CN110079316A - A kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application - Google Patents
A kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 51
- TTXOCPWHRPZIJA-UHFFFAOYSA-N [F].[Nb] Chemical compound [F].[Nb] TTXOCPWHRPZIJA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- 239000010955 niobium Substances 0.000 claims abstract description 35
- 239000011575 calcium Substances 0.000 claims abstract description 33
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 33
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- -1 niobium ion Chemical class 0.000 claims description 16
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 229910001460 tantalum ion Inorganic materials 0.000 claims description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 239000012769 display material Substances 0.000 claims description 2
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- 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 2
- 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 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract 1
- 238000001778 solid-state sintering Methods 0.000 abstract 1
- 239000004570 mortar (masonry) Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 230000003760 hair shine Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 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
- C09K11/7732—Halogenides
- C09K11/7733—Halogenides with alkali or alkaline earth metals
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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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Abstract
The invention discloses a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application, the chemical formula of the fluorescent powder are Ca3‑2xEu2xNb2Ta2‑2xTi2xO12F2, x is Eu3+Ion and Ti4+Ion replaces Ca respectively2+Ion and Ta5+The molal quantity of ion, 0.003≤x≤0.15 are the presoma Ca that not calcium fluoride containing is prepared using solid-phase synthesis first2‑2xEu2xNb2Ta2‑2xTi2xO12(0.003≤x≤0.15)；Then calcirm-fluoride and ammonium fluoride are added in presoma, is sufficiently mixed, briquet, reuses synthesis in solid state sintering and is made.Fluorescent powder provided by the invention can absorb black light well, and issue the very pure feux rouges of coloration, which can be well matched with near ultraviolet semi-conductor LED chips, be a kind of red luminescent powder for potentially preparing White-light LED illumination device.
Description
Technical field
The present invention relates to inorganic fluorescent material fields, and in particular to a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping and its
Synthesis and application.
Background technique
It shines and generally refers to excitation of the object by energy, Electron absorption energy then exists from ground state transition to excitation state
It back to dischargeing energy during ground state, and radiates in the form of light, realizes shining for material.Such as rare earth phosphor is just
It is most important luminescent material, rare-earth luminescent material is compared with corresponding non-rare-earth luminescent material, luminous efficiency and photochromic etc.
Performance is all even better.Therefore the purposes of rare-earth luminescent material is more and more extensive in recent years, and annual consumption increases rapidly.
Among rare earth phosphor, rare earth ion is most important luminescent activator, and rare earth ion has electricity very rich
Sub- energy level, the 4f track of internal layer realize splitting in crystalline field, create condition for the energy level transition of a variety of electronics, to obtain
Obtain a variety of luminescent spectrums.Red, blue, green three-colour light-emitting material based on rare earth ion plays important in illumination and display
Effect.
In recent years, with the innovation of semiconductor and development, the LED illumination based on semiconductor has obtained great attention, blue
Illumination based on light and black light semiconductor chip forms the White-light LED illumination device of current mainstream commercialization, with biography
Fluorescent lamp, energy-saving illumination and the other light sources of system are compared, and fast-developing a new generation's illumination based on LED chip has very big
Advantage.Red emission during current semi-conductor LED illuminating is luminous is insufficient, and colour temperature (> 4500K) and colour rendering index (< 80) are poor,
These disadvantages greatly limit its some application in general illumination.Therefore in fluorescent powder using it is red shine it is glimmering
Light powder is necessary.
In the red luminescent phosphor of business developed at present, trivalent europium Eu3+The red luminescent phosphor of ion excitation is most heavy
The one kind wanted, mainly Y2O3:Eu3+、Y2O2S:Eu3+, but these fluorescent powders are in the launching efficiency of black light wavelength region
It is low.Meanwhile Eu3+The absorption of itself has to the structure of doped substrate and its important dependence, it is therefore desirable to new matrix is researched and developed,
Realize trivalent europium Eu3+Ion effectively shines.
Summary of the invention
An object of the present invention is to provide a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping, in black light and blue light
Section has good launching efficiency.
The second object of the present invention is to provide above-mentioned Eu3+The synthetic method of the fluorine niobium tantalates fluorescent powder of doping.
The third object of the present invention is to provide above-mentioned Eu3+The application of the fluorine niobium tantalates fluorescent powder of doping.
To achieve the above object, The technical solution adopted by the invention is as follows: a kind of Eu3+The fluorine niobium tantalates fluorescence of doping
Powder, chemical formula Ca3-2xEu2xNb2Ta2-2xTi2xO12F2, x is Eu3+Ion and Ti4+Ion replaces Ca respectively2+Ion and Ta5+
The molal quantity of ion, x value range are 0.003≤x≤0.15.
The matrix of the fluorescent powder is Ca3Nb2Ta2O12F2, Eu3+Ion and Ti4+Ion is Doped ions.
The present invention also provides above-mentioned Eu3+The synthetic method of the fluorine niobium tantalates fluorescent powder of doping, using solid-phase synthesis, tool
Body step is:
(1) according to chemical formula Ca2-2xEu2xNb2Ta2-2xTi2xO12, the stoichiometric ratio of each element in 0.003≤x≤0.15
Weigh compound, the compound containing europium ion, the compound containing niobium ion, the compound containing tantalum ion, titaniferous of calcium ions
The compound of ion, according still further to chemical formula Ca2-2xEu2xNb2Ta2-2xTi2xO12·CaF2, CaF in 0.003≤x≤0.152Change
It learns metering ratio and weighs CaF2, finally weigh and CaF2Equimolar NH4F；
(2) raw material for claiming step (1): the compounds of calcium ions, the compound containing europium ion, containing the change of niobium ion
Object, the compound containing tantalum ion, the compound containing titanium ion are closed, ground and mixed is subsequently placed in precalcining in air atmosphere, calcines
Temperature is 850~1200 DEG C, and calcination time is 1~10 hour；
(3) the precalcining raw material for obtaining step (2) is regrind, and obtained mixture is pressed into bulk, is placed in air
Secondary clacining in atmosphere, calcination temperature are 1200~1400 DEG C, and calcination time is 1~10 hour；
(4) the product natural cooling for obtaining step (3), is ground into powder, and the powder and step (1) is weighed
CaF2And NH4The thorough ground and mixed of F, obtained mixture are pressed into bulk, calcine in air atmosphere, calcination temperature be 850~
1000 DEG C, calcination time is 1~10 hour, naturally cools to room temperature, is ground to get a kind of Eu is arrived3+The fluorine niobium tantalates of doping
Fluorescent powder.
Preferably, the compound of the calcium ions is calcium carbonate CaCO3, calcium nitrate Ca (NO3)2One of；It is described
The compound containing europium ion be europium oxide Eu2O3；The compound containing niobium ion is niobium pentaoxide Nb2O5；Described
Compound containing titanium ion is titanium dioxide TiO2；The compound containing tantalum ion is tantalum oxide Ta2O5。
The present invention also provides above-mentioned Eu3+The luminous application of the fluorine niobium tantalates fluorescent powder of doping.
The fluorescent powder can in ultraviolet between 200~500 nanometers to blue region by effective laser, issue central wavelength
613 nanometers of feux rouges is suitble to preparation using black light, blue-light semiconductor chip as the LED illumination of excitation light source or display device,
It also is used as in the manufacture of light emitting diode, display material, three-color fluorescent lamp and Field Emission Display.
Compared with prior art, the invention has the following beneficial effects:
1, Eu of the invention3+The fluorine niobium tantalates fluorescent powder of doping, there are many ion polyhedrons to form in parent lattice
(Nb, Ta, Ti) has the bonding of F ion in anion again, therefore has very high lattice intensity, and therefore, fluorescent powder has excellent
Elegant thermal stability, is suitable for preparing high-power lighting apparatus.
2, cation Ca2+It is filled in the very high skeleton of rigid, Eu3+The doping of ion can make the centre of luminescence
It is adequately disturbed, Eu3+The forbidden transition of ion is thoroughly broken, and realizes that it is effective red luminous.
3, it is experimentally confirmed that Ti4+The co-doped of ion not only plays because of Eu3+Doping caused by charge balance, also increase
The strong cleanliness of fluorescent powder and red luminous intensity.
4 compare with the existing common red luminescent phosphor of commercialization, such as Y2O3:Eu3+, Y2O2S:Eu3+, provided by the invention
Fluorescent powder has a very strong launching efficiency in black light wavelength region, more preferably in preparing the cooperation of near ultraviolet LED diode chip for backlight unit
The White-light LED illumination equipment of preparation.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure that the embodiment of the present invention 1 prepares fluorescent powder.
Fig. 2 is the SEM figure that the embodiment of the present invention 1 prepares fluorescent powder.
Fig. 3 is the photoluminescence spectra that the embodiment of the present invention 1 prepares fluorescent powder.
Fig. 4 is that the embodiment of the present invention 1 prepares the red luminous decay of luminescence curve of fluorescent powder 613.
Fig. 5 is that the embodiment of the present invention 4 prepares the red luminous decay of luminescence curve of fluorescent powder 613.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1:Ca2.8Eu0.2Nb2Ta1.8Ti0.2O12F2
According to chemical formula Ca1.8Eu0.2Nb2Ta1.8Ti0.2O12The stoichiometric ratio of middle each element weighs: CaCO3: 3.6 grams；
Eu2O3: 0.704 gram；Nb2O5: 5.316 grams；Ta2O5: 7.956 grams；TiO2: 0.32 gram；The raw material claimed is put into agate mortar,
Carefully grinding obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 850 DEG C, calcination time 10
Hour；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in air atmosphere
Middle secondary clacining, calcination temperature are 1400 DEG C, and calcination time is 1 hour, natural cooling, and being put into agate mortar grinding becomes powder
Shape obtains precalcining mixture.
According to Ca1.8Eu0.2Nb2Ta1.8Ti0.2O12·CaF2Middle CaF2Molar ratio weigh CaF2: 1.56 grams and and
NH4F:0.74 grams；Precalcining mixture and weighed CaF2And NH4F grinding, obtains mixture and is pressed into bulk, in air
It is calcined in atmosphere, calcination temperature is 1000 DEG C, and calcination time is 1 hour.The bulk sample grinding for naturally cooling to room temperature, i.e.,
Obtain a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping.
It is the X-ray powder diffraction figure that embodiment 1 prepares fluorescent powder referring to attached drawing 1, the results showed that the material of preparation is single
One object phase Ca3Nb2Ta2O12F2, exist without other impurities, such as not extra fluoride；
It is the SEM figure that fluorescent powder is prepared by embodiment 1 referring to attached drawing 2, crystallinity is very good；
Referring to attached drawing 3, it is the photoluminescence spectra that fluorescent powder is prepared by embodiment 1, and excitation spectrum shows red luminous
It excites source mainly ultraviolet to blue region between 200~500 nanometers, near ultraviolet LED chip emission can be well matched with；
It is that coloration is very pure, center emission wavelength is that 613 nanometers red shines that luminescent spectrum, which shows that this shines,.
Referring to attached drawing 4, it is that the red luminous decay of luminescence curve of fluorescent powder 613 is prepared by embodiment 1, and luminescent lifetime is
1.16 milliseconds, it can satisfy the needs of luminous lighting and display without there is twilight sunset.
Embodiment 2:Ca2.994Eu0.006Nb2Ta1.994Ti0.006O12F2
According to chemical formula Ca1.994Eu0.006Nb2Ta1.994Ti0.006O12The stoichiometric ratio of middle each element weighs: Ca
(NO3)2: 19.62 grams；Eu2O3: 0.0634 gram；Nb2O5: 15.948 grams；Ta2O5: 26.44 grams；TiO2: 0.029 gram；By what is claimed
Raw material is put into agate mortar, carefully grinds, obtains mixture precalcining in air atmosphere of these raw materials, calcination temperature is
1200 DEG C, calcination time is 1 hour；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture pressure
Bulk is made, the secondary clacining in air atmosphere, calcination temperature is 1200 DEG C, and calcination time is 10 hours, and natural cooling is put into
Agate mortar grinding becomes powdered, obtains precalcining mixture.
According to Ca1.994Eu0.006Nb2Ta1.994Ti0.006O12·CaF2Middle CaF2Molar ratio weigh CaF2: 4.68 grams and
NH4F:2.22 grams；Precalcining mixture and weighed CaF2And NH4F ground and mixed, obtained mixture are pressed into bulk,
It is calcined in air atmosphere, calcination temperature is 850 DEG C, and calcination time is 10 hours.The bulk sample for naturally cooling to room temperature
It grinds to get a kind of Eu is arrived3+The fluorine niobium tantalates fluorescent powder of doping.
Its main structural behaviour, excitation spectrum, luminescent spectrum and luminescent lifetime are similar to Example 1.
Embodiment 3:Ca2.7Eu0.3Nb2Ta1.7Ti0.3O12F2
According to chemical formula Ca1.7Eu0.3Nb2Ta1.7Ti0.3O12The stoichiometric ratio of middle each element weighs: CaCO3: 5.95 grams；
Eu2O3: 1.848 grams；Nb2O5: 9.303 grams；Ta2O5: 13.15 grams；TiO2: 0.84 gram；The raw material claimed is put into agate mortar,
Carefully grinding obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 900 DEG C, and calcination time is 3 small
When；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in air atmosphere
Secondary clacining, calcination temperature are 1300 DEG C, and calcination time is 4 hours, and the product natural cooling that above step is obtained obtains pre-
Calcined material.
According to Ca1.7Eu0.3Nb2Ta1.7Ti0.3O12·CaF2Middle CaF2Molar ratio weigh CaF2: 2.73 grams and NH4F:
1.295 gram；Precalcining mixture and weighed CaF2And NH4F ground and mixed, obtained mixture is pressed into bulk, in sky
It is calcined in gas atmosphere, calcination temperature is 900 DEG C, and calcination time is 5 hours.The bulk sample for naturally cooling to room temperature is ground,
Obtain a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping.
Its main structural behaviour, excitation spectrum, luminescent spectrum and its luminescent lifetime are similar to Example 1.
Embodiment 4:Ca2.9Eu0.1Nb2Ta1.9Ti0.1O12F2
According to chemical formula Ca1.9Eu0.1Nb2Ta1.9Ti0.1O12The stoichiometric ratio of middle each element weighs: CaCO3: 2.85 grams；
Eu2O3: 0.264 gram；Nb2O5: 3.987 grams；Ta2O5: 6.299 grams；TiO2: 0.12 gram；The raw material claimed is put into agate mortar,
Carefully grinding obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 880 DEG C, and calcination time is 5 small
When；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in air atmosphere
Secondary clacining, calcination temperature are 1250 DEG C, and calcination time is 6 hours, natural cooling, and being put into agate mortar grinding becomes powder
Shape obtains precalcining mixture.
According to Ca1.9Eu0.1Nb2Ta1.9Ti0.1O12·CaF2Middle CaF2Molar ratio weigh CaF2: 1.17 grams and NH4F:
0.555 gram；Precalcining mixture and weighed CaF2And NH4F ground and mixed, obtained mixture is pressed into bulk, in sky
It is calcined in gas atmosphere, calcination temperature is 950 DEG C, and calcination time is 3 hours.The bulk sample for naturally cooling to room temperature is ground,
Obtain a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping.
Its main structural behaviour, excitation spectrum, luminescent spectrum are similar to Example 1.Referring to attached drawing 5, it is by implementation
4 technical solution of example prepares the red luminous decay of luminescence curve of fluorescent powder 613, and luminescent lifetime is 1.03 milliseconds, can satisfy luminous
The needs of illumination and display are without there is twilight sunset.
Embodiment 5:Ca2.76Eu0.24Nb2Ta1.76Ti0.24O12F2
According to chemical formula Ca1.76Eu0.24Nb2Ta1.76Ti0.24O12The stoichiometric ratio of middle each element weighs: CaCO3: 3.872
Gram；Eu2O3: 0.929 gram；Nb2O5: 5.847 grams；Ta2O5: 8.557 grams；TiO2: 0.4224 gram；The raw material claimed is put into agate
Mortar is carefully ground, and obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 950 DEG C, calcination time
It is 2 hours；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in air
Secondary clacining in atmosphere, calcination temperature are 1350 DEG C, and calcination time is 5 hours, the product natural cooling that above step is obtained,
Obtain precalcining object.
According to Ca1.76Eu0.24Nb2Ta1.76Ti0.24O12·CaF2Middle CaF2Molar ratio weigh CaF2: 1.716 grams and NH4F:
0.814 gram；Precalcining mixture and weighed CaF2And NH4F ground and mixed, obtained mixture is pressed into bulk, in sky
It is calcined in gas atmosphere, calcination temperature is 890 DEG C, and calcination time is 7 hours.The bulk sample for naturally cooling to room temperature is ground,
Obtain a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping.
Its main structural behaviour, excitation spectrum, luminescent spectrum and its luminescent lifetime are similar to Example 4.
Embodiment 6:Ca2.84Eu0.16Nb2Ta1.84Ti0.16O12F2
According to chemical formula Ca1.84Eu0.16Nb2Ta1.84Ti0.16O12The stoichiometric ratio of middle each element weighs: CaCO3: 5.52
Gram；Eu2O3: 0.8448 gram；Nb2O5: 7.974 grams；Ta2O5: 12.199 grams；TiO2: 0.384 gram；The raw material claimed is put into Ma
Nao mortar carefully grinds, obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 900 DEG C, when calcining
Between be 3 hours；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in sky
Secondary clacining in gas atmosphere, calcination temperature are 1330 DEG C, and calcination time is 6 hours, and the product that above step is obtained is naturally cold
But, precalcining object is obtained.
According to Ca1.84Eu0.16Nb2Ta1.84Ti0.16O12·CaF2Middle CaF2Molar ratio weigh CaF2: 2.34 grams and NH4F:
1.11 gram；Precalcining mixture and weighed CaF2And NH4F ground and mixed, obtained mixture is pressed into bulk, in sky
It is calcined in gas atmosphere, calcination temperature is 900 DEG C, and calcination time is 6 hours.The bulk sample for naturally cooling to room temperature is ground,
Obtain a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping.
Its main structural behaviour, excitation spectrum, luminescent spectrum and its luminescent lifetime are similar to Example 4.
Claims (5)
1. a kind of Eu3+The fluorine niobium tantalates fluorescent powder of doping, which is characterized in that its chemical formula is Ca3-2xEu2xNb2Ta2- 2xTi2xO12F2, x is Eu3+Ion and Ti4+Ion replaces Ca respectively2+Ion and Ta5+The molal quantity of ion, x value range are
0.003≤x≤0.15。
2. a kind of Eu described in claim 13+The synthetic method of the fluorine niobium tantalates fluorescent powder of doping, which is characterized in that use
Solid-phase synthesis comprises the concrete steps that:
(1) according to chemical formula Ca2-2xEu2xNb2Ta2-2xTi2xO12, the stoichiometric ratio of each element weighs in 0.003≤x≤0.15
The compound of calcium ions, the compound containing niobium ion, the compound containing tantalum ion, contains titanium ion at the compound containing europium ion
Compound, according still further to chemical formula Ca2-2xEu2xNb2Ta2-2xTi2xO12·CaF2, CaF in 0.003≤x≤0.152Chemistry meter
Amount ratio weighs CaF2, finally weigh and CaF2Equimolar NH4F；
(2) raw material for claiming step (1): the compounds of calcium ions, the compound containing europium ion, containing the chemical combination of niobium ion
Object, the compound containing tantalum ion, the compound containing titanium ion, ground and mixed are subsequently placed in precalcining in air atmosphere, calcining temperature
Degree is 850~1200 DEG C, and calcination time is 1~10 hour；
(3) the precalcining raw material for obtaining step (2) is regrind, and obtained mixture is pressed into bulk, is placed in air atmosphere
Middle secondary clacining, calcination temperature are 1200~1400 DEG C, and calcination time is 1~10 hour；
(4) the product natural cooling for obtaining step (3), is ground into powder, and the powder and step (1) weighed CaF2
And NH4The thorough ground and mixed of F, obtained mixture are pressed into bulk, calcine in air atmosphere, calcination temperature be 850~
1000 DEG C, calcination time is 1~10 hour, naturally cools to room temperature, is ground to get a kind of Eu is arrived3+The fluorine niobium tantalates of doping
Fluorescent powder.
3. Eu according to claim 23+The synthetic method of the fluorine niobium tantalates fluorescent powder of doping, which is characterized in that described
Calcium ions compound be one of calcium carbonate, calcium nitrate；The compound containing europium ion is europium oxide；It is described
The compound containing niobium ion be niobium pentaoxide；The compound containing titanium ion is titanium dioxide；It is described containing tantalum from
The compound of son is tantalum oxide.
4. Eu described in claim 13+The fluorine niobium tantalates fluorescent powder of doping is in preparation with black light, blue-light semiconductor chip
For the application in the LED illumination or display device of excitation light source.
5. Eu described in claim 13+The fluorine niobium tantalates fluorescent powder of doping is preparing light emitting diode, display material, three bases
Application in color fluorescent lamp and Field Emission Display.
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| CN111138191A (en) * | 2019-12-27 | 2020-05-12 | 江苏师范大学 | Eu (Eu)3+Ion activated tantalate fluorescent ceramic and synthesis method and application thereof |
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|---|---|---|---|---|
| CN1793004A (en) * | 2006-01-05 | 2006-06-28 | 武汉理工大学 | Low temp. sintering niobate microwave dielectric ceramic and preparation process thereof |
| CN101074373A (en) * | 2007-03-22 | 2007-11-21 | 罗维鸿 | Cubic-crystal structured inorganic garnet fluorescent powder for short-wave LED |
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| CN1793004A (en) * | 2006-01-05 | 2006-06-28 | 武汉理工大学 | Low temp. sintering niobate microwave dielectric ceramic and preparation process thereof |
| CN101074373A (en) * | 2007-03-22 | 2007-11-21 | 罗维鸿 | Cubic-crystal structured inorganic garnet fluorescent powder for short-wave LED |
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| CN111138191A (en) * | 2019-12-27 | 2020-05-12 | 江苏师范大学 | Eu (Eu)3+Ion activated tantalate fluorescent ceramic and synthesis method and application thereof |
| CN111138191B (en) * | 2019-12-27 | 2022-03-22 | 江苏师范大学 | Eu (Eu)3+Ion activated tantalate fluorescent ceramic and synthesis method and application thereof |
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