CN110129047A - A kind of Tb3+The green luminescent phosphor of niobium tantalates of activation and its preparation and application - Google Patents
A kind of Tb3+The green luminescent phosphor of niobium tantalates of activation and its preparation and application Download PDFInfo
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- CN110129047A CN110129047A CN201910530826.1A CN201910530826A CN110129047A CN 110129047 A CN110129047 A CN 110129047A CN 201910530826 A CN201910530826 A CN 201910530826A CN 110129047 A CN110129047 A CN 110129047A
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- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 30
- 239000010955 niobium Substances 0.000 title claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000004913 activation Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000005286 illumination Methods 0.000 claims abstract description 14
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 13
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 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 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 17
- -1 terbium ion Chemical class 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 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 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012769 display material Substances 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
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001778 solid-state sintering Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004645 aluminates Chemical class 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
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 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
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7747—Halogenides
- C09K11/7748—Halogenides with alkali or alkaline earth metals
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of Tb3+The green luminescent phosphor of niobium tantalates of activation and its preparation and application, the chemical formula of the fluorescent powder are NaCa1‑2xTbxLixTaNbO6F, x are Tb3+Ion and Li+Ion replaces Ca respectively2+Molal quantity, 0.001≤x≤0.2 is to prepare not fluorine-containing presoma Ca using solid-phase synthesis first1‑ 2xTbxLixTaNbO6(0.001≤x≤0.2)；Then sodium 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 green light of coloration, which can be well matched with near ultraviolet semi-conductor LED chips, be a kind of green 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 Tb3+The green luminescent phosphor of niobium tantalates of activation
And its preparation and application.
Background technique
In recent years, with the innovation of semiconductor and development, the LED illumination based on semiconductor has obtained great attention, purple
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, such as long service life, LED illumination can be no-failure operation 50000 hours or more, and the service life is the hundreds of times of incandescent lamp；
Power saving: the power consumption of LED is only the 1/10 of incandescent lamp, wide using voltage range；Brightness is also considerably beyond incandescent lamp, etc..
Current most important illumination is by blue-light semiconductor chip and yellow Y3Al5O12:Ce3+(YAG:Ce3+) fluorescent powder group
Close encapsulation realize, it is this illumination have many advantages, but it is this illumination have the shortcomings that it is inevitable: in illumination light-emitting
Red emission it is insufficient, colour temperature (> 4500K) and colour rendering index (< 80) are poor, and which greatly limits it for these disadvantages
Some applications in general illumination.For this purpose, people's blue-light LED chip to be used excitation green and red fluorescence powder be combined into it is white
Light improves the colour rendering of white light LEDs to make up the missing of feux rouges.Cost is relatively low and not by commercial monopoly for said combination mode,
There is great development potentiality.However the white light that this combination shows may deviate from standard white light, need thus green
The fluorescence property of color or red fluorescence powder.
As a kind of activator rare earth ion of most important green emitting, Tb3+Characteristic emission derive from5D4→7FJ(J
=0,1,2,3,4,5,6) transition, the green luminescent material of activation are to be applied to light-emitting LED first choice.Tb3+Luminescent properties
Host material is also depended on, researcher both domestic and external is constantly searching for being suitble to Tb3+The host material of doping.Currently,
The Tb of report3+The matrix of the green luminescent phosphor of doping has RE phosphate, silicate, aluminate, niobates, vanadate, tungsten
Hydrochlorate etc..But it is had not been reported by the green luminescent phosphor of matrix of niobium tantalates.
Summary of the invention
An object of the present invention is to provide a kind of Tb3+The green luminescent phosphor of niobium tantalates of activation.
The second object of the present invention is to provide above-mentioned Tb3+The preparation method of the green luminescent phosphor of niobium tantalates of activation.
The third object of the present invention is to provide above-mentioned Tb3+The application of the green luminescent phosphor of niobium tantalates of activation.
To achieve the above object, The technical solution adopted by the invention is as follows: a kind of Tb3+The niobium tantalates of activation is green shine it is glimmering
Light powder, chemical formula NaCa1-2xTbxLixTaNbO6F, x are trivalent terbium ion Tb3+With monovalence lithium ion Li+Replace Ca respectively2+
Molal quantity, x value range be 0.001≤x≤0.2.
The matrix of the fluorescent powder is NaCaTaNbO6F, Tb3+Ion is activator.
The present invention also provides above-mentioned Tb3+The preparation method of the green luminescent phosphor of niobium tantalates of activation, using synthesis in solid state
Method comprises the concrete steps that:
(1) according to chemical formula Ca1-2xTbxLixTaNbO6, the stoichiometric ratio of each element, which weighs, in 0.001≤x≤0.2 contains
The compound of calcium ion, the compound containing terbium ion, the compound containing lithium ion, the compound containing tantalum ion, containing niobium ion
Compound；According to chemical formula NaCa1-2xTbxLixTaNbO6F, the stoichiometric ratio of sodium element weighs fluorine in 0.001≤x≤0.2
Change sodium, then weighs the ammonium fluoride with sodium fluoride equimolar amounts；
(2) raw material for claiming step (1): the compounds of calcium ions, the compound containing terbium ion, containing the change of lithium ion
Object, the compound containing niobium ion, the compound containing tantalum 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
Sodium fluoride and the thorough ground and mixed of ammonium fluoride, obtained mixture are pressed into bulk, calcine in air atmosphere, and calcination temperature is
850~1000 DEG C, calcination time is 1~10 hour, naturally cools to room temperature, is ground to get a kind of Tb is arrived3+The niobium tantalic acid of activation
The green luminescent phosphor of salt.
Preferably, the compound of the calcium ions is calcium carbonate CaCO3, calcium nitrate Ca (NO3)2One of；It is described
The compound containing terbium ion be terbium oxide Tb2O3；The compound containing lithium ion is lithium carbonate Li2CO3；Described contains
The compound of niobium ion is niobium pentaoxide Nb2O5；The compound containing tantalum ion is tantalum oxide Ta2O5。
The present invention also provides above-mentioned Tb3+The luminous application of the green luminescent phosphor of niobium tantalates of activation.
The fluorescent powder can in ultraviolet between 200~400 nanometers to blue region by effective laser, issue central wavelength
550 nanometers of green light 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, Tb of the invention3+The green luminescent phosphor of niobium tantalates of activation, there are many ion polyhedrons in parent lattice
It forms (Nb, Ta), has the bonding of F ion in anion again, therefore there is very high lattice intensity, therefore, fluorescent powder has
Outstanding thermal stability is suitable for preparing high-power lighting apparatus.
2, cation Ca2+It is filled in the very high skeleton of rigid, Tb3+The doping of ion can make the centre of luminescence
It is adequately disturbed, Tb3+The forbidden transition of ion is thoroughly broken, and realizes that it is effective green luminous.
3、Li+The co-doped of ion not only plays because of Tb3+Doping caused by charge balance, also enhance fluorescent powder
Cleanliness and green luminous intensity.
4, the excitation spectrum of the green emitting phosphor is in 200nm~400nm, main excitation peak 240nm, and emission spectrum exists
470nm~620nm, main peak have chemical property stabilization, good luminous performance, luminous intensity height and colour rendering good near 550nm
The advantages of；The present invention is using niobium tantalates as the preparation method of the terbium-doped green fluorescent powder of matrix, wherein it is based on solid-phase synthesis, behaviour
The property made is strong, mainly prepares in air atmosphere, and temperature-rise period is simple, and entire method is simple and easy, favorable reproducibility and manufacturing cycle
It is short.
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 that the embodiment of the present invention 1 prepares excitation spectrum of the fluorescent powder under 540 nanometers of monitoring.
Fig. 4 is that the embodiment of the present invention 1 prepares emission spectrum of the fluorescent powder under 240 nanometers of excitations.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1:NaCa0.7Tb0.15Li0.15TaNbO6F
According to chemical formula Ca0.7Tb0.15Li0.15TaNbO6The stoichiometric ratio of middle each element weighs: CaCO3: 3.5 grams；
Tb2O3: 1.37 grams；Ta2O5: 11.051 grams；Li2CO3: 0.277 gram；Nb2O5: 6.645 grams；The raw material claimed is put into agate to grind
Alms bowl is carefully ground, and obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 900 DEG C, and calcination time is
9 hours；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in air gas
Secondary clacining in atmosphere, calcination temperature are 1400 DEG C, and calcination time is 1 hour, natural cooling, and being put into agate mortar grinding becomes powder
Last shape obtains precalcining mixture.
According to NaCa0.7Tb0.15Li0.15TaNbO6The stoichiometric ratio of sodium element weighs NaF:2.1 grams in F, and weigh and
The NH of NaF equimolar amounts4F:1.85 grams；Precalcining mixture and weighed NaF and NH4F grinding obtains mixture compacting
It at bulk, is calcined in air atmosphere, calcination temperature is 1000 DEG C, and calcination time is 1 hour.The bulk sample of natural cooling
It grinds to get a kind of Tb is arrived3+The green luminescent phosphor of niobium tantalates of activation.
It is the X-ray powder diffraction figure that 1 technical solution of embodiment prepares fluorescent powder, the results showed that preparation referring to attached drawing 1
Material is single object phase, is existed without other impurity；
It is the SEM figure that fluorescent powder is prepared by 1 technical solution of embodiment referring to attached drawing 2, crystal property is good；
Referring to attached drawing 3, excitation spectrum of the fluorescent powder under 540 nanometers of monitoring is prepared by 1 technical solution of embodiment.Exciting light
Spectrum indicates that green luminous excitation source is mainly ultraviolet to blue region between 200~400 nanometers, can be well matched with nearly purple
Outer LED chip transmitting；
Referring to attached drawing 4, it is the emission spectrum under 240 nanometers of excitations that fluorescent powder is prepared by 1 technical solution of embodiment.
It is that coloration is very pure, center emission wavelength is that 550 nanometers green shines that luminescent spectrum, which shows that this shines,.
Embodiment 2:NaCa0.998Tb0.001Li0.001TaNbO6F
According to chemical formula Ca0.998Tb0.001Li0.001TaNbO6The stoichiometric ratio of middle each element weighs: Ca (NO3)2:
14.73 grams；Tb2O3: 0.017 gram；Ta2O5: 19.89 grams；Li2CO3: 0.0004 gram；Nb2O5: 11.96 grams；The raw material claimed is put
Entering agate mortar, carefully grind, 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 briquet
Shape, the secondary clacining in air atmosphere, calcination temperature are 1200 DEG C, and calcination time is 10 hours, and natural cooling is put into agate and grinds
Alms bowl grinding becomes powdered, obtains precalcining mixture.
According to NaCa0.998Tb0.001Li0.001TaNbO6The stoichiometric ratio of sodium element weighs NaF:3.78 grams in F, and claims
Take the NH with NaF equimolar amounts4F:3.33 grams；Precalcining mixture and weighed NaF and NH4F ground and mixed, obtains
Mixture is pressed into bulk, calcines in air atmosphere, and calcination temperature is 850 DEG C, and calcination time is 10 hours.Natural cooling
Bulk sample grinding to get arrive a kind of Tb3+The green luminescent phosphor of niobium tantalates of activation.
Its main structural behaviour, excitation spectrum, luminescent spectrum are similar to Example 1.
Embodiment 3:NaCa0.6Tb0.2Li0.2TaNbO6F
According to chemical formula Ca0.6Tb0.2Li0.2TaNbO6The stoichiometric ratio of middle each element weighs: CaCO3: 3.6 grams；
Tb2O3: 2.196 grams；Ta2O5: 13.26 grams；Li2CO3: 0.443 gram；Nb2O5: 7.974 grams；The raw material claimed is put into agate to grind
Alms bowl is carefully ground, and obtains mixture precalcining in air atmosphere of these raw materials, and calcination temperature is 850 DEG C, and calcination time is
10 hours；Obtained precalcining raw material is placed again into agate mortar grinding, obtained mixture is pressed into bulk, in air gas
Secondary clacining in atmosphere, calcination temperature are 1300 DEG C, and calcination time is 4 hours, and the product natural cooling that above step is obtained obtains
To precalcining object.
According to NaCa0.6Tb0.2Li0.2TaNbO6The stoichiometric ratio of sodium element weighs NaF:2.52 grams in F, and weigh and
The NH of NaF equimolar amounts4F:2.22 grams；Precalcining mixture and weighed NaF and NH4F ground and mixed, obtained mixing
Object is pressed into bulk, calcines in air atmosphere, and calcination temperature is 900 DEG C, and calcination time is 5 hours.The block of natural cooling
Shape sample grinds to arrive a kind of Tb3+The green luminescent phosphor of niobium tantalates of activation.
Its main structural behaviour, excitation spectrum, luminescent spectrum are similar to Example 1.
Claims (5)
1. a kind of Tb3+The green luminescent phosphor of niobium tantalates of activation, which is characterized in that its chemical formula is NaCa1- 2xTbxLixTaNbO6F, x are trivalent terbium ion Tb3+With monovalence lithium ion Li+Replace Ca respectively2+Molal quantity, x value range is
0.001≤x≤0.2。
2. a kind of Tb described in claim 13+The preparation method of the green luminescent phosphor of niobium tantalates of activation, which is characterized in that
Using solid-phase synthesis, comprise the concrete steps that:
(1) according to chemical formula Ca1-2xTbxLixTaNbO6, the stoichiometric ratio of each element weighs respectively in 0.001≤x≤0.2 contains
The compound of calcium ion, the compound containing terbium ion, the compound containing lithium ion, the compound containing tantalum ion, containing niobium ion
Compound；According to chemical formula NaCa1-2xTbxLixTaNbO6F, the stoichiometric ratio of sodium element weighs fluorine in 0.001≤x≤0.2
Change sodium, then weighs the ammonium fluoride with sodium fluoride equimolar amounts；
(2) raw material for claiming step (1): the compounds of calcium ions, the compound containing terbium ion, containing the chemical combination of lithium ion
Object, the compound containing niobium ion, the compound containing tantalum 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 fluorination
Sodium and the thorough ground and mixed of ammonium fluoride, obtained mixture are pressed into bulk, calcine in air atmosphere, calcination temperature 850
~1000 DEG C, calcination time is 1~10 hour, naturally cools to room temperature, is ground to get a kind of Tb is arrived3+The niobium tantalates of activation
Green luminescent phosphor.
3. Tb according to claim 23+The preparation method of the green luminescent phosphor of niobium tantalates of activation, which is characterized in that
The compound of the calcium ions is one of calcium carbonate, calcium nitrate；The compound containing terbium ion is terbium oxide；
The compound containing lithium ion is lithium carbonate；The compound containing niobium ion is niobium pentaoxide；Described contains tantalum
The compound of ion is tantalum oxide.
4. Tb described in claim 13+The green luminescent phosphor of niobium tantalates of activation is in preparation with black light, blue-light semiconductor
The LED illumination or the application in display device that chip is excitation light source.
5. Tb described in claim 13+The green luminescent phosphor of niobium tantalates of activation prepare light emitting diode, display material,
Application in three-color fluorescent lamp and Field Emission Display.
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