CN113717724A - Eu (Eu)3+Doped transition metal tellurium oxide fluorescent powder and preparation method and application thereof - Google Patents
Eu (Eu)3+Doped transition metal tellurium oxide fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 35
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 69
- -1 rare earth ions Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 9
- 230000005284 excitation Effects 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 4
- 239000010955 niobium Substances 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 11
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 229910001940 europium oxide Inorganic materials 0.000 claims description 5
- 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 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- OFDISMSWWNOGFW-UHFFFAOYSA-N 1-(4-ethoxy-3-fluorophenyl)ethanamine Chemical compound CCOC1=CC=C(C(C)N)C=C1F OFDISMSWWNOGFW-UHFFFAOYSA-N 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 9
- 230000007704 transition Effects 0.000 abstract description 5
- 238000005090 crystal field Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract 2
- 238000004020 luminiscence type Methods 0.000 description 26
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000005424 photoluminescence Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 description 3
- 229910003069 TeO2 Inorganic materials 0.000 description 3
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle 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
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- SWLJJEFSPJCUBD-UHFFFAOYSA-N tellurium tetrachloride Chemical compound Cl[Te](Cl)(Cl)Cl SWLJJEFSPJCUBD-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide 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
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/886—Chalcogenides with rare earth metals
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- H01L33/50—Wavelength conversion elements
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Abstract
The invention discloses Eu3+Doped transition metal tellurium oxide fluorescent powder and a preparation method and application thereof, belonging to the technical field of luminescent materials. The fluorescent powder is prepared from rare earth ions Eu3+A doped transition metal tellurium oxide having the chemical formula: nb1.5V0.5Te4‑4xEu4xO13In the formula, x is Eu3+Doping of Te4+The molar ratio of x is more than or equal to 0.005 and less than or equal to 0.05. Under the excitation of near ultraviolet light, Eu is under the action of a crystal field due to strong polarizability of the crystal field environment3+The method can realize sufficient electric dipole transition, so that the phosphor prepared by the method has pure color and high luminous efficiency, and can be widely applied to luminescent devices or display devices. The fluorescent powder is prepared by adopting a high-temperature solid-phase method, and the preparation method is simple and easy to implement, low in production cost, pollution-free and pollution-freeThe waste gas and liquid are discharged, the calcining temperature is low, the energy consumption is saved, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to an inorganic fluorescent material and a preparation method and application thereof, in particular to Eu3+Doped transition metal tellurium oxide fluorescent powder and a preparation method and application thereof, belonging to the technical field of luminescent materials.
Background
The rare earth ion activated fluorescent powder can emit fluorescent light with various chromaticities from rare earth ions under the excitation of external energy, and Eu is used3+、Sm3+、Er3+、Tb3+Rare earth ions represented by the above-mentioned rare earth ions have narrow light-emitting band, concentrated light-emitting energy and good chromaticity; with Eu2+、Ce3+、Yb2+The rare earth ion luminescence represented by the general formula is characterized by broadband spectrum, high luminous efficiency, rich chromaticity change and the like. The rare earth ion activated fluorescent powder can be excited by ultraviolet light, near ultraviolet light or blue light wavelength, has the characteristics of high stability, good high-temperature characteristic and the like, and is widely applied to various industries such as luminescence, display, information storage, biological marking, medical treatment and the like.
The rare earth ion activated fluorescent powder has rich varieties, and at present, common matrix materials comprise phosphate, silicate, borate, aluminate, aluminosilicate and the like, and the matrix materials have stable physical and chemical properties, good thermal stability and simpler preparation. Compared with these matrix materials, the phosphor based on transition metal oxide is developed less.
Disclosure of Invention
One of the objectives of the present invention is to provide a Eu with pure chromaticity, high luminous efficiency, low manufacturing cost, simple preparation process, and no pollution3+Doped transition metal tellurium oxide fluorescent powder and preparation method thereof, and Eu is expanded3+Doping other kinds of matrix materials to prepare the application range of the fluorescent powder.
Another object of the present invention is to provide the above Eu3+The application of doped transition metal tellurium oxide fluorescent powder.
In order to achieve the purpose, the invention adopts the technical scheme that: eu (Eu)3+Doped transition metal tellurium oxide fluorescent powder with the chemical formula of Nb1.5V0.5Te4-4xEu4xO13In the formula, x is Eu3+Doping of Te4+The molar ratio of x is more than or equal to 0.005 and less than or equal to 0.05.
The invention also provides the Eu3+Transition of dopingThe preparation method of the tellurium oxide phosphor adopts a high-temperature solid phase method and comprises the following steps:
(1) by containing niobium ions Nb5+Compound of (2), vanadium ion-containing compound V5+Compound of (2), tellurium ion-containing Te4+Compound of (1), Eu ion-containing Eu3+Is taken as a raw material and has a molecular formula of Nb1.5V0.5Te4-4xEu4xO13Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, wherein x is Eu3+Doping of Te4+The molar ratio of the bits is more than or equal to 0.05 and less than or equal to 0.05; weighing Nb ions5+Compound of (2), vanadium ion-containing compound V5+Compound of (2), tellurium ion-containing Te4+Compound of (1), Eu ion-containing Eu3+Respectively grinding the compounds, and uniformly mixing to obtain a raw material mixture;
(2) calcining the raw material mixture obtained in the step (1) for the first time in an air atmosphere, wherein the calcining temperature is 350-400 ℃, and the calcining time is 1-5 h;
(3) naturally cooling the mixture obtained by the first calcination to room temperature, grinding and uniformly mixing, and carrying out second calcination in an air atmosphere, wherein the calcination temperature is 400-500 ℃, and the calcination time is 1-10 h;
(4) naturally cooling the mixture obtained by the second calcination to room temperature, grinding and uniformly mixing, carrying out third calcination in air atmosphere, wherein the calcination temperature is 530-600 ℃, the calcination time is 1-10 h, and naturally cooling to room temperature to obtain Eu3+Doped transition metal tellurium oxide phosphor.
Preferably, the niobium ion Nb is contained5+The compound of (1) is niobium pentoxide or niobium chloride; the vanadium ion V5 +The compound of (A) is ammonium metavanadate or vanadium pentoxide; the tellurium ion-containing Te4+The compound of (1) is tellurium dioxide or tellurium tetrachloride; the Eu ion containing europium3+The compound of (1) is europium oxide.
Preferably, the first calcination temperature in the step (2) is 400 ℃, and the calcination time is 1 h; the second calcination in the step (3) is carried out at the temperature of 400 ℃ for 10 h; the third calcination temperature in the step (4) is 530 ℃, and the calcination time is 10 h.
The invention also provides the Eu3+The doped transition metal tellurium oxide fluorescent powder is applied to the preparation of a luminescent device or a display device which takes ultraviolet light-near ultraviolet light as an excitation light source.
Containing Nb5+The oxide is a common matrix material, the prepared fluorescent powder generally has the characteristics of good thermal stability, high luminous efficiency and good physical and chemical properties, and in addition, the Nb content5+The optical absorption of the oxide of (A) is mostly from Nb5+-O2-Generally in the ultraviolet range, and therefore contains Nb5+The prepared fluorescent powder is not beneficial to near ultraviolet excitation, and is not suitable for preparing a white light LED. Based on this, the invention uses V5+Substituting part of Nb5+Thereby increasing the light absorption in the visible light region and realizing Eu3+The effective excitation of (1). Te in the matrix of the invention4+Contains stereo active lone pair electrons with very characteristic and strong polarization characteristic, so that it has piezoelectric and ferroelectric properties, therefore Te in crystal lattice4+Is doped with rare earth Eu in lattice position3+Polarization of lattice site can realize Eu3+The effective energy transfer of photo-generated charges is realized under the action of external exciting light, and finally Eu is realized3+Is/are as follows5D0→7F2The light emitting transition has pure chromaticity and high light emitting efficiency.
Compared with the prior art, the invention has the following advantages:
(1) the inorganic fluorescent powder prepared by the invention has a tellurate Nb of transition metal Nb-V as a matrix1.5V0.5Te4O13Can exert Nb5+And V5+Synergistic optical properties of (a);
(2) the doped ion for preparing the fluorescent powder is Eu3+The substitution site is Te4+The crystal lattice site and the crystal field environment have strong polarization performance, and Eu is under the action of the crystal field3+Can realize sufficient electric dipole transition, thereby leading toThe phosphor prepared by the invention has pure chroma and high luminous efficiency; the fluorescent powder has good light absorption capacity in an ultraviolet region, can realize red luminescence with pure chromaticity, and can be widely applied to luminescent devices or display devices which take ultraviolet light-near ultraviolet light as excitation light sources;
(3) the fluorescent powder is prepared by adopting a high-temperature solid-phase method, the preparation method is simple and easy to implement, the production cost is low, no pollution is caused, no waste gas and liquid is discharged, the calcining temperature is low, the energy consumption is saved, the industrial production is easy to realize, and the Eu is expanded3+Doping other kinds of matrix materials to prepare the application range of the fluorescent powder.
Drawings
FIG. 1 sample Nb prepared in comparative example of the invention1.5V0.5Te4O13X-ray powder diffraction pattern of (a);
FIG. 2 Nb sample prepared in comparative example of the invention1.5V0.5Te4O13A luminescence spectrum of (a);
FIG. 3 Nb sample prepared in comparative example of the invention1.5V0.5Te4O13The luminescence decay curve of (a);
FIG. 4 sample Nb prepared in accordance with one embodiment of the present invention1.5V0.5Te3.8Eu0.2O13X-ray powder diffraction pattern of (a);
FIG. 5 sample Nb prepared in accordance with one embodiment of the present invention1.5V0.5Te3.8Eu0.2O13SEM picture of (1);
FIG. 6A sample Nb prepared in accordance with an embodiment of the present invention1.5V0.5Te3.8Eu0.2O13EDS test and element content result chart thereof;
FIG. 7 sample Nb prepared in accordance with one embodiment of the present invention1.5V0.5Te3.8Eu0.2O13A photoluminescence map of (a);
FIG. 8 sample Nb prepared in accordance with one embodiment of the present invention1.5V0.5Te3.8Eu0.2O13The luminescence decay curve of (a);
FIG. 9 prepared according to example II of the present inventionObtaining a sample Nb1.5V0.5Te3.88Eu0.12O13X-ray powder diffraction pattern of (a);
FIG. 10 sample Nb obtained in example two of the present invention1.5V0.5Te3.88Eu0.12O13A photoluminescence map of (a);
FIG. 11 sample Nb obtained in example two of the present invention1.5V0.5Te3.88Eu0.12O13The luminescence decay curve of (a);
FIG. 12 sample Nb prepared in the third embodiment of the present invention1.5V0.5Te3.98Eu0.02O13X-ray powder diffraction pattern of (a);
FIG. 13 sample Nb obtained in the third embodiment of the present invention1.5V0.5Te3.98Eu0.02O13A photoluminescence map of (a);
FIG. 14 shows Nb sample obtained in the third embodiment of the present invention1.5V0.5Te3.98Eu0.02O13The luminescence decay curve of (1).
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Comparison group: eu is not doped in the preparation process3+
Preparation of Nb1.5V0.5Te4O13: according to the chemical formula Nb1.5V0.5Te4O13The stoichiometric ratio of each element in the niobium pentoxide is respectively weighed2O5: 1.994 g of ammonium metavanadate NH4VO3: 0.585 g tellurium dioxide TeO2: 6.4 g, grinding and uniformly mixing the raw materials to obtain a raw material mixture; putting the obtained raw material mixture into a crucible, and carrying out primary calcination in a muffle furnace in an air atmosphere, wherein the calcination temperature is 350 ℃, and the pre-calcination time is 5 hours; naturally cooling the mixture obtained by the first calcination to room temperature, fully grinding and uniformly mixing, putting the mixture into the crucible again, and carrying out second calcination in a muffle furnace in air atmosphere at the calcination temperature of 500 DEG CThe time is 1 h; naturally cooling the mixture obtained in the second calcination to room temperature, fully grinding and mixing, putting into a crucible, carrying out third calcination in a muffle furnace in air atmosphere at the calcination temperature of 600 ℃ for 1h, and naturally cooling to room temperature to obtain the Nb1.5V0.5Te4O13And (3) fluorescent powder.
Referring to FIG. 1, the X-ray powder diffraction pattern of the material sample prepared according to the technical scheme of the comparison group is shown, and the prepared material and Nb in the database can be seen from the figure2Te4O13(PDF #53-1077) are completely matched without any impurity phase, and the prepared material is proved to be a single-phase material, has high diffraction intensity and is sharp, which shows that the crystallinity of the synthesized fluorescent powder is good.
Referring to FIG. 2, the luminescence spectrum of the material sample prepared according to the embodiment of this comparison group is shown, and it can be seen from the graph that the substrate has luminescence property when doped with Eu3+After ionization, these transition energies can be transferred to Eu3+Ions and realizes their luminescence.
Referring to fig. 3, which is a graph showing the luminescence decay curve of a sample of material prepared according to the embodiment of this comparative group, it can be seen that the luminescence lifetime of the substrate is 14.13 μ s.
Example one
Preparation of Nb1.5V0.5Te4-4xEu4xO13(x ═ 0.05): according to the chemical formula Nb1.5V0.5Te3.8Eu0.2O13The stoichiometric ratio of each element in the niobium pentoxide is respectively weighed2O5: 2.1936 g of ammonium metavanadate NH4VO3: 0.643 g of tellurium tetrachloride TeCl4: 11.289 g of europium oxide Eu2O3: 0.387 g, grinding the raw materials and uniformly mixing to obtain a raw material mixture; putting the obtained raw material mixture into a crucible, and carrying out primary calcination in a muffle furnace in an air atmosphere, wherein the calcination temperature is 400 ℃, and the pre-calcination time is 1 h; naturally cooling the mixture obtained by the first calcination to room temperature, fully grinding and uniformly mixing, putting into the crucible again, and calcining in the crucibleCarrying out secondary calcination in a muffle furnace in an air atmosphere, wherein the calcination temperature is 400 ℃, and the calcination time is 10 h; naturally cooling the mixture obtained in the second calcination to room temperature, fully grinding and mixing, putting into a crucible, carrying out third calcination in a muffle furnace in air atmosphere at 530 ℃ for 10h, and naturally cooling to room temperature to obtain the Nb1.5V0.5Te3.8Eu0.2O13And (3) fluorescent powder.
Referring to FIG. 4, it is an X-ray powder diffraction pattern of a sample of the material prepared according to the embodiment of this example, from which it can be seen that the material prepared and Nb in the database2Te4O13(PDF #53-1077) are completely matched without any impurity phase, and the prepared material is proved to be a single-phase material, has high diffraction intensity and is sharp, which shows that the crystallinity of the synthesized fluorescent powder is good.
Referring to FIG. 5, which is an SEM image of a sample of material prepared according to the embodiment of this example, it can be seen that the sample has a particle size of about 14 microns and is well crystallized.
Referring to FIG. 6, the EDS test and the element content of the material sample prepared according to the embodiment are shown, and it can be seen that Nb is added5+/V5+Molar ratio of 3.02, Te4+/Eu3+The molar ratio was 19.06, which is essentially consistent with the ratio of the formula.
Referring to FIG. 7, it is a photoluminescence chart of a material sample prepared according to the embodiment of the present invention, and it can be seen that the sample is obtained from Eu3+The characteristic red luminescence of the ion, the strongest luminescence peak position is 613 nm, which is typical of Eu3+Is/are as follows5D0→7F2Is detected.
Referring to fig. 8, it is the luminescence decay curve of the material sample prepared according to the technical scheme of this example, and it can be seen from the graph that the luminescence lifetime of the sample is 1.08 ms, which completely meets the requirements of luminescence and display.
Example two
Preparation of Nb1.5V0.5Te4-4xEu4xO13(x ═ 0.03): according to the chemical formula Nb1.5V0.5Te3.88Eu0.12O13The stoichiometric ratio of each element in the niobium pentachloride NbCl is respectively weighed5: 6.889 g of ammonium metavanadate NH4VO3: 0.995 g tellurium dioxide TeO2: 1.554 g, europium oxide Eu2O3: 0.359 g, grinding and uniformly mixing the raw materials to obtain a raw material mixture; putting the obtained raw material mixture into a crucible, and carrying out primary calcination in a muffle furnace in an air atmosphere, wherein the calcination temperature is 370 ℃, and the pre-calcination time is 3 h; naturally cooling the mixture obtained by the first calcination to room temperature, fully grinding and uniformly mixing, putting into the crucible again, and carrying out second calcination in a muffle furnace in air atmosphere, wherein the calcination temperature is 480 ℃ and the calcination time is 3 hours; naturally cooling the mixture obtained in the second calcination to room temperature, fully grinding and mixing, putting into a crucible, carrying out third calcination in a muffle furnace in air atmosphere at 550 ℃ for 5h, and naturally cooling to room temperature to obtain the Nb1.5V0.5Te3.88Eu0.12O13And (3) fluorescent powder.
Referring to FIG. 9, it is an X-ray powder diffraction pattern of a sample of the material prepared according to the embodiment of the present invention, and it can be seen from the X-ray powder diffraction pattern that the prepared material and Nb in the database are obtained2Te4O13(PDF #53-1077) are completely matched without any impurity phase, and the prepared material is proved to be a single-phase material, has high diffraction intensity and is sharp, which shows that the crystallinity of the synthesized fluorescent powder is good.
Referring to FIG. 10, it is a photoluminescence chart of a sample of the material prepared according to the embodiment of the present invention, and it can be seen that the sample is obtained from Eu3+The characteristic red luminescence of the ion, the strongest luminescence peak position is 613 nm, which is typical of Eu3+Is/are as follows5D0→7F2Is detected.
Referring to fig. 11, it is the luminescence decay curve of the material sample prepared according to the technical solution of this example, and it can be seen from the graph that the luminescence lifetime of the sample is 1.41 ms, which completely meets the requirements of luminescence and display.
EXAMPLE III
Preparation of Nb1.5V0.5Te4-4xEu4xO13(x ═ 0.005): according to the chemical formula Nb1.5V0.5Te3.98Eu0.02O13The stoichiometric ratio of each element in the niobium pentoxide is respectively weighed2O5: 5.98 g of vanadium pentoxide V2O5: 1.364 g tellurium dioxide TeO2: 19.1 g of europium oxide Eu2O3: 0.106 g, grinding and uniformly mixing the raw materials to obtain a raw material mixture; putting the obtained raw material mixture into a crucible, and carrying out primary calcination in a muffle furnace in an air atmosphere, wherein the calcination temperature is 360 ℃, and the pre-calcination time is 4 h; naturally cooling the mixture obtained by the first calcination to room temperature, fully grinding and uniformly mixing, putting into the crucible again, and carrying out second calcination in a muffle furnace in air atmosphere, wherein the calcination temperature is 450 ℃ and the calcination time is 5 hours; naturally cooling the mixture obtained in the second calcination to room temperature, fully grinding and mixing, putting into a crucible, carrying out third calcination in a muffle furnace in air atmosphere at 570 ℃ for 6h, and naturally cooling to room temperature to obtain the Nb1.5V0.5Te3.98Eu0.02O13And (3) fluorescent powder.
Referring to FIG. 12, there is shown an X-ray powder diffraction pattern of a sample of the material prepared according to the embodiment of the present invention, from which it can be seen that the material prepared and Nb in the database2Te4O13(PDF #53-1077) are completely matched without any impurity phase, and the prepared material is proved to be a single-phase material, has high diffraction intensity and is sharp, which shows that the crystallinity of the synthesized fluorescent powder is good.
Referring to FIG. 13, it is a photoluminescence chart of a sample of the material prepared according to the embodiment, and it can be seen that the sample is obtained from Eu3+The characteristic red luminescence of the ion, the strongest luminescence peak position is 613 nm, which is typical of Eu3+Is/are as follows5D0→7F2Is detected.
Referring to fig. 14, the luminescence decay curve of the material sample prepared according to the embodiment of the present invention is shown, and it can be seen from the graph that the luminescence lifetime of the sample is 1.74 ms, which completely satisfies the requirements of luminescence and display.
Claims (5)
1. Eu (Eu)3+The doped transition metal tellurium oxide fluorescent powder is characterized in that the chemical formula is Nb1.5V0.5Te4- 4xEu4xO13In the formula, x is Eu3+Doping of Te4+The molar ratio of x is more than or equal to 0.005 and less than or equal to 0.05.
2. Eu according to claim 13+The preparation method of the doped transition metal tellurium oxide fluorescent powder is characterized by adopting a high-temperature solid phase method and comprising the following steps of:
(1) by containing niobium ions Nb5+Compound of (2), vanadium ion-containing compound V5+Compound of (2), tellurium ion-containing Te4+Compound of (1), Eu ion-containing Eu3+Is taken as a raw material and has a molecular formula of Nb1.5V0.5Te4-4xEu4xO13Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, wherein x is Eu3+Doping of Te4+The molar ratio of the bits is more than or equal to 0.05 and less than or equal to 0.05; weighing Nb ions5+Compound of (2), vanadium ion-containing compound V5+Compound of (2), tellurium ion-containing Te4+Compound of (1), Eu ion-containing Eu3+Respectively grinding the compounds, and uniformly mixing to obtain a raw material mixture;
(2) calcining the raw material mixture obtained in the step (1) for the first time in an air atmosphere, wherein the calcining temperature is 350-400 ℃, and the calcining time is 1-5 h;
(3) naturally cooling the mixture obtained by the first calcination to room temperature, grinding and uniformly mixing, and carrying out second calcination in an air atmosphere, wherein the calcination temperature is 400-500 ℃, and the calcination time is 1-10 h;
(4) naturally cooling the mixture obtained by the second calcination to room temperature, grinding and mixingUniformly mixing, calcining for the third time in an air atmosphere at the temperature of 530-600 ℃ for 1-10 h, and naturally cooling to room temperature to obtain Eu3+Doped transition metal tellurium oxide phosphor.
3. Eu according to claim 23+The preparation method of the doped transition metal tellurium oxide fluorescent powder is characterized in that the fluorescent powder contains niobium ions Nb5+The compound of (1) is niobium pentoxide or niobium chloride; the vanadium ion V5+The compound of (A) is ammonium metavanadate or vanadium pentoxide; the tellurium ion-containing Te4+The compound of (1) is tellurium dioxide or tellurium tetrachloride; the Eu ion containing europium3+The compound of (1) is europium oxide.
4. A Eu according to claim 2 or 33+The preparation method of the doped transition metal tellurium oxide fluorescent powder is characterized in that the first calcination temperature in the step (2) is 400 ℃, and the calcination time is 1 h; the second calcination in the step (3) is carried out at the temperature of 400 ℃ for 10 h; the third calcination temperature in the step (4) is 530 ℃, and the calcination time is 10 h.
5. Eu according to claim 13+The doped transition metal tellurium oxide fluorescent powder is applied to the preparation of a luminescent device or a display device which takes ultraviolet light-near ultraviolet light as an excitation light source.
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| CN108587627A (en) * | 2018-06-01 | 2018-09-28 | 苏州大学张家港工业技术研究院 | Eu3+Ion-activated fluorine chlorine telluric acid bismuth and its preparation method and application |
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| US3509064A (en) * | 1966-12-01 | 1970-04-28 | Gen Telephone & Elect | Alkaline earth tellurate phosphors |
| CN102690659A (en) * | 2012-06-07 | 2012-09-26 | 中国计量学院 | Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof |
| CN102690660A (en) * | 2012-06-07 | 2012-09-26 | 中国计量学院 | Red fluorescent powder for light-emitting diode (LED) and preparation method for red fluorescent powder |
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