CN105694886A - Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material - Google Patents
Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material Download PDFInfo
- Publication number
- CN105694886A CN105694886A CN201510977993.2A CN201510977993A CN105694886A CN 105694886 A CN105694886 A CN 105694886A CN 201510977993 A CN201510977993 A CN 201510977993A CN 105694886 A CN105694886 A CN 105694886A
- Authority
- CN
- China
- Prior art keywords
- fluorate
- doping
- preparation
- luminescent material
- calcium
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000005284 excitation Effects 0.000 claims abstract description 12
- -1 rare earth ion Chemical class 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 66
- 239000011575 calcium Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910001940 europium oxide Inorganic materials 0.000 claims description 12
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 9
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 238000004020 luminiscence type Methods 0.000 claims description 5
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims description 5
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 4
- TUDPVASEPFIHNB-UHFFFAOYSA-J tetrafluoroniobium Chemical compound F[Nb](F)(F)F TUDPVASEPFIHNB-UHFFFAOYSA-J 0.000 claims description 4
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 3
- 238000003836 solid-state method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910019695 Nb2O6 Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005424 photoluminescence Methods 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000000695 excitation spectrum Methods 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019660 Nb(OH)5 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UKRAWUDNDRUQDW-UHFFFAOYSA-J dicalcium tetrafluoride Chemical compound F[Ca]F.F[Ca]F UKRAWUDNDRUQDW-UHFFFAOYSA-J 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- OWFHVHWXOGAVRB-UHFFFAOYSA-J sodium;gadolinium(3+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Gd+3] OWFHVHWXOGAVRB-UHFFFAOYSA-J 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
-
- 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
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)
Abstract
The invention discloses Eu2+The doped fluoate fluorescent material is prepared by rare earth ion activated fluoate base material with chemical formula of Ca2Nb2O6F，<i>x</i>Is Eu2+The doping amount of (A) is not more than 0.0001<i>x</i>Less than or equal to 0.15. The fluosilicate-based luminescent material disclosed by the invention emits blue light with the wavelength of 400-480 nanometers under the excitation of ultraviolet light, and can be applied to various illumination displays and photoluminescence chromaticity adjustment by taking the ultraviolet light as an excitation source. The invention adopts a high-temperature solid phase method to obtain the fluorescent powder with uniform granularity, good dispersibility, high luminous efficiency and good chemical stability, and the preparation method has lower requirements on production cost and equipment and is easy to carry out industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of luminescent material and application thereof, particularly to a kind of Eu2+The preparation method and application of the fluorate based luminescent material of doping, belong to phosphor technical field。
Background technology
In recent years, white light LEDs is paid close attention to, and becomes new generation of green environmental protection, energy-conservation lighting source。Owing to the synthesis of W-LED fluorescent material is simple, and stable performance, cost is low, and luminescence response is fast, is therefore studied by increasing people, and rare earth ion doped advanced luminescent material also becomes material science and the study hotspot in illumination display field therewith。
Illuminating history from the mankind, white light LEDs is described as the forth generation lighting source most possibly replacing conventional illumination device (such as electric filament lamp, daylight lamp)。Rare-earth trichromatic fluorescent lamp is to adopt three kinds of fluorescent material red, blue, green, illuminated object pure color, undistorted, environmentally safe。But the luminous efficiency of current commercial white light LEDs is generally relatively low, it does not have reach the minimum efficiency required by standard daylight lamp, it is necessary to improve constantly the quantum efficiency of chip。Simultaneously, yellow both domestic and external and green emitting phosphor are very ripe in package application, and the luminous efficiency of blue colour fluorescent powder can not be compared with other powder far away with stability, therefore, the blue colour fluorescent powder that development of new is efficient, Heat stability is good, life-span length, cost are low can be effectively improved the quality that white light LEDs is luminous。
The shortcomings such as the blue colour fluorescent powder that the LED europium ion of research and development excites at present mainly has the compounds such as phosphate base, vanadic acid alkali, boric acid alkali, oxyfluoride base, and due to poor stability, cost is high, and synthesis technique is complicated limit application in the led。The advantages such as fluorate is also the phosphor host of a kind of function admirable, has high stability, and cost is low and preparation technology is simple。Patent CN201410079962.0 reports Eu3+Ion doping gadolinium fluoride/controllable luminous powder, preparation method thereof of gadolinium fluoride sodium crystalline phase；Patent CN201110048219.5 reports a kind of method adopting multicomponent solvent full-boiled process to prepare rare earth doped lanthanum fluoride luminous hollow nano powder, belongs to rare earth ion doped Illuminant nanometer powder body fabricating technology field；Patent CN201010567623.9 reports a kind of fluorine-containing electroluminescent material and preparation method thereof。The novel fluorophosphate base blue colour fluorescent powder Ca of present invention synthesis2-2xEu2xNbO6F has not seen reported, and adopts high temperature solid-state method synthesis, and reaction temperature is low, saves the energy, simple to operate, it is easy to industrialized production, has potential application prospect。
Summary of the invention
Preparation technology is simple, cost of material is low, degree of crystallinity is high, luminous efficiency is high to it is an object of the present invention to provide one, environmentally friendly, launches preparation method and the application thereof of the fluorate fluorescent material of blue light under ultraviolet excitation。
For reaching object above, the technical solution used in the present invention is: a kind of Eu2+The fluorate based luminescent material of doping, it is characterised in that: chemical formula is Ca2-2xEu2xNbO6F, wherein x is Eu2+Doping substitutes Ca2+Mole percent, span is 0.0001≤x≤0.15；This fluorescent material, under the ultraviolet excitation that wavelength is 270 nanometers, launches the wavelength blue-fluorescence in 400-480 nano-area。
A kind of Eu2+The preparation method of the fluorate based luminescent material of doping, it is characterised in that adopt high temperature solid-state method, comprise the following steps:
(1) according to formula Ca2-2xEu2xNbO6In F, the stoichiometric proportion of corresponding element weighs raw material, the compound of calcium ions, the compound containing europium ion and the compound containing niobium ion, grinds and makes mix homogeneously, and wherein, x is Eu2+Replace Ca2+Molar percentage coefficient, 0.0001≤x≤0.15；
(2) being calcined in air atmosphere by mixture, calcining heat is 300～650 DEG C, and calcination time is 2～10 hours, repeats this step 2 times；
(3) by the mixture natural cooling after calcining, grinding and mix homogeneously, calcine under carbon reducing agent atmosphere, calcining heat is 650～900 DEG C, and calcination time is 5～12 hours, obtains a kind of fluorate blue colour fluorescent powder。
The compound of described calcium ions is the one in calcium carbonate, calcium bicarbonate, calcium hydroxide, calcium nitrate, calcium oxide, calcium fluoride。
The described compound containing europium ion is the one in europium oxide, europium nitrate, europium。
The described compound containing niobium ion includes the one in niobium pentaoxide, columbium dioxide, niobium hydroxide, tetrafluoride niobium, Columbium pentafluoride.。
Calcining heat described in step (2) is 350～600 DEG C, and calcination time is 3～8 hours；Calcining heat described in step (3) is 600～850 DEG C, and calcination time is 5～10 hours。
A kind of Eu2+The various illumination displays that the fluorate based luminescent material of doping may apply to so that ultraviolet light is excitaton source regulate with luminescence generated by light colourity。
Compared with prior art, the advantage of technical solution of the present invention is in that:
1, fluorate prepared by the present invention has good chemical stability, is also the fluorescent synthetic materials with high-luminous-efficiency simultaneously, and has higher crystallinity and visible light permeability。The Eu of the present invention2+Activate blue colour fluorescent powder can send under ultraviolet excitation 400～480 nanometers blue light, colourity is pure。
2, novel fluorate base blue colour fluorescent powder preparation technique provided by the invention is simple, cost of material is low, degree of crystallinity is high, environmentally friendly, preparation process synthesis temperature is low, reduces energy resource consumption and cost。
3, the fluorate base blue colour fluorescent powder that prepared by the present invention has good heat stability and color rendering properties, and luminous efficiency is high, is conducive to preparing high-power LED。
Accompanying drawing explanation
Fig. 1 is the Ca prepared by the embodiment of the present invention 1 technical scheme1.9998Eu0.0002NbO6The X-ray powder diffraction pattern of F。
Fig. 2 is the Ca prepared by the embodiment of the present invention 1 technical scheme1.9998Eu0.0002NbO6The SEM figure of F。
Fig. 3 is the Ca prepared by the embodiment of the present invention 1 technical scheme1.9998Eu0.0002NbO6The exciting light spectrogram that F obtains under the light detection of 440 nanometers。
Fig. 4 is the Ca prepared by the embodiment of the present invention 1 technical scheme1.9998Eu0.0002NbO6F luminescent spectrum figure under the light of 310 nanometers excites。
Fig. 5 is the Ca prepared by the embodiment of the present invention 2 technical scheme1.9998Eu0.0002NbO6F is 310 nanometers in excitation wavelength, and monitoring wavelength is the attenuation curve figure of 440 nanometers。
Fig. 6 is the Ca prepared by the embodiment of the present invention 2 technical scheme1.998Eu0.002NbO6The X-ray powder diffraction pattern of F。
Fig. 7 is the Ca prepared by the embodiment of the present invention 2 technical scheme1.998Eu0.002NbO6The SEM figure of F。
Fig. 8 is the Ca prepared by the embodiment of the present invention 2 technical scheme1.998Eu0.002NbO6The exciting light spectrogram that F obtains under the light detection of 430 nanometers。
Fig. 9 is the Ca prepared by the embodiment of the present invention 2 technical scheme1.998Eu0.002NbO6F luminescent spectrum figure under the light of 270 nanometers excites。
Figure 10 is the Ca prepared by the embodiment of the present invention 2 technical scheme1.998Eu0.002NbO6F is 270 nanometers in excitation wavelength, and monitoring wavelength is the attenuation curve figure of 430 nanometers。
Detailed description of the invention
Below in conjunction with drawings and Examples, technical solution of the present invention is further described。
Embodiment 1:
Preparation Ca1.9998Eu0.0002NbO6F
According to chemical formula Ca1.9998Eu0.0002NbO6F, weighs niobium pentaoxide Nb respectively2O5: 1.33 grams, europium oxide Eu2O3: 0.0004 gram。By niobium pentaoxide Nb2O5With europium oxide Eu2O3Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 350 DEG C, calcination time 3 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 600 DEG C, calcination time 8 hours, be then cooled to room temperature, take out sample；Weigh calcium fluoride CaF again2: 1.56 grams, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 850 DEG C, and calcination time is 10 hours, namely obtains powder shaped fluorate blue emitting material。
Referring to accompanying drawing 1, it is the X-ray powder diffraction pattern preparing sample by the embodiment of the present invention 1 technical scheme, and XRD test result shows, prepared material is fluorate Ca1.9998Eu0.0002NbO6F is monophase materials, it does not have other impurity thing any exists mutually。
Referring to accompanying drawing 2, it is the SEM figure of the material sample prepared by the embodiment of the present invention 1 technical scheme, and this material crystalline is functional, and particle diameter is comparatively uniform, and mean diameter is at 20 microns。
Referring to accompanying drawing 3, it is to prepare sample monitoring by the embodiment of the present invention 1 technical scheme to launch 440 nanometers of excitation spectrums obtained of light, it can be seen that exciting of the blue-light-emitting of this material is originated mainly at the ultraviolet region of 250～350 nanometers, it is possible to prepare ultraviolet excitation fluorescent lamp well。
Referring to accompanying drawing 4, it is to prepare sample by the embodiment of the present invention 1 technical scheme to excite the luminescent spectrum figure obtained with ultraviolet light 310 nanometers, the blue-light-emitting wave band that center emission wavelength is 440 nanometers that this material is main, calculate through CIE simultaneously, the coordinate learning it is x=0.171, y=0.026, also just drops on blue region。
Referring to accompanying drawing 5, it be the material sample prepared by this case technology scheme excitation wavelength 310 nanometers, the decay of luminescence curve of monitoring wavelength 440 nanometers, the die-away time that can calculate this blue colour fluorescent powder from figure is 2.853 microseconds。
Embodiment 2:
Preparation Ca1.998Eu0.002NbO6F
According to chemical formula Ca1.998Eu0.002NbO6F, weighs calcium carbonate CaCO respectively3: 2.00 grams, niobium pentaoxide Nb2O5: 1.33 grams。By calcium carbonate CaCO3With niobium pentaoxide Nb2O5Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 380 DEG C, calcination time 4 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 500 DEG C, calcination time 5 hours, be then cooled to room temperature, take out sample；Weigh europium EuF again3: 0.0042 gram, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 600 DEG C, and calcination time is 5 hours, namely obtains powder shaped fluorate blue emitting material。
Referring to accompanying drawing 6, it is the X-ray powder diffraction pattern preparing sample by the embodiment of the present invention 2 technical scheme, and XRD test result shows, prepared material is fluorate Ca1.998Eu0.002NbO6F is monophase materials, it does not have other impurity thing any exists mutually。
Referring to accompanying drawing 7, it is the SEM figure of the material sample prepared by the embodiment of the present invention 2 technical scheme, and this material crystalline is functional, and particle diameter is comparatively uniform, and mean diameter is at 15 microns。
Referring to accompanying drawing 8, it is to prepare sample monitoring by the embodiment of the present invention 2 technical scheme to launch 430 nanometers of excitation spectrums obtained of light, it can be seen that exciting of the blue-light-emitting of this material is originated mainly at the ultraviolet region of 240～300 nanometers, it is possible to prepare ultraviolet excitation fluorescent lamp well。
Referring to accompanying drawing 9, it is to prepare sample by the embodiment of the present invention 2 technical scheme to excite the luminescent spectrum figure obtained with ultraviolet light 270 nanometers, calculates through CIE simultaneously, learns that its coordinate is x=0.154, y=0.036, also just drop on blue region。
Referring to accompanying drawing 10, it be the material sample prepared by this case technology scheme excitation wavelength 270 nanometers, the decay of luminescence curve of monitoring wavelength 430 nanometers, the die-away time that can calculate this blue colour fluorescent powder from figure is 11.35 microseconds。
Embodiment 3:
Preparation Ca1.99Eu0.01NbO6F
According to chemical formula Ca1.99Eu0.01NbO6F, weighs calcium oxide CaO:1.12 gram, europium nitrate Eu (NO respectively3)3·6H2O:0.045 gram。By calcium oxide CaO and europium nitrate Eu (NO3)3·6H2O grinds and after mix homogeneously in agate mortar, selects air atmosphere first time calcining, and temperature is 400 DEG C, calcination time 4 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 450 DEG C, calcination time 6 hours, be then cooled to room temperature, take out sample；Weigh Columbium pentafluoride. NbF again5: 1.88 grams, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 650 DEG C, and calcination time is 6 hours, namely obtains powder shaped fluorate blue emitting material。Its main structural behaviour, excitation spectrum and luminescent spectrum, attenuation curve are similar to embodiment 1。
Embodiment 4:
Preparation Ca1.98Eu0.02NbO6F
According to chemical formula Ca1.98Eu0.02NbO6F, weighs calcium hydroxide Ca(OH respectively)2: 1.47 grams, europium oxide Eu2O3: 0.036 gram。By calcium hydroxide Ca(OH)2With europium oxide Eu2O3Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 450 DEG C, calcination time 5 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 500 DEG C, calcination time 6 hours, be then cooled to room temperature, take out sample；Weigh tetrafluoride niobium NbF again4: 1.69 grams, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 700 DEG C, and calcination time is 7 hours, namely obtains powder shaped fluorate blue emitting material。Its main structural behaviour, excitation spectrum and luminescent spectrum, attenuation curve are similar to embodiment 1。
Embodiment 5:
Preparation Ca1.9Eu0.1NbO6F
According to chemical formula Ca1.9Eu0.1NbO6F, weighs calcium bicarbonate Ca(HCO respectively3)2: 3.07 grams, niobium pentaoxide Nb2O5: 1.33 grams。By calcium bicarbonate Ca(HCO3)2With niobium pentaoxide Nb2O5Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 500 DEG C, calcination time 6 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 550 DEG C, calcination time 7 hours, be then cooled to room temperature, take out sample；Weigh europium EuF again3: 0.21 gram, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 700 DEG C, and calcination time is 7 hours, namely obtains powder shaped fluorate blue emitting material。Its main structural behaviour, excitation spectrum and luminescent spectrum, attenuation curve are similar to embodiment 1。
Embodiment 6:
Preparation Ca1.84Eu0.16NbO6F
According to chemical formula Ca1.84Eu0.16NbO6F, weighs niobium hydroxide Nb(OH respectively)5: 1.78 grams, europium oxide Eu2O3: 0.29 gram。By niobium hydroxide Nb(OH)5With europium oxide Eu2O3Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 550 DEG C, calcination time 6 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 600 DEG C, calcination time 8 hours, be then cooled to room temperature, take out sample；Weigh calcium fluoride CaF again2: 1.44 grams, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 750 DEG C, and calcination time is 8 hours, namely obtains powder shaped fluorate blue emitting material。Its main structural behaviour, excitation spectrum and luminescent spectrum, attenuation curve are similar to embodiment 2。
Embodiment 7:
Preparation Ca1.8Eu0.2NbO6F
According to chemical formula Ca1.8Eu0.2NbO6F, weighs calcium nitrate Ca(NO respectively3)2: 2.96 grams, europium oxide Eu2O3: 0.29 gram。By calcium nitrate Ca(NO3)2With europium oxide Eu2O3Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 350 DEG C, calcination time 6 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 500 DEG C, calcination time 6 hours, be then cooled to room temperature, take out sample；Weigh tetrafluoride niobium NbF again4: 1.69 grams, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 800 DEG C, and calcination time is 8 hours, namely obtains powder shaped fluorate blue emitting material。Its main structural behaviour, excitation spectrum and luminescent spectrum, attenuation curve are similar to embodiment 2。
Embodiment 8:
Preparation Ca1.7Eu0.3NbO6F
According to chemical formula Ca1.7Eu0.3NbO6F, weighs columbium dioxide NbO respectively2: 2.50 grams, europium oxide Eu2O3: 0.53 gram。By columbium dioxide NbO2With europium oxide Eu2O3Grinding in agate mortar and after mix homogeneously, select air atmosphere first time calcining, temperature is 400 DEG C, calcination time 6 hours, is subsequently cooled to room temperature, takes out sample；The raw material of first time calcining is sufficiently mixed grinding uniformly again, again sinters in air atmosphere, temperature 550 DEG C, calcination time 7 hours, be then cooled to room temperature, take out sample；Weigh tetrafluoride calcium CaF again2: 1.33 grams, adding in the mixture obtained, be placed in Muffle furnace, calcine under carbon reducing agent atmosphere after being again fully ground, calcining heat is 850 DEG C, and calcination time is 10 hours, namely obtains powder shaped fluorate blue emitting material。Its main structural behaviour, excitation spectrum and luminescent spectrum, attenuation curve are similar to embodiment 2。
Claims (7)
1. an Eu2+The fluorate based luminescent material of doping, it is characterised in that: chemical formula is Ca2-2xEu2xNbO6F, wherein x is Eu2+Doping substitutes Ca2+Mole percent, span is 0.0001≤x≤0.15；This fluorescent material, under the ultraviolet excitation that wavelength is 270 nanometers, launches the wavelength blue-fluorescence in 400-480 nano-area。
2. an Eu2+The preparation method of the fluorate based luminescent material of doping, it is characterised in that adopt high temperature solid-state method, comprise the following steps:
According to formula Ca2-2xEu2xNbO6In F, the stoichiometric proportion of corresponding element weighs raw material, the compound of calcium ions, the compound containing europium ion and the compound containing niobium ion, grinds and makes mix homogeneously, and wherein, x is Eu2+Replace Ca2+Molar percentage coefficient, 0.0001≤x≤0.15；
Being calcined in air atmosphere by mixture, calcining heat is 300～650 DEG C, and calcination time is 2～10 hours, repeats this step 2 times；
By the mixture natural cooling after calcining, grinding and mix homogeneously, calcine under carbon reducing agent atmosphere, calcining heat is 650～900 DEG C, and calcination time is 5～12 hours, obtains a kind of fluorate blue colour fluorescent powder。
3. a kind of Eu according to claim 22+The fluorate based luminescent material preparation method of doping, it is characterised in that: the compound of described calcium ions is the one in calcium carbonate, calcium bicarbonate, calcium hydroxide, calcium nitrate, calcium oxide, calcium fluoride。
4. a kind of Eu according to claim 22+The preparation method of the fluorate based luminescent material of doping, it is characterised in that: the described compound containing europium ion is the one in europium oxide, europium nitrate, europium。
5. a kind of Eu according to claim 22+The preparation method of the fluorate based luminescent material of doping, it is characterised in that: the described compound containing niobium ion includes the one in niobium pentaoxide, columbium dioxide, niobium hydroxide, tetrafluoride niobium, Columbium pentafluoride.。
6. a kind of Eu according to claim 22+The preparation method of the fluorate based luminescent material of doping, it is characterised in that: the calcining heat described in step (2) is 350～600 DEG C, and calcination time is 3～8 hours；Calcining heat described in step (3) is 600～850 DEG C, and calcination time is 5～10 hours。
7. an Eu2+The application of fluorate based luminescent material of doping, it is characterised in that: be applied to ultraviolet light be excitaton source various illumination displays and luminescence generated by light colourity regulate。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510977993.2A CN105694886B (en) | 2015-12-23 | 2015-12-23 | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510977993.2A CN105694886B (en) | 2015-12-23 | 2015-12-23 | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105694886A true CN105694886A (en) | 2016-06-22 |
| CN105694886B CN105694886B (en) | 2017-12-26 |
Family
ID=56228296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510977993.2A Active CN105694886B (en) | 2015-12-23 | 2015-12-23 | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105694886B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163934A (en) * | 2017-07-28 | 2017-09-15 | 江西理工大学 | Tetravalence manganese ion doping fluorine alumina lithium red fluorescence powder and preparation method thereof |
| CN110129046A (en) * | 2019-05-30 | 2019-08-16 | 江苏师范大学 | A kind of Tb3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application |
| CN110129047A (en) * | 2019-06-19 | 2019-08-16 | 江苏师范大学 | A kind of Tb3+The green luminescent phosphor of niobium tantalates of activation and its preparation and application |
| CN110129048A (en) * | 2019-06-19 | 2019-08-16 | 江苏师范大学 | A kind of Mn2+The niobium tantalates Huang luminescent phosphor of activation and its preparation and application |
| CN110184055A (en) * | 2019-06-19 | 2019-08-30 | 江苏师范大学 | A kind of Eu3+The red luminescent phosphor of niobium tantalates of activation and its preparation and application |
| CN111139073A (en) * | 2019-12-27 | 2020-05-12 | 江苏师范大学 | Eu (Eu)3+Ion activated tantalate fluorescent powder and synthetic method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050179009A1 (en) * | 2003-12-23 | 2005-08-18 | Gyun-Joong Kim | Phosphor and a method of preparing the same |
| CN101962542A (en) * | 2010-09-14 | 2011-02-02 | 南昌大学 | Niobate-based red fluorescent powder for white LED as well as preparation method and application thereof |
| CN103173225A (en) * | 2013-04-03 | 2013-06-26 | 苏州大学 | Blue fluosilicate fluorescent powder as well as preparation method and application |
| CN103289685A (en) * | 2013-06-27 | 2013-09-11 | 苏州大学 | Eu<2+> activated fluosilicate blue fluorescent powder, and preparation method and application thereof |
-
2015
- 2015-12-23 CN CN201510977993.2A patent/CN105694886B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050179009A1 (en) * | 2003-12-23 | 2005-08-18 | Gyun-Joong Kim | Phosphor and a method of preparing the same |
| CN101962542A (en) * | 2010-09-14 | 2011-02-02 | 南昌大学 | Niobate-based red fluorescent powder for white LED as well as preparation method and application thereof |
| CN103173225A (en) * | 2013-04-03 | 2013-06-26 | 苏州大学 | Blue fluosilicate fluorescent powder as well as preparation method and application |
| CN103289685A (en) * | 2013-06-27 | 2013-09-11 | 苏州大学 | Eu<2+> activated fluosilicate blue fluorescent powder, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHIGUO XIA，ET AL.: "Luminescence properties of Ba5SiO4(F,Cl)6:Eu2+ phosphor", 《MATERIALS LETTERS》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163934A (en) * | 2017-07-28 | 2017-09-15 | 江西理工大学 | Tetravalence manganese ion doping fluorine alumina lithium red fluorescence powder and preparation method thereof |
| CN107163934B (en) * | 2017-07-28 | 2020-03-31 | 江西理工大学 | Quadrivalent manganese ion doped fluorine aluminum oxide lithium red fluorescent powder and preparation method thereof |
| CN110129046A (en) * | 2019-05-30 | 2019-08-16 | 江苏师范大学 | A kind of Tb3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application |
| CN110129046B (en) * | 2019-05-30 | 2021-09-17 | 江苏师范大学 | Tb3+Doped fluoroniobium tantalate fluorescent powder and synthesis and application thereof |
| CN110129047A (en) * | 2019-06-19 | 2019-08-16 | 江苏师范大学 | A kind of Tb3+The green luminescent phosphor of niobium tantalates of activation and its preparation and application |
| CN110129048A (en) * | 2019-06-19 | 2019-08-16 | 江苏师范大学 | A kind of Mn2+The niobium tantalates Huang luminescent phosphor of activation and its preparation and application |
| CN110184055A (en) * | 2019-06-19 | 2019-08-30 | 江苏师范大学 | A kind of Eu3+The red luminescent phosphor of niobium tantalates of activation and its preparation and application |
| CN110184055B (en) * | 2019-06-19 | 2022-03-22 | 江苏师范大学 | Eu (Eu)3+Activated niobium tantalate red luminescent phosphor and preparation and application thereof |
| CN110129048B (en) * | 2019-06-19 | 2022-03-22 | 江苏师范大学 | Mn (manganese)2+Activated niobium tantalate yellow luminescent phosphor and preparation and application thereof |
| CN110129047B (en) * | 2019-06-19 | 2022-03-22 | 江苏师范大学 | Tb3+Activated niobium tantalate green luminescent fluorescent powder and preparation and application thereof |
| CN111139073A (en) * | 2019-12-27 | 2020-05-12 | 江苏师范大学 | Eu (Eu)3+Ion activated tantalate fluorescent powder and synthetic method and application thereof |
| CN111139073B (en) * | 2019-12-27 | 2022-07-22 | 江苏师范大学 | Eu (Eu)3+Ion activated tantalate fluorescent powder and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105694886B (en) | 2017-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105694886B (en) | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material | |
| CN103627392B (en) | A kind of stibnate base red fluorescent powder and its preparation method and application | |
| CN103242830B (en) | Fluorosilicate-based blue-green fluorescent powder as well as preparation method and applications of fluorescent powder | |
| CN103173225B (en) | Blue fluosilicate fluorescent powder as well as preparation method and application | |
| CN113403074A (en) | Mn4+ activated antimonate narrow-band red fluorescent powder and preparation method thereof | |
| CN102585831B (en) | Europium-ion-excited fluoromolybdate red fluorescent powder and preparation method and application thereof | |
| CN103305216B (en) | Borate red fluorescent powder and preparation method and application thereof | |
| CN103122244B (en) | Eu<2+> activated silicate white light fluorescent powder and preparation method thereof | |
| CN103275713A (en) | Rare earth molybdate red phosphor, and preparation method and application thereof | |
| CN103289698B (en) | A kind of europium ion Eu 3+the phosphate base red fluorescence powder activated, preparation method and application | |
| CN108034423B (en) | Mn (manganese)2+Ion-doped silicate red fluorescent powder, preparation method and application | |
| CN103320131B (en) | Phosphate based red phosphor, preparation method and application thereof | |
| CN102660262A (en) | Eu<2+> activated chloride calcium silicate fluorescent powder, preparation method and application | |
| CN108893108A (en) | A kind of double-perovskite type silicate blue fluorescent powder and preparation method thereof | |
| CN105419798B (en) | A kind of preparation method and application of orange red antimonate luminescent materials | |
| CN109825296B (en) | Europium ion Eu3+Activated fluorine antimonate orange red fluorescent powder and preparation method thereof | |
| CN103497769B (en) | Red phosphor adaptable to ultraviolet light or blue light excitation and preparation method thereof | |
| CN103627393B (en) | Tungsten molybdate red phosphor powder and preparation method and application thereof | |
| CN106867524B (en) | Preparation and application of alkaline earth aluminate blue fluorescent material | |
| CN104804731A (en) | Eu<2+>-activated magnesium potassium silicate blue-green fluorescent powder as well as preparation method and application thereof | |
| Xianghong et al. | Luminescent properties and application of Eu3+-activated Gd2 (MoO4) 3 red-emitting phosphor with pseudo-pompon shape for solid-state lighting | |
| CN103497761A (en) | Eu<2+>-activated aluminum-barium fluoborate fluorescent powder as well as preparation method and application thereof | |
| CN108913141B (en) | Eu3+Ion-activated fluorescent material, preparation and application thereof | |
| CN113549457B (en) | Europium (III) -doped scheelite type red fluorescent powder, preparation and application | |
| CN103468255B (en) | Chlorine borate luminescent material 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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190816 Address after: 221300 No. 88 Liaohe West Road, Pizhou Economic Development Zone, Xuzhou City, Jiangsu Province Patentee after: SU Normal University Semiconductor Materials and Equipment Research Institute (Pizhou) Co., Ltd. Address before: 221000 Shanghai Road, Copper Mt. District, Jiangsu, No. 101, No. Patentee before: Jiangsu Normal University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220526 Address after: 221300 506, block B, electronic industrial park, Pizhou Economic Development Zone, Xuzhou City, Jiangsu Province Patentee after: Xuzhou Bochuang Construction Development Group Co.,Ltd. Address before: No.88 Liaohe West Road, Pizhou Economic Development Zone, Xuzhou City, Jiangsu Province Patentee before: SU Normal University Semiconductor Materials and Equipment Research Institute (Pizhou) Co.,Ltd. |