CN110184055B - Eu (Eu)3+Activated niobium tantalate red luminescent phosphor and preparation and application thereof - Google Patents
Eu (Eu)3+Activated niobium tantalate red luminescent phosphor and preparation and application thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 150000002821 niobium Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 25
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical class [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 10
- 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
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000227 grinding Methods 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 29
- 238000005303 weighing Methods 0.000 claims description 23
- -1 europium ion Chemical class 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 15
- 239000002994 raw material Substances 0.000 claims description 15
- 229910052693 Europium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 230000005284 excitation Effects 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001460 tantalum ion Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-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
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims 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 1
- 150000002500 ions Chemical class 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 238000005286 illumination Methods 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 9
- 239000012856 weighed raw material Substances 0.000 description 6
- 238000001748 luminescence spectrum Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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- 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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- H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
- H01J29/18—Luminescent screens
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- 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
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Abstract
The invention discloses Eu3+Activated niobium tantalate red luminescent phosphor and preparation and application thereof, wherein the chemical formula of the phosphor is NaCa1‑xEuxTa1‑xTixNbO6F, x is Eu3+Ions and Ti4+Ion substitution of Ca2+And Ta5+X is more than or equal to 0.001 and less than or equal to 0.2, firstly, preparing a precursor Ca without fluorine by using a solid-phase synthesis method1‑xEuxTa1‑xTixNbO6(x is more than or equal to 0.001 and less than or equal to 0.2); then adding sodium fluoride and ammonium fluoride into the precursor, fully mixing, pressing into blocks, and sintering by solid-phase synthesis again to obtain the catalyst. The fluorescent powder provided by the invention can well absorb near ultraviolet light and emit red light with very pure color, can be well matched with a near ultraviolet semiconductor LED chip, and is a potential red light emitting powder for preparing a white light LED lighting device.
Description
Technical Field
The invention relates to the field of inorganic fluorescent materials, in particular to Eu3+Activated niobium tantalate red luminescent phosphor and preparation and application thereof.
Background
In recent years, with the innovation and development of semiconductors, the LED illumination based on semiconductors is greatly valued, the illumination based on purple light and near ultraviolet light semiconductor chips forms the mainstream commercial white light LED illumination device at present, and compared with the traditional fluorescent lamp, energy-saving illumination and other light sources, the rapidly developed new generation illumination based on the LED chips has great advantages, such as long service life, the LED illumination can work for more than 50000 hours without faults, and the service life is hundreds of times of that of an incandescent lamp; power saving: the power consumption of the LED is only 1/10 of an incandescent lamp, and the using voltage range is wide; brightness far exceeds that of incandescent lamps, etc.
The most important illumination today is made of a blue semiconductor chip and yellow Y3Al5O12:Ce3+(YAG:Ce3+) The illumination achieved by the combined packaging of the fluorescent powder has a plurality of advantages, butSuch lighting has inevitable drawbacks: insufficient red emission in illumination luminescence, color temperature>4500K) And poor color rendering index (< 80), which largely limits some of its applications in general lighting. Therefore, it is necessary to use a red-emitting phosphor in the phosphor, but the red-emitting phosphor must have a good excitation efficiency in the near-ultraviolet and blue regions. Rare earth ion, Eu, as the most important activator of red luminescence3+Characteristic emission of (A) is derived from5D0→7FJ(J ═ 0,1,2,3,4), the red emissive material activated is the first choice for use in light emitting LEDs. Among the commercial red-emitting phosphors currently being developed, Y is predominant2O3:Eu3+、 Y2O2S:Eu3+However, these phosphors have low excitation efficiency in the near-ultraviolet wavelength region. At the same time, Eu3+The absorption itself has a very important dependence on the structure of the doped matrix, so that a new matrix needs to be developed to realize trivalent europium Eu3+The ions effectively emit light.
Disclosure of Invention
An object of the present invention is to provide a Eu3+Activated niobium tantalate red luminescent phosphor.
Another object of the present invention is to provide the above Eu3+A preparation method of activated niobium tantalate red luminescent phosphor.
It is another object of the present invention to provide the above Eu3+The application of the activated niobium tantalate red luminescent phosphor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: eu (Eu)3+Activated tantalate-niobate red-emitting phosphor, NaCa1-xEuxTa1-xTixNbO6F, x is trivalent europium ion Eu3+And tetravalent titanium ion Ti4+Respectively substituted for Ca2+And Ta5+The value range of x is more than or equal to 0.001 and less than or equal to 0.2.
The matrix of the fluorescent powder is NaCaTaNbO6F，Eu3+The ions are activators.
The invention also providesFor the above Eu3+The preparation method of the activated niobium tantalate red luminescent phosphor adopts a solid-phase synthesis method, and comprises the following specific steps:
(1) according to the chemical formula Ca1-xEuxTa1-xTixNbO6The stoichiometric ratio of each element in the x is more than or equal to 0.001 and less than or equal to 0.2 is respectively called a calcium ion-containing compound, a europium ion-containing compound, a tantalum ion-containing compound, a titanium ion-containing compound and a niobium ion-containing compound; according to the chemical formula NaCa1-xEuxTa1-xTixNbO6F, weighing sodium fluoride according to the stoichiometric ratio of sodium element in the x which is more than or equal to 0.001 and less than or equal to 0.2, and then weighing ammonium fluoride with the same molar quantity as the sodium fluoride;
(2) weighing the raw materials obtained in the step (1): grinding and mixing a calcium ion-containing compound, a europium ion-containing compound, a tantalum ion-containing compound, a titanium ion-containing compound and a niobium ion-containing compound, and then placing the mixture in an air atmosphere for pre-calcination at the calcination temperature of 850-1200 ℃ for 1-10 hours;
(3) grinding the pre-calcined raw material obtained in the step (2) again, pressing the obtained mixture into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the calcination temperature is 1200-1400 ℃, and the calcination time is 1-10 hours;
(4) naturally cooling the product obtained in the step (3), grinding the product into powder, thoroughly grinding and mixing the powder and the sodium fluoride and the ammonium fluoride weighed in the step (1), pressing the obtained mixture into blocks, calcining the blocks in air atmosphere at 850-1000 ℃ for 1-10 hours, naturally cooling the blocks to room temperature, and grinding the blocks to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
Preferably, the compound containing calcium ions is calcium carbonate CaCO3Ca (NO), Ca nitrate3)2One of (1); the compound containing europium ions is europium oxide Eu2O3(ii) a The compound containing tantalum ions is tantalum oxide Ta2O5(ii) a The compound containing titanium ions is titanium oxide TiO2The compound containing niobium ions is niobium pentoxide Nb2O5。
The invention also provides the Eu3+The luminescent application of the activated niobium tantalate red luminescent phosphor.
The fluorescent powder can be effectively lasered in an ultraviolet-to-blue light region between 200 and 500 nanometers to emit red light with a central wavelength of 615 nanometers, is suitable for preparing an LED (light-emitting diode) lighting or display device taking a near ultraviolet and blue light semiconductor chip as an excitation light source, and can also be used in the manufacture of light-emitting diodes, display materials, three-primary-color fluorescent lamps and field emission displays.
Compared with the prior art, the invention has the following beneficial effects:
1. eu according to the invention3+The activated niobium tantalate red luminescent phosphor has matrix crystal lattice comprising multiple ion polyhedrons (Nb, Ta, Ti), and negative ions bonded by F ions, so that the phosphor has very high crystal lattice strength, excellent thermal stability and is suitable for preparing high-power lighting equipment.
2. Cation Ca2+Filled in a skeleton with high rigidity and strength, Eu3+The doping of ions can cause the luminescence center to be fully disturbed, and Eu3+The forbidden transition of ions is broken completely, and effective red luminescence is realized.
3、Ti4+The co-doping of ions not only plays a role in that Eu3+The charge balance caused by doping of the phosphor also enhances the cleanliness and the intensity of red light emission of the phosphor.
4. The excitation spectrum of the red luminescent phosphor is 200 nm-500 nm, the main excitation peak is 395nm, the emission spectrum is 575 nm-720 nm, and the main peak is near 615nm, so that the red luminescent phosphor has the advantages of stable chemical property, good luminescent property, high luminescent intensity and good color rendering property; the preparation method of the europium-doped red fluorescent powder with niobium tantalate as the matrix is based on a solid-phase synthesis method, has strong operability, is mainly prepared in air atmosphere, has simple heating process, is simple and easy to implement, has good reproducibility and short preparation period.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a phosphor prepared in example 1 of the present invention.
FIG. 2 is an SEM image of phosphor prepared in example 1 of the present invention.
FIG. 3 shows the excitation spectrum of the phosphor prepared in example 1 of the present invention at 615 nm.
FIG. 4 shows the emission spectrum of the phosphor prepared in example 1 of the present invention under 395nm excitation.
FIG. 5 is a graph showing the red luminescence decay curve of the phosphor 615 prepared in example 1.
FIG. 6 is a graph showing the red luminescence decay curve of the phosphor 615 prepared in example 4 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1: NaCa0.85Eu0.15Ta0.85Ti0.15NbO6F
According to the chemical formula Ca0.85Eu0.15Ta0.85Ti0.15NbO6Weighing the following elements in stoichiometric ratio: CaCO3: 4.25 g; eu (Eu)2O3: 1.32 g; ta2O5: 9.393 g; TiO 22: 0.6 g; nb2O5: 6.645 g; placing the weighed raw materials into an agate mortar, carefully grinding to obtain a mixture of the raw materials, and pre-calcining the mixture in an air atmosphere at the calcining temperature of 900 ℃ for 9 hours; and grinding the obtained pre-calcined raw material in an agate mortar again, pressing the obtained mixture into blocks, calcining for the second time in the air atmosphere at the calcining temperature of 1400 ℃ for 1 hour, naturally cooling, and grinding the blocks in the agate mortar into powder to obtain the pre-calcined mixture.
According to NaCa0.85Eu0.15Ta0.85Ti0.15NbO6Weighing NaF in the stoichiometric ratio of sodium element in F: 2.1 g, and weighing NH with the same molar quantity as NaF4F: 1.85 g; mixing the pre-calcined mixture with weighed NaF and NH4And F, grinding to obtain a mixture, pressing into blocks, and calcining in an air atmosphere at the calcining temperature of 1000 ℃ for 1 hour. Handle of bicycleThen grinding the cooled block-shaped sample to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
Referring to the attached figure 1, the X-ray powder diffraction pattern of the fluorescent powder prepared by the technical scheme of the embodiment 1 shows that the prepared material is a single phase and has no other impurities;
referring to the attached figure 2, the SEM image of the phosphor prepared according to the technical scheme of the embodiment 1 is good in crystallization property;
referring to the attached figure 3, the excitation spectrum of the fluorescent powder prepared according to the technical scheme of the embodiment 1 at 615nm is monitored. The excitation spectrum shows that the excitation source of red light is mainly in the ultraviolet to blue light region between 200 and 500 nanometers, and the emission of the near ultraviolet LED chip can be well matched;
referring to FIG. 4, it shows the emission spectrum of the phosphor prepared according to the technical scheme of example 1 under the excitation of near ultraviolet 395 nm. The emission spectrum showed that the emission was a red emission having a very pure chromaticity and a central emission wavelength of 615 nm.
Referring to fig. 5, it is a luminescence decay curve of red luminescence of the phosphor 615 prepared according to the technical solution of example 1, the luminescence lifetime is 1.41 ms, which can meet the requirements of luminescence illumination and display without afterglow.
Example 2: NaCa0.999Eu0.001Ta0.999Ti0.001NbO6F
According to the chemical formula Ca0.999Eu0.001Ta0.999Ti0.001NbO6Weighing the following elements in stoichiometric ratio: ca (NO)3)2: 14.74 g; eu (Eu)2O3: 0.016 g; ta2O5: 19.87 g; TiO 22: 0.01 g; nb2O5: 11.96 g; placing the weighed raw materials into an agate mortar, carefully grinding to obtain a mixture of the raw materials, and pre-calcining the mixture in an air atmosphere at the calcining temperature of 1200 ℃ for 1 hour; grinding the obtained pre-calcined raw material in an agate mortar again, pressing the obtained mixture into blocks, calcining for the second time in the air atmosphere at the calcining temperature of 1200 ℃ for 10 hours, naturally cooling,grinding into powder in an agate mortar to obtain a pre-calcined mixture.
According to NaCa0.999Eu0.001Ta0.999Ti0.001NbO6Weighing NaF in the stoichiometric ratio of sodium element in F: 3.78 g, and weighing NH in an amount equimolar to NaF4F: 3.33 g; mixing the pre-calcined mixture with weighed NaF and NH4And F, grinding and mixing, pressing the obtained mixture into blocks, and calcining in an air atmosphere at 850 ℃ for 10 hours. Grinding the naturally cooled block sample to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
The main structural properties, excitation spectrum, luminescence spectrum and luminescence lifetime are similar to those of example 1.
Example 3: NaCa0.8Eu0.2Ta0.8Ti0.2NbO6F
According to the chemical formula Ca0.8Eu0.2Ta0.8Ti0.2NbO6Weighing the following elements in stoichiometric ratio: CaCO3: 4.8 g; eu (Eu)2O3: 2.112 g; ta2O5: 10.61 g; TiO 22: 0.96 g; nb2O5: 7.974 g; placing the weighed raw materials into an agate mortar, carefully grinding to obtain a mixture of the raw materials, and pre-calcining the mixture in an air atmosphere at 850 ℃ for 10 hours; and (3) grinding the obtained pre-calcined raw material in an agate mortar again, pressing the obtained mixture into blocks, calcining for the second time in an air atmosphere, wherein the calcining temperature is 1300 ℃, the calcining time is 4 hours, and naturally cooling the product obtained in the step to obtain a pre-calcined substance.
According to NaCa0.8Eu0.2Ta0.8Ti0.2NbO6Weighing NaF in the stoichiometric ratio of sodium element in F: 2.52 g, and weighing NH in an amount equimolar to NaF4F: 2.22 g; mixing the pre-calcined mixture with weighed NaF and NH4Grinding and mixing F, pressing the obtained mixture into blocks, calcining in air atmosphere at 900 ℃ for 5And (4) hours. Grinding the naturally cooled block sample to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
The main structural properties, excitation spectrum, luminescence spectrum and luminescence lifetime are similar to those of example 1.
Example 4: NaCa0.9Eu0.1Ta0.9Ti0.1NbO6F
According to the chemical formula Ca0.9Eu0.1Ta0.9Ti0.1NbO6Weighing the following elements in stoichiometric ratio: CaCO3: 6.3 g; eu (Eu)2O3: 1.232 g; ta2O5: 13.923 g; TiO 22: 0.56 g; nb2O5: 9.303 g; putting the weighed raw materials into an agate mortar, carefully grinding to obtain a mixture of the raw materials, and pre-calcining the mixture in an air atmosphere at 880 ℃ for 8 hours; and (3) grinding the obtained pre-calcined raw material in an agate mortar again, pressing the obtained mixture into blocks, calcining for the second time in an air atmosphere, wherein the calcining temperature is 1250 ℃, the calcining time is 6 hours, and naturally cooling the product obtained in the step to obtain a pre-calcined substance.
According to NaCa0.9Eu0.1Ta0.9Ti0.1NbO6Weighing NaF in the stoichiometric ratio of sodium element in F: 2.94 g, and weighing NH in an amount equimolar to NaF4F: 2.59 g; mixing the pre-calcined mixture with weighed NaF and NH4And F, grinding and mixing, pressing the obtained mixture into blocks, and calcining in an air atmosphere at the temperature of 950 ℃ for 3 hours. Grinding the naturally cooled block sample to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 1.
Referring to fig. 6, it is a luminescence decay curve of red luminescence of the phosphor 615 prepared according to the technical solution of example 4, the luminescence lifetime is 1.18 ms, which can meet the requirements of luminescence illumination and display without afterglow.
Example 5: NaCa0.88Eu0.12Ta0.88Ti0.12NbO6F
According to the chemical formula Ca0.88Eu0.12Ta0.88Ti0.12NbO6Weighing the following elements in stoichiometric ratio: CaCO3: 4.84 g; eu (Eu)2O3: 1.161 g; ta2O5: 10.696 g; TiO 22: 0.528 g; nb2O5: 7.309 g; placing the weighed raw materials into an agate mortar, carefully grinding to obtain a mixture of the raw materials, and pre-calcining the mixture in an air atmosphere at the calcining temperature of 950 ℃ for 2 hours; and (3) grinding the obtained pre-calcined raw material in an agate mortar again, pressing the obtained mixture into blocks, calcining for the second time in an air atmosphere, wherein the calcining temperature is 1350 ℃, the calcining time is 4 hours, and naturally cooling the product obtained in the step to obtain a pre-calcined substance.
According to NaCa0.88Eu0.12Ta0.88Ti0.12NbO6Weighing NaF in the stoichiometric ratio of sodium element in F: 2.31 g, and weighing NH in an amount equimolar to NaF4F: 2.04 g; mixing the pre-calcined mixture with weighed NaF and NH4And F, grinding and mixing, pressing the obtained mixture into blocks, and calcining in an air atmosphere at 880 ℃ for 4 hours. Grinding the naturally cooled block sample to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
The main structural properties, excitation spectrum, luminescence spectrum and luminescence lifetime are similar to those of example 4.
Example 6: NaCa0.82Eu0.18Ta0.82Ti0.18NbO6F
According to the chemical formula Ca0.82Eu0.18Ta0.82Ti0.18NbO6Weighing the following elements in stoichiometric ratio: CaCO3: 5.002 g; eu (Eu)2O3: 1.932 g; ta2O5: 10.054 g; TiO 22: 0.439 g; nb2O5: 8.107 g; will be provided withPutting the weighed raw materials into an agate mortar, carefully grinding to obtain a mixture of the raw materials, and pre-calcining the mixture in air atmosphere at 860 ℃ for 1 hour; and (3) grinding the obtained pre-calcined raw material in an agate mortar again, pressing the obtained mixture into blocks, calcining for the second time in the air atmosphere, wherein the calcining temperature is 1300 ℃, the calcining time is 5 hours, and naturally cooling the product obtained in the step to obtain a pre-calcined substance.
According to NaCa0.82Eu0.18Ta0.82Ti0.18NbO6Weighing NaF in the stoichiometric ratio of sodium element in F: 2.562 g, and weighing NH in an amount equimolar to NaF4F: 2.257 g; mixing the pre-calcined mixture with weighed NaF and NH4And F, grinding and mixing, pressing the obtained mixture into blocks, and calcining in an air atmosphere at 900 ℃ for 5 hours. Grinding the naturally cooled block sample to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
The main structural properties, excitation spectrum, luminescence spectrum and luminescence lifetime are similar to those of example 4.
Claims (4)
1. Eu (Eu)3+The activated niobium tantalate red luminescent phosphor is characterized in that the chemical formula of the activated niobium tantalate red luminescent phosphor is NaCa1-xEuxTa1- xTixNbO6F, x is trivalent europium ion Eu3+And tetravalent titanium ion Ti4+Respectively substituted for Ca2+And Ta5+The value range of x is more than or equal to 0.001 and less than or equal to 0.2; the Eu being3+The preparation method of the activated niobium tantalate red luminescent phosphor adopts a solid-phase synthesis method, and comprises the following specific steps:
(1) according to the chemical formula Ca1-xEuxTa1-xTixNbO6The stoichiometric ratio of each element in the x is more than or equal to 0.001 and less than or equal to 0.2 is respectively called a calcium ion-containing compound, a europium ion-containing compound, a tantalum ion-containing compound, a titanium ion-containing compound and a niobium ion-containing compound; according to the chemical formula NaCa1-xEuxTa1-xTixNbO6F, weighing sodium fluoride according to the stoichiometric ratio of sodium element in the x which is more than or equal to 0.001 and less than or equal to 0.2, and then weighing ammonium fluoride with the same molar quantity as the sodium fluoride;
(2) grinding and mixing the calcium ion-containing compound, the europium ion-containing compound, the tantalum ion-containing compound, the titanium ion-containing compound and the niobium ion-containing compound which are weighed in the step (1), and then placing the mixture in an air atmosphere for pre-calcination at the calcination temperature of 850-1200 ℃ for 1-10 hours;
(3) grinding the pre-calcined raw material obtained in the step (2) again, pressing the obtained mixture into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the calcination temperature is 1200-1400 ℃, and the calcination time is 1-10 hours;
(4) naturally cooling the product obtained in the step (3), grinding the product into powder, thoroughly grinding and mixing the powder and the sodium fluoride and the ammonium fluoride weighed in the step (1), pressing the obtained mixture into blocks, calcining the blocks in air atmosphere at 850-1000 ℃ for 1-10 hours, naturally cooling the blocks to room temperature, and grinding the blocks to obtain the Eu3+Activated niobium tantalate red luminescent phosphor.
2. Eu according to claim 13+The activated niobium tantalate red luminescent phosphor is characterized in that the compound containing calcium ions is one of calcium carbonate and calcium nitrate; the compound containing europium ions is europium oxide; the compound containing tantalum ions is tantalum oxide; the titanium ion-containing compound is titanium oxide; the compound containing niobium ions is niobium pentoxide.
3. Eu according to claim 13+The activated niobium tantalate red luminescent phosphor is applied to the preparation of LED lighting or display devices which take near ultraviolet and blue semiconductor chips as excitation light sources.
4. Eu according to claim 13+Activated niobium tantalate red luminescent phosphor in preparing light emitting diode, display material, tricolor fluorescent lamp and field emission displayThe use of (1).
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| CN104275199A (en) * | 2014-10-28 | 2015-01-14 | 桂林理工大学 | Visible light responding fluorine-containing photocatalyst and preparation method thereof |
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| CN109395713A (en) * | 2018-11-13 | 2019-03-01 | 江苏师范大学 | A kind of cerium, titanium doped niobium bismuth tantalate catalysis material and the preparation method and application thereof |
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| CN105694886A (en) * | 2015-12-23 | 2016-06-22 | 江苏师范大学 | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material |
| CN109395713A (en) * | 2018-11-13 | 2019-03-01 | 江苏师范大学 | A kind of cerium, titanium doped niobium bismuth tantalate catalysis material and the preparation method and application thereof |
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