low, can make luminous efficiency and the color rendition of LED
Property is subject to large effect；Secondly, the complex process of white light LED part is made, cost is excessive.
The content of the invention
The technical problem to be solved in the present invention is overcomes shortcoming of the prior art, there is provided a kind of single-matrix it is glimmering
Light powder directly sends the organic-inorganic hybrid nanometer powder of the praseodymium doped lanthanum fluoride of white light after being stimulated.
The invention solves another technical problem to provide a kind of organic inorganic hybridization of above-mentioned praseodymium doped lanthanum fluoride
The preparation method of nano-powder.
The invention solves another technical problem to provide a kind of organic inorganic hybridization of above-mentioned praseodymium doped lanthanum fluoride
The purposes of nano-powder.
To solve the technical problem of the present invention, used technical solution is：The organic inorganic hybridization of praseodymium doped lanthanum fluoride
Nano-powder includes having LaF3The lanthanum fluoride base of chemical formula composition, particularly,
Chemical formula composition after the lanthanum fluoride is base and doped is La1-xPrxF3, 10 in chemical formula-3≤x≤10-1, and
La1-xPrxF3In fluorine be connected with the carbon in surfactant with C-F chemical bonds and form organic-inorganic hybrid material；
The organic-inorganic hybrid material is powder, and the powder is graininess, and the particle diameter of the particle is 20~70nm.
The further of organic-inorganic hybrid nanometer powder as praseodymium doped lanthanum fluoride is improved：
Preferably, particle is spherical, or elliposoidal.
To solve another technical problem of the present invention, another used technical solution is：Above-mentioned praseodymium doped fluorination
The organic-inorganic hybrid nanometer raw powder's production technology of lanthanum includes hydrothermal synthesis method, and particularly key step is as follows：
Step 1, first according to La1-xPrxF3Lanthana (La of the component than weighing respective amount2O3) and praseodymium oxide (Pr2O3)
Afterwards, by the aqueous solution of nitric acid of lanthana, praseodymium oxide and 6~15mol/L be configured to stirring total rare earth (TRE) ion concentration for 0.1~
The rare earth nitrate aqueous solution of 0.5mol/L, then successively respectively by the aqueous surfactant solution of 0.1~0.5mol/L and fluorination
Ammonium (NH4F) add in rare earth nitrate aqueous solution, stir that the reaction was complete to it, obtain precursor solution, wherein, precursor is molten
The molar ratio of total rare earth (TRE) ion in liquid, the surfactant in aqueous surfactant solution and ammonium fluoride is 1：0.5~2：3~
4；
Step 2, precursor solution is first placed in air-tight state, at least 8h is reacted at 140~220 DEG C, obtains reaction solution,
Separation of solid and liquid, washing and the processing of drying are carried out successively to the reaction solution cooled again, organic nothing of praseodymium doped lanthanum fluoride is made
Machine hybridized nanometer powder.
The further of organic-inorganic hybrid nanometer raw powder's production technology as praseodymium doped lanthanum fluoride is improved：
Preferably, surfactant is neopelex (SDBS), or polyvinylpyrrolidone (PVP), or lemon
Lemon acid sodium, or cetyl trimethylammonium bromide (CTAB), or lauryl sodium sulfate (SDS).
Preferably, the reaction time for being placed in the precursor solution of air-tight state is 8~24h.
Preferably, solid-liquid separation treatment is centrifuges, its rotating speed is 8000~12000r/min, the time be 5~
15min。
Preferably, carrying out washing treatment is to carry out the alternating of 2~3 times to isolated solid using deionized water and ethanol
Cleaning, solid is separated during cleaning to centrifuge.
Preferably, drying process is dried for the solid after cleaning is placed at 60~100 DEG C.
To solve another technical problem of the present invention, another used technical solution is：Above-mentioned praseodymium doped fluorination
The purposes of the organic-inorganic hybrid nanometer powder of lanthanum is,
Using the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride as fluorescent powder, for being carried out using ultraviolet light to it
Excite and send white light.
The further of purposes as the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride is improved：
Preferably, the wavelength of ultraviolet light is 320~410nm.
It is relative to the beneficial effect of the prior art：
First, to obtained purpose product respectively using X-ray diffractometer, transmission electron microscope, intelligent fourier infrared-drawing
Graceful spectrometer and steady-state lifetime Fluorescence Spectrometer is characterized, and from its result, the chemical formula composition of purpose product is La1- xPrxF3, 10 in chemical formula-3≤x≤10-1, and La1-xPrxF3In fluorine with the carbon in surfactant with C-F chemical bond phases
Connection composition organic-inorganic hybrid material, which is the graininess powder of 20~70nm of particle diameter, and particle is
It is spherical, or elliposoidal.It is this by La1-xPrxF3In fluorine be connected what is be assembled into the carbon in surfactant with C-F chemical bonds
Purpose product, white light is have issued by the excitation of ultraviolet light.
Second, preparation method is simple, science, efficiently.Not only be made single-matrix fluorescent powder be stimulated after directly send out
Go out the purpose product of white light --- the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride；Also there is making white light LED part
The characteristics of technique is simple, cost is low, and working service is convenient；And then make purpose product be extremely easy to widely commercial applications in
The illuminations of LED indoors.
Brief description of the drawings
Fig. 1 is one of result characterized to purpose product made from preparation method using X-ray diffraction (XRD) instrument.
XRD spectra shows purpose product by rare earth praseodymium doped lanthanum fluoride (LaF3：Pr3+) formed with surfactant hydridization, table therein
Face activating agent is neopelex.
Fig. 2 be the result that is characterized to obtained purpose product using intelligent fourier infrared-Raman spectrometer it
One.Curve A in figure is rare earth praseodymium doped lanthanum fluoride (LaF3：Pr3+) spectral line, curve B be purpose product spectral line；Can by it
Know, rare earth praseodymium doped lanthanum fluoride (LaF3：Pr3+) with foring new organic-inorganic hybrid material after surfactant hydridization ---
Purpose product, surfactant therein are neopelex.
Fig. 3 is one of result characterized to obtained purpose product using transmission electron microscope (TEM).TEM image is shown
It is nano level particulate matter to go out purpose product.
Fig. 4 is one of result characterized to obtained purpose product using steady-state lifetime Fluorescence Spectrometer.Its result
Confirm that purpose product have issued white light under the ultraviolet excitation of 320~410nm.
Embodiment
The preferred embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Buy from market or be voluntarily made first：
Lanthana；Praseodymium oxide；Aqueous solution of nitric acid；Neopelex, polyvinyl pyrrole as surfactant
Alkanone, sodium citrate, cetyl trimethylammonium bromide and lauryl sodium sulfate；Ammonium fluoride.
Then,
Embodiment 1
What is prepared concretely comprises the following steps：
Step 1, first according to La0.999Pr0.001F3Lanthana and praseodymium oxide of the component than weighing respective amount after, will aoxidize
The aqueous solution of nitric acid of lanthanum, praseodymium oxide and 6mol/L is configured to the rare earth nitric acid that total rare earth (TRE) ion concentration is 0.1mol/L with stirring
Saline solution.The aqueous surfactant solution of 0.5mol/L and ammonium fluoride are added into rare earth nitrate aqueous solution respectively successively again
In, stir that the reaction was complete to it, obtain precursor solution；Wherein, total rare earth (TRE) ion, the surfactant water in precursor solution
The molar ratio of surfactant and ammonium fluoride in solution is 1：0.5：4, surfactant is neopelex.
Step 2, precursor solution is first placed in air-tight state, reacts 24h at 140 DEG C, obtain reaction solution.Again to cooling
Reaction solution carry out separation of solid and liquid, washing and the processing of drying successively；Wherein, solid-liquid separation treatment is centrifuges, its turn
Speed is 8000r/min, time 15min, and carrying out washing treatment is to carry out 2 to isolated solid using deionized water and ethanol
Secondary alternating cleaning, when cleaning, separate solid to centrifuge, and the solid after cleaning is is placed at 60 DEG C by drying process
Drying.It is made and is similar to shown in Fig. 3, and the organic inorganic hybridization of the praseodymium doped lanthanum fluoride shown in curve as in Figure 1 and Figure 2
Nano-powder.
Embodiment 2
What is prepared concretely comprises the following steps：
Step 1, first according to La0.995Pr0.005F3Lanthana and praseodymium oxide of the component than weighing respective amount after, will aoxidize
The aqueous solution of nitric acid of lanthanum, praseodymium oxide and 9mol/L is configured to the rare earth nitric acid that total rare earth (TRE) ion concentration is 0.2mol/L with stirring
Saline solution.The aqueous surfactant solution of 0.4mol/L and ammonium fluoride are added into rare earth nitrate aqueous solution respectively successively again
In, stir that the reaction was complete to it, obtain precursor solution；Wherein, total rare earth (TRE) ion, the surfactant water in precursor solution
The molar ratio of surfactant and ammonium fluoride in solution is 1：0.9：3.8, surfactant is neopelex.
Step 2, precursor solution is first placed in air-tight state, reacts 20h at 160 DEG C, obtain reaction solution.Again to cooling
Reaction solution carry out separation of solid and liquid, washing and the processing of drying successively；Wherein, solid-liquid separation treatment is centrifuges, its turn
Speed is 9000r/min, time 13min, and carrying out washing treatment is to carry out 2 to isolated solid using deionized water and ethanol
Secondary alternating cleaning, when cleaning, separate solid to centrifuge, and the solid after cleaning is is placed at 70 DEG C by drying process
Drying.It is made and is similar to shown in Fig. 3, and the organic inorganic hybridization of the praseodymium doped lanthanum fluoride shown in curve as in Figure 1 and Figure 2
Nano-powder.
Embodiment 3
What is prepared concretely comprises the following steps：
Step 1, first according to La0.99Pr0.01F3Lanthana and praseodymium oxide of the component than weighing respective amount after, by lanthana,
The aqueous solution of nitric acid of praseodymium oxide and 11mol/L are configured to the rare earth nitrades that total rare earth (TRE) ion concentration is 0.3mol/L with stirring
Aqueous solution.The aqueous surfactant solution of 0.3mol/L and ammonium fluoride are added in rare earth nitrate aqueous solution respectively successively again,
To it, the reaction was complete for stirring, obtains precursor solution；Wherein, total rare earth (TRE) ion, the surfactant in precursor solution are water-soluble
The molar ratio of surfactant and ammonium fluoride in liquid is 1：1.3：3.5, surfactant is neopelex.
Step 2, precursor solution is first placed in air-tight state, reacts 16h at 180 DEG C, obtain reaction solution.Again to cooling
Reaction solution carry out separation of solid and liquid, washing and the processing of drying successively；Wherein, solid-liquid separation treatment is centrifuges, its turn
Speed is 10000r/min, time 10min, and carrying out washing treatment is that isolated solid is carried out using deionized water and ethanol
The alternating cleaning of 3 times, solid is separated during cleaning to centrifuge, and the solid after cleaning is is placed at 80 DEG C by drying process
Drying.It is made as shown in figure 3, and the organic-inorganic hybrid nanometer of the praseodymium doped lanthanum fluoride shown in curve as in Figure 1 and Figure 2
Powder.
Embodiment 4
What is prepared concretely comprises the following steps：
Step 1, first according to La0.95Pr0.05F3Lanthana and praseodymium oxide of the component than weighing respective amount after, by lanthana,
The aqueous solution of nitric acid of praseodymium oxide and 13mol/L are configured to the rare earth nitrades that total rare earth (TRE) ion concentration is 0.4mol/L with stirring
Aqueous solution.The aqueous surfactant solution of 0.2mol/L and ammonium fluoride are added in rare earth nitrate aqueous solution respectively successively again,
To it, the reaction was complete for stirring, obtains precursor solution；Wherein, total rare earth (TRE) ion, the surfactant in precursor solution are water-soluble
The molar ratio of surfactant and ammonium fluoride in liquid is 1：1.6：3.3, surfactant is neopelex.
Step 2, precursor solution is first placed in air-tight state, reacts 12h at 200 DEG C, obtain reaction solution.Again to cooling
Reaction solution carry out separation of solid and liquid, washing and the processing of drying successively；Wherein, solid-liquid separation treatment is centrifuges, its turn
Speed is 11000r/min, time 8min, and carrying out washing treatment is to carry out 3 to isolated solid using deionized water and ethanol
Secondary alternating cleaning, when cleaning, separate solid to centrifuge, and the solid after cleaning is is placed at 90 DEG C by drying process
Drying.It is made and is similar to shown in Fig. 3, and the organic inorganic hybridization of the praseodymium doped lanthanum fluoride shown in curve as in Figure 1 and Figure 2
Nano-powder.
Embodiment 5
What is prepared concretely comprises the following steps：
Step 1, first according to La0.9Pr0.1F3Lanthana and praseodymium oxide of the component than weighing respective amount after, by lanthana,
The aqueous solution of nitric acid of praseodymium oxide and 15mol/L are configured to the rare earth nitrades that total rare earth (TRE) ion concentration is 0.5mol/L with stirring
Aqueous solution.The aqueous surfactant solution of 0.1mol/L and ammonium fluoride are added in rare earth nitrate aqueous solution respectively successively again,
To it, the reaction was complete for stirring, obtains precursor solution；Wherein, total rare earth (TRE) ion, the surfactant in precursor solution are water-soluble
The molar ratio of surfactant and ammonium fluoride in liquid is 1：2：3, surfactant is neopelex.
Step 2, precursor solution is first placed in air-tight state, reacts 8h at 220 DEG C, obtain reaction solution.Again to cooling
Reaction solution carry out separation of solid and liquid, washing and the processing of drying successively；Wherein, solid-liquid separation treatment is centrifuges, its turn
Speed is 12000r/min, time 5min, and carrying out washing treatment is to carry out 3 to isolated solid using deionized water and ethanol
Secondary alternating cleaning, when cleaning, separate solid to centrifuge, and the solid after cleaning is is placed at 100 DEG C by drying process
Drying.It is made and is similar to shown in Fig. 3, and the organic inorganic hybridization of the praseodymium doped lanthanum fluoride shown in curve as in Figure 1 and Figure 2
Nano-powder.
Select the polyvinylpyrrolidone or sodium citrate or cetyl trimethyl bromine as surfactant respectively again
Change ammonium or lauryl sodium sulfate, repeat above-described embodiment 1~5, be equally made as or be similar to shown in Fig. 3, and as or
It is similar to the organic-inorganic hybrid nanometer powder of the praseodymium doped lanthanum fluoride shown in the curve in Fig. 1 and Fig. 2.
The purposes of the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride is,
Using the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride as fluorescent powder, for being carried out using ultraviolet light to it
Excite and send white light, obtain result as shown in Figure 4；Wherein, the wavelength of ultraviolet light is 320~410nm.
Obviously, those skilled in the art can be to the organic-inorganic hybrid nanometer powder of the praseodymium doped lanthanum fluoride of the present invention
And its preparation method and application carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, to this
These modifications and variations of invention belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to wrap
Including these modification and variations.
Claims (10)
1. a kind of organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride, including with LaF3The lanthanum fluoride base of chemical formula composition,
It is characterized in that：
Chemical formula composition after the lanthanum fluoride is base and doped is La1-xPrxF3, 10 in chemical formula-3≤x≤10-1, and La1- xPrxF3In fluorine be connected with the carbon in surfactant with C-F chemical bonds and form organic-inorganic hybrid material；
The organic-inorganic hybrid material is powder, and the powder is graininess, and the particle diameter of the particle is 20~70nm.
2. the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride according to claim 1, it is characterized in that particle is ball
Shape, or elliposoidal.
3. a kind of organic-inorganic hybrid nanometer raw powder's production technology of praseodymium doped lanthanum fluoride described in claim 1, including hydro-thermal
Synthetic method, it is characterised in that key step is as follows：
Step 1, first according to La1-xPrxF3Lanthana and praseodymium oxide of the component than weighing respective amount after, by lanthana, praseodymium oxide
The rare earth nitric acid that total rare earth (TRE) ion concentration is 0.1~0.5mol/L is configured to stirring with the aqueous solution of nitric acid of 6~15mol/L
Saline solution, then the aqueous surfactant solution of 0.1~0.5mol/L and ammonium fluoride are added into rare earth nitrades water respectively successively
In solution, stir that the reaction was complete to it, obtain precursor solution, wherein, the total rare earth (TRE) ion in precursor solution, surface-active
The molar ratio of surfactant and ammonium fluoride in agent aqueous solution is 1：0.5~2：3~4；
Step 2, precursor solution is first placed in air-tight state, at least 8h is reacted at 140~220 DEG C, obtain reaction solution, then it is right
The reaction solution cooled carries out separation of solid and liquid, washing and the processing of drying successively, and the organic-inorganic that praseodymium doped lanthanum fluoride is made is miscellaneous
Change nano-powder.
4. the organic-inorganic hybrid nanometer raw powder's production technology of praseodymium doped lanthanum fluoride according to claim 3, its feature
It is that surfactant is neopelex, or polyvinylpyrrolidone, or sodium citrate, or cetyl trimethyl bromine
Change ammonium, or lauryl sodium sulfate.
5. the organic-inorganic hybrid nanometer raw powder's production technology of praseodymium doped lanthanum fluoride according to claim 3, its feature
The reaction time for being placed in the precursor solution of air-tight state is 8~24h.
6. the organic-inorganic hybrid nanometer raw powder's production technology of praseodymium doped lanthanum fluoride according to claim 3, its feature
It is that solid-liquid separation treatment is to centrifuge, its rotating speed is 8000~12000r/min, the time is 5~15min.
7. the organic-inorganic hybrid nanometer raw powder's production technology of praseodymium doped lanthanum fluoride according to claim 3, its feature
It is that carrying out washing treatment is cleaned to be carried out the alternating of 2~3 times to isolated solid using deionized water and ethanol, cleans the time-division
It is centrifugation from solid.
8. the organic-inorganic hybrid nanometer raw powder's production technology of praseodymium doped lanthanum fluoride according to claim 3, its feature
It is that drying process is dried for the solid after cleaning is placed at 60~100 DEG C.
A kind of 9. purposes of the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride described in claim 1, it is characterised in that：
Using the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride as fluorescent powder, for being excited using ultraviolet light to it
And send white light.
10. the purposes of the organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride according to claim 9, it is characterized in that purple
The wavelength of outer light is 320~410nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610420314.6A CN106085432B (en) | 2016-06-07 | 2016-06-07 | Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610420314.6A CN106085432B (en) | 2016-06-07 | 2016-06-07 | Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106085432A CN106085432A (en) | 2016-11-09 |
| CN106085432B true CN106085432B (en) | 2018-04-20 |
Family
ID=57846220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610420314.6A Active CN106085432B (en) | 2016-06-07 | 2016-06-07 | Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106085432B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192616B (en) * | 2018-01-25 | 2021-02-12 | 重庆文理学院 | LaF3:Ce3+,Tb3+Nanoparticle phosphor and method for preparing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241968A (en) * | 2011-06-28 | 2011-11-16 | 吉林大学 | Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase |
| CN102676171A (en) * | 2011-03-14 | 2012-09-19 | 中国科学院福建物质结构研究所 | Method for synthesizing amino functionalized rare earth-doped lanthanum fluoride nano fluorescent marker material |
| CN103275722A (en) * | 2013-06-20 | 2013-09-04 | 南京大学 | Magneto-optical bimodal imaging probe rare earth nanoparticle, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130320263A1 (en) * | 2012-05-29 | 2013-12-05 | Rutgers, The State University Of New Jersey | Surfactant effects on efficiency enhancement of luminescent particles |
-
2016
- 2016-06-07 CN CN201610420314.6A patent/CN106085432B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676171A (en) * | 2011-03-14 | 2012-09-19 | 中国科学院福建物质结构研究所 | Method for synthesizing amino functionalized rare earth-doped lanthanum fluoride nano fluorescent marker material |
| CN102241968A (en) * | 2011-06-28 | 2011-11-16 | 吉林大学 | Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase |
| CN103275722A (en) * | 2013-06-20 | 2013-09-04 | 南京大学 | Magneto-optical bimodal imaging probe rare earth nanoparticle, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Self-assembly of LaF3:Yb,Er/Tm nanoplates into colloidal spheres and tailoring their upconversion emissions with fluorescent dyes;Longyi Bao等;《J. Mater. Chem. C》;20140905;8949-8955 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106085432A (en) | 2016-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lv et al. | The formation mechanism, improved photoluminescence and LED applications of red phosphor K 2 SiF 6: Mn 4+ | |
| Zhang et al. | Fluorescent nanomaterial-derived white light-emitting diodes: what's going on | |
| Guo et al. | A red-emitting perovskite-type SrLa (1− x) MgTaO6: xEu3+ for white LED application | |
| CN102851026B (en) | Red light material for bi-primary-color white light LEDs (light-emitting diodes) and preparation method thereof | |
| JP5005759B2 (en) | Fluorescent powder, method for producing the same, and light-emitting device using the same | |
| Li et al. | Carbon dots/ZnO quantum dots composite-based white phosphors for white light-emitting diodes | |
| CN105152147A (en) | Method for preparation of water-soluble luminous graphite-phase carbon nitride nano kelp | |
| CN103627392B (en) | A kind of stibnate base red fluorescent powder and its preparation method and application | |
| Wu et al. | Synthesis and photoluminescence of Dy-doped ZnO nanowires | |
| CN108003872B (en) | Fluoride red fluorescent powder for blue light excited white light LED and preparation and modification method thereof | |
| Zhou et al. | A promising red phosphor MgMoO4: Eu3+ for white light emitting diodes | |
| Wang et al. | A single-phase heteroatom doped carbon dot phosphor toward white light-emitting diodes | |
| CN107502338B (en) | OLED or flexible transparent display device using blue light emitting layer | |
| CN102517017A (en) | Phosphor and its preparation method and white LED plane light source containing phosphor | |
| CN109266325B (en) | Preparation method of blue light emitting perovskite quantum dot based on surface modifier | |
| Sun et al. | Thermal stable Eu-doped CaTiO3 phosphors with morphology-control for high-power tricolor white LEDs | |
| CN106753359A (en) | A kind of blue light excites Mn4+The oxyfluoride red fluorescence powder and preparation method of doping | |
| CN106085432B (en) | Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application | |
| Chen et al. | Enhanced high-order upconversion luminescence of hexagonal phase NaYF4: Yb3+, Tm3+ crystals coated with homogeneous shell | |
| Guan et al. | The luminescence properties and energy transfer from Ce 3+ to Pr 3+ for YAG: Ce 3+ Pr 3+ phosphors | |
| Zhang et al. | Enhanced white light emission from GdAl3 (BO3) 4: Dy3+, Ce3+ nanorods | |
| Chen et al. | Continuous production of K2SiF6: Mn4+ red phosphor by green route synthesis method for warm WLEDs application | |
| Yang et al. | A novel color-tunable phosphor, Na 5 Gd 9 F 32: Ln 3+(Ln= Eu, Tb, Dy, Sm, Ho) sub-microcrystals: structure, luminescence and energy transfer properties | |
| Xiaojun et al. | Hydrothermal synthesis and photoluminescent properties of Li2Sr0. 996SiO4: Pr3+ 0.004 phosphors for white-LED lightings | |
| CN109722092B (en) | Super-sensitization light-emitting of red fluorescent powder for blue light excited LED and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |