CN110003901A - A kind of Eu3+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, preparation method and applications - Google Patents
A kind of Eu3+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, preparation method and applications Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 101
- 239000010955 niobium Substances 0.000 title claims abstract description 55
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000005284 excitation Effects 0.000 claims abstract description 7
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 47
- 150000002500 ions Chemical class 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005286 illumination Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- -1 europium ion Chemical group 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 8
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 238000012805 post-processing Methods 0.000 claims description 8
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 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 7
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001460 tantalum ion Inorganic materials 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 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
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 238000010671 solid-state reaction Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003760 hair shine Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with 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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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a kind of Eu3+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, preparation method and applications, chemical expression LiCa2‑2xEu2xNb2‑2xTi2xTaO10, x is Eu3+And Ti4+Doped and substituted Ca respectively2+And Nb5+Molal quantity, 0.003≤x≤0.25.Fluorescent powder of the present invention has stronger launching efficiency near ultraviolet and blue light wavelength region, main peak is issued under the excitation of 200~500nm light in the feux rouges of 615nm, and luminescent lifetime is at 1.0 milliseconds or more, meet the needs of luminous lighting and display and twilight sunset do not occur, is with a wide range of applications in black light or blue-light semiconductor chip light emitting device field；In addition the preparation method of fluorescent powder provided by the invention is synthesis by solid state reaction, and synthesis step is simple, practical.
Description
Technical field
The invention belongs to inorganic fluorescent material technical fields, and in particular to a kind of Eu3+And Ti4+Ion co-doped niobium tantalum
Silicate red fluorescent powder, preparation method and applications.
Background technique
In the development process of human society, one of the important topic of illumination and display always scientific research.In modern age,
The illumination of the mankind is discharged under high voltages using with mercury metal Hg mostly, so that activated phosphor brings luminous method to realize
Various illuminations.But this method has apparent disadvantage, for example, luminous efficiency lowly causes the loss of the energy, preparation and photograph
Bright equipment scrapping process, which all exists, greatly to be polluted the mankind etc..
The green revolution of illumination is the fluorescent conversion type white light LED part illumination based on semiconductor diode preparation.And biography
The illumination based on Hg of system is compared, and the LED illumination based on semiconductor has very big advantage, for example, soft color, service life
Long, LED illumination can be no-failure operation 50000 hours or more, and the service life is the hundreds of times of incandescent lamp；LED power saving, the electric energy of LED
Consumption is only the 1/10 of incandescent lamp；Wide using voltage range, brightness is also considerably beyond incandescent lamp；LED illumination light is concentrated, can be with
It gives prominence to the key points or emphasizes an object or space；LED illumination change is more, and different projections is made using small bulbs, etc.
Deng.Along with the development of semi-conductor LED illuminating, the research of fluorescent powder also obtains extremely extensive concern in recent years.One is managed
The LED illumination fluorescent powder thought, not only requires high brightness, also to there is the optics product such as low color temperature, high color rendering index (CRI), low dazzle
Matter.Current LED illumination device is prepared based on blue LED die cooperation yellow fluorescent powder, obvious disadvantage
It is colour temperature deficiency, shows apparent cool tone.The rare-earth trichromatic fluorescent powder being widely used at present has very big advantage, example
Such as, photoluminescent band is narrow, and luminous energy is more concentrated, and high in short-wave ultraviolet ray excited stability inferior, and hot properties is good, more suitable
For high load fluorescent lamp slimline and various one-end compact fluorescent lamps.
In three primary colors fluorescent powder, the use of red fluorescence powder can significantly improve the colour rendering index of lighting apparatus, simultaneously
Colour temperature can also be reduced, therefore its research and development receives more and more attention.Wherein Eu3+Ion-activated red fluorescence powder
It is most important candidate, Eu3+The characteristic emission of ion derives from5D0,1,2,3 -7FJThe transition of (J=4 ..., 0), light-emitting junction
Structure is very sensitive to crystalline field, can obtain different luminescence features by the regulation of structure, realize red luminous regulation, this
It is just that searching is suitable, can accommodate Eu3+The parent lattice of ion, so that designing that outstanding red fluorescence powder provides can
Energy.
Summary of the invention
It is an object of the present invention to overcome defect existing in the prior art, a kind of Eu is provided3+And Ti4+It is ion co-doped
Niobium tantalates red fluorescence powder, fluorescent powder of the present invention has stronger launching efficiency near ultraviolet and blue light wavelength region,
Main peak is issued under the excitation of 200~500nm light in the feux rouges of 615nm, and luminescent lifetime meets and shines at 1.0 milliseconds or more
Illumination and display needs and there is not twilight sunset, be suitable for the White-light LED illumination for preparing near ultraviolet LED diode chip for backlight unit and preparing
Equipment.In addition the preparation method of fluorescent powder provided by the invention is synthesis by solid state reaction, and synthesis step is simple, practical.
To achieve the above object, the technical scheme is to design a kind of Eu3+And Ti4+Ion co-doped niobium tantalic acid
Salt red fluorescence powder, chemical expression LiCa2-2xEu2xNb2-2xTi2xTaO10, x is europium ion Eu3+With titanium ion Ti4+Respectively
Doped and substituted divalent calcium ions Ca2+With pentavalent niobium ion Nb5+Molal quantity, x value range be 0.003≤x≤0.25.
For the ease of the preparation and implementation of the fluorescent powder, it is proposed that a kind of Eu3+And Ti4+Ion co-doped niobium tantalates
The preparation method of red fluorescence powder prepares above-mentioned Eu3+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, including it is as follows
Step:
S1: it weighs, according to chemical expression LiCa2-2xEu2xNb2-2xTi2xTaO10The stoichiometric ratio of middle each element weighs
Raw material: contain lithium ion Li+Compound, contain calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium
Ion Nb5+Compound, contain titanium ion Ti4+Compound, contain tantalum ion Ta5+Compound, 0.003≤x≤0.25；
S2: the step S1 raw material weighed is ground, obtains raw mixture powder by precalcining, by raw mixture powder
Body is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 800~1000 DEG C, and precalcination time is 1~10
Hour, obtain precalcining product；
S3: secondary clacining by the precalcining product natural cooling in step S2 and is ground, and obtains precalcining product powder, will
Precalcining product powder squeezes blocking, is placed in secondary clacining in air atmosphere, and secondary clacining temperature is 1000~1250 DEG C, and two
Secondary calcination time is 1~10 hour, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Further preferred technical solution is in addition, described contain lithium ion Li+Compound be lithia Li2O or lithium carbonate
Li2CO3One of；It is described to contain calcium ion Ca2+Compound be calcium carbonate Ca2CO3Or Ca (NO3)2One of；It is described to contain
There is europium ion Eu3+Compound be europium oxide Eu2O3；It is described to contain niobium ion Nb5+Compound be niobium oxide Nb2O5；It is described to contain
There is titanium ion Ti4+Compound be titanium oxide TiO2；It is described to contain tantalum ion Ta5+Compound be Ta2O5。
Further preferred technical solution is in addition, the precalcining temperature of the step S2 is 830~880 DEG C, when precalcining
Between be 2~5h, the secondary clacining temperature of step S3 is 1100~1200 DEG C, and the secondary clacining time is 3~6h.
For the ease of the application implementation and popularization of the fluorescent powder, it is proposed that Eu described in one kind3+And Ti4+It is ion co-doped
Niobium tantalates red fluorescence powder application, by the fluorescent powder prepare using black light or blue-light semiconductor chip as exciting light
The LED illumination or display device in source.
Further preferred technical solution is in addition, prepare light emitting diode, three-color fluorescent lamp or field for the fluorescent powder
Emission display.
The advantages and beneficial effects of the present invention are:
1, compared with existing commercially available red fluorescence powder, such as Y2O3:Eu3+, Y2O2S:Eu3+, fluorescent powder of the present invention is close purple
There is stronger launching efficiency in outer and blue light wavelength region, and main peak is issued under the excitation of 200~500nm light in the red of 615nm
Light, and luminescent lifetime meets the needs of luminous lighting and display and twilight sunset does not occur at 1.0 milliseconds or more, is suitable for that preparation is close
The White-light LED illumination equipment that ultraviolet LED diode chip for backlight unit prepares.
2, the matrix of fluorescent powder of the present invention is LiCa2-2xEu2xNb2-2xTi2xTaO10, lattice maximum feature is: skeleton by
Different kinds of ions polyhedron forms (Nb, Ta, Ti), and lattice has very high intensity, therefore fluorescent powder of the present invention is with very outstanding
Thermal stability.Calcium ion Ca2+It is filled in the lattice framework of fluorescent powder of the present invention, Eu3+The substitution of ion can make lattice
It is disturbed, thus Eu3+The forbidden transition of ion is broken, and Eu may be implemented3+It effectively shines, therefore the light-emitting phosphor is imitated
Rate is high, is with a wide range of applications in black light or blue-light semiconductor chip light emitting device field.
3, the calcium ion Ca in the parent lattice of fluorescent powder2+The Eu for being filled in the higher skeleton of rigid, and adulterating3 +The parent lattice position of ion pair fluorescent powder have sufficient perturbation action, thus when Eu3+The forbidden transition of ion is thoroughly beaten
It is broken, realize Eu3+Effective emitting red light of ion.
4 and Eu3+The Ti of ion co-doped4+Ion is not only played and is made up due to Eu3+Charge caused by the doping of ion
Imbalance, and also improve the cleanliness of fluorescent powder and the intensity of emitting red light.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction pattern according to the fluorescent powder of 1 technical solution of embodiment preparation；
Fig. 2 is the SEM figure according to the fluorescent powder of 1 technical solution of embodiment preparation；
Fig. 3 is to emit the exciting light obtained under light 615nm in monitoring according to the fluorescent powder of 1 technical solution of embodiment preparation
Spectrum；
What the fluorescent powder that Fig. 4 is prepared according to 1 technical solution of embodiment obtained under wavelength 465nm near ultraviolet excitation shines
Spectrum；
Fig. 5 is the decay of luminescence curve according to the fluorescent powder of 1 technical solution of embodiment preparation under 615nm Detection wavelength；
Fig. 6 is the decay of luminescence curve according to the fluorescent powder of 4 technical solution of embodiment preparation under 615nm Detection wavelength.
Specific embodiment
With reference to the accompanying drawings and examples, further description of the specific embodiments of the present invention.Following embodiment is only
For clearly illustrating technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
Prepare LiCa1.6Eu0.4Nb1.6Ti0.4TaO10, include the following steps:
S1: it weighs, according to chemical expression LiCa1.6Eu0.4Nb1.6Ti0.4TaO10(x=0.2) the chemistry meter of each element in
Amount ratio weighs raw material: Li2O:1.35 grams；CaCO3: 14.4 grams；Eu2O3: 6.336 grams, Nb2O5: 19.1374 grams；Ta2O5: 19.89
Gram, TiO2: 2.88 grams；
S2: the step S1 raw material weighed is put into agate mortar and ground by precalcining, obtains raw mixture powder, will
Raw mixture powder is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 850 DEG C, precalcination time
It is 4 hours, obtains precalcining product；
S3: secondary clacining, by the precalcining product in step S2 it is naturally cold after, be put into agate mortar and regrind,
Precalcining product powder is obtained, the extruding of precalcining product powder is blocking, it is placed in secondary clacining in air atmosphere, secondary clacining temperature
Degree is 1150 DEG C, and the secondary clacining time is 5 hours, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Referring to attached drawing 1, according to the X-ray powder diffraction pattern of the fluorescent powder of 1 technical solution of embodiment preparation, XRD test
The result shows that prepared material is single-phase；
Referring to attached drawing 2, scheme according to the SEM of the fluorescent powder of 1 technical solution of embodiment preparation, SEM test result shows to crystallize
It is functional；
Referring to attached drawing 3, sample is prepared according to 1 technical solution of embodiment and emits the exciting light obtained under light 615nm in monitoring
Spectrum, it can be seen that the excitation source of its emitting red light mainly the near ultraviolet between 200~500nm of wave-length coverage to blue region,
Near ultraviolet to blue-light LED chip can be well matched with to emit；
Referring to attached drawing 4, according to the fluorescent powder of 1 technical solution of embodiment preparation under wavelength 465nm near ultraviolet excitation
The luminescent spectrum arrived, main center emission wavelength are the emitting red light of 615nm；
Referring to attached drawing 5, it is bent that decay of luminescence of the fluorescent powder under 615nm Detection wavelength is prepared according to 1 technical solution of embodiment
Line, luminescent lifetime are 1.23 milliseconds, can satisfy the needs of luminous lighting and display and twilight sunset do not occur.
Embodiment 2
Prepare LiCa1.994Eu0.006Nb1.994Ti0.006TaO10, include the following steps:
S1: it weighs, according to chemical expression LiCa1.994Eu0.006Nb1.994Ti0.006TaO10(x=0.003) each element in
Stoichiometric ratio weigh raw material: Li2CO3: 1.85 grams； Ca(NO3)2: 16.35 grams；Eu2O3: 0.0528 gram, Nb2O5: 13.25
Gram；Ta2O5: 11.05 grams, TiO2: 0.024 gram；
S2: the step S1 raw material weighed is put into agate mortar and ground by precalcining, obtains raw mixture powder, will
Raw mixture powder is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 800 DEG C, precalcination time
It is 10 hours, obtains precalcining product；
S3: secondary clacining, by the precalcining product in step S2 it is naturally cold after, be put into agate mortar and regrind,
Precalcining product powder is obtained, the extruding of precalcining product powder is blocking, it is placed in secondary clacining in air atmosphere, secondary clacining temperature
Degree is 1250 DEG C, and the secondary clacining time is 1 hour, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Test result shows: the primary structure of fluorescent powder product prepared by embodiment 2, excitation spectrum, luminescent spectrum and its
Luminescent lifetime is similar to fluorescent powder prepared by embodiment 1.
Embodiment 3
Prepare LiCa1.5Eu0.5Nb1.5Ti0.5TaO10, include the following steps:
S1: it weighs, according to chemical expression LiCa1.5Eu0.5Nb1.5Ti0.5TaO10(x=0.25) chemistry of each element in
Metering ratio weighs raw material: Li2CO3: 1.48 grams；CaCO3: 6 grams；Eu2O3: 3.52 grams, Nb2O5: 7.974 grams；Ta2O5: 8.84 grams,
TiO2: 1.6 grams；
S2: the step S1 raw material weighed is put into agate mortar and ground by precalcining, obtains raw mixture powder, will
Raw mixture powder is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 1000 DEG C, precalcination time
It is 1 hour, obtains precalcining product；
S3: secondary clacining, by the precalcining product in step S2 it is naturally cold after, be put into agate mortar and regrind,
Precalcining product powder is obtained, the extruding of precalcining product powder is blocking, it is placed in secondary clacining in air atmosphere, secondary clacining temperature
Degree is 1000 DEG C, and the secondary clacining time is 10 hours, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Test result shows: the primary structure of fluorescent powder product prepared by embodiment 3, excitation spectrum, luminescent spectrum and its
Luminescent lifetime is similar to fluorescent powder prepared by embodiment 1.
Embodiment 4
Prepare LiCa1.8Eu0.2Nb1.8Ti0.2TaO10, include the following steps:
S1: it weighs, according to chemical expression LiCa1.8Eu0.2Nb1.8Ti0.2TaO10(x=0.1) the chemistry meter of each element in
Amount ratio weighs raw material: Li2CO3: 1.85 grams；CaCO3: 9 grams；Eu2O3: 1.76 grams, Nb2O5: 11.96 grams；Ta2O5: 11.05 grams,
TiO2: 0.8 gram；
S2: the step S1 raw material weighed is put into agate mortar and ground by precalcining, obtains raw mixture powder, will
Raw mixture powder is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 880 DEG C, precalcination time
It is 2 hours, obtains precalcining product；
S3: secondary clacining, by the precalcining product in step S2 it is naturally cold after, be put into agate mortar and regrind,
Precalcining product powder is obtained, the extruding of precalcining product powder is blocking, it is placed in secondary clacining in air atmosphere, secondary clacining temperature
Degree is 1200 DEG C, and the secondary clacining time is 3 hours, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Test result shows: the primary structure of fluorescent powder product prepared by embodiment 4, excitation spectrum, luminescent spectrum and its
Luminescent lifetime is similar to fluorescent powder prepared by embodiment 1.
Referring to attached drawing 6, according to decay of luminescence of the fluorescent powder of 4 technical solution of embodiment preparation under 615nm Detection wavelength
Curve, luminescent lifetime are 1.05 milliseconds, can satisfy the needs of luminous lighting and display and twilight sunset do not occur.
Embodiment 5
Prepare LiCa1.7Eu0.3Nb1.7Ti0.3TaO10, include the following steps:
S1: it weighs, according to chemical expression LiCa1.7Eu0.3Nb1.7Ti0.3TaO10(x=0.15) chemistry of each element in
Metering ratio weighs raw material: Li2CO3: 1.48 grams；CaCO3: 6.8 grams； Eu2O3: 2.112 grams, Nb2O5: 9.037 grams；Ta2O5: 8.84
Gram, TiO2: 0.96 gram；
S2: the step S1 raw material weighed is put into agate mortar and ground by precalcining, obtains raw mixture powder, will
Raw mixture powder is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 830 DEG C, precalcination time
It is 5 hours, obtains precalcining product；
S3: secondary clacining, by the precalcining product in step S2 it is naturally cold after, be put into agate mortar and regrind,
Precalcining product powder is obtained, the extruding of precalcining product powder is blocking, it is placed in secondary clacining in air atmosphere, secondary clacining temperature
Degree is 1150 DEG C, and the secondary clacining time is 4 hours, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Test result shows: the primary structure of fluorescent powder product prepared by embodiment 5, excitation spectrum, luminescent spectrum and its
Luminescent lifetime is similar to fluorescent powder prepared by embodiment 1.
Embodiment 6
Prepare LiCa1.64Eu0.36Nb1.64Ti0.36TaO10, include the following steps:
S1: it weighs, according to chemical expression LiCa1.7Eu0.3Nb1.7Ti0.3TaO10(x=0.18) chemistry of each element in
Metering ratio weighs raw material: Li2CO3: 1.48 grams；CaCO3: 6.56 grams； Eu2O3: 2.53 grams, Nb2O5: 8.71 grams；Ta2O5: 8.84
Gram, TiO2: 0.576 gram；
S2: the step S1 raw material weighed is put into agate mortar and ground by precalcining, obtains raw mixture powder, will
Raw mixture powder is squeezed into bulk, is placed in precalcining in air atmosphere, and precalcining temperature is 850 DEG C, precalcination time
It is 6 hours, obtains precalcining product；
S3: secondary clacining, by the precalcining product in step S2 it is naturally cold after, be put into agate mortar and regrind,
Precalcining product powder is obtained, the extruding of precalcining product powder is blocking, it is placed in secondary clacining in air atmosphere, secondary clacining temperature
Degree is 1100 DEG C, and the secondary clacining time is 6 hours, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion is co-doped with
Miscellaneous niobium tantalates red fluorescence powder product.
Test result shows: the primary structure of fluorescent powder product prepared by embodiment 6, excitation spectrum, luminescent spectrum and its
Luminescent lifetime is similar to fluorescent powder prepared by embodiment 1.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of Eu3+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, which is characterized in that chemical expression is
LiCa2-2xEu2xNb2-2xTi2xTaO10, x is europium ion Eu3+With titanium ion Ti4+Doped and substituted divalent calcium ions Ca respectively2+With five
Valence niobium ion Nb5+Molal quantity, x value range be 0.003≤x≤0.25.
2. a kind of Eu3+And Ti4+The preparation method of ion co-doped niobium tantalates red fluorescence powder, which is characterized in that preparation is such as
Eu described in claim 13+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, includes the following steps:
S1: it weighs, according to chemical expression LiCa2-2xEu2xNb2-2xTi2xTaO10The stoichiometric ratio of middle each element weighs raw material:
Contain lithium ion Li+Compound, contain calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion
Nb5+Compound, contain titanium ion Ti4+Compound, contain tantalum ion Ta5+Compound, 0.003≤x≤0.25；
S2: the step S1 raw material weighed is ground, obtains raw mixture powder, raw mixture powder is squeezed by precalcining
It is pressed into bulk, is placed in precalcining in air atmosphere, precalcining temperature is 800~1000 DEG C, and precalcination time is 1~10 small
When, obtain precalcining product；
S3: secondary clacining by the precalcining product natural cooling in step S2 and grinds, obtains precalcining product powder, will be pre-calcined
It is blocking to burn the extruding of product powder, is placed in secondary clacining in air atmosphere, secondary clacining temperature is 1000~1250 DEG C, secondary to forge
Burning the time is 1~10 hour, obtains secondary clacining product；
S4: post-processing by the secondary clacining product natural cooling in step S3 and grinds, obtains Eu3+And Ti4+Ion co-doped niobium
Tantalates red fluorescence powder product.
3. Eu as claimed in claim 23+And Ti4+The preparation method of ion co-doped niobium tantalates red fluorescence powder, it is special
Sign is, described to contain lithium ion Li+Compound be lithia Li2O or lithium carbonate Li2CO3One of；It is described to contain calcium
Ion Ca2+Compound be calcium carbonate Ca2CO3Or Ca (NO3)2One of；It is described to contain europium ion Eu3+Compound be oxygen
Change europium Eu2O3；It is described to contain niobium ion Nb5+Compound be niobium oxide Nb2O5；It is described to contain titanium ion Ti4+Compound be oxygen
Change titanium TiO2；It is described to contain tantalum ion Ta5+Compound be Ta2O5。
4. Eu as claimed in claim 23+And Ti4+Ion co-doped niobium tantalates red fluorescence powder, which is characterized in that described
The precalcining temperature of step S2 is 830~880 DEG C, and precalcination time is 2~5h, the secondary clacining temperature of step S3 is 1100~
1200 DEG C, the secondary clacining time is 3~6h.
5. a kind of Eu as described in claim 13+And Ti4+The application of ion co-doped niobium tantalates red fluorescence powder, it is special
Sign is, prepares using black light or blue-light semiconductor chip as the LED illumination of excitation light source or display device.
6. Eu as claimed in claim 53+And Ti4+The application of ion co-doped niobium tantalates red fluorescence powder, feature exist
In preparing light emitting diode, three-color fluorescent lamp or Field Emission Display.
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