CN103396795B - Vanadate fluorescent powder, and preparation method and application thereof - Google Patents
Vanadate fluorescent powder, and preparation method and application thereof Download PDFInfo
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- CN103396795B CN103396795B CN201310324640.3A CN201310324640A CN103396795B CN 103396795 B CN103396795 B CN 103396795B CN 201310324640 A CN201310324640 A CN 201310324640A CN 103396795 B CN103396795 B CN 103396795B
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 title claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 230000005284 excitation Effects 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical group 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- -1 boron ion Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 29
- 238000004020 luminiscence type Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 4
- 108010043121 Green Fluorescent Proteins Proteins 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 12
- 238000012544 monitoring process Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 230000006399 behavior Effects 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 4
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 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 description 1
- 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 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000003836 solid-state method Methods 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
- 229910001934 tungsten pentoxide Inorganic materials 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a vanadate green fluorescent powder, and a preparation method and application thereof, belonging to the technical field of fluorescent materials. The chemical formula of the vanadate fluorescent powder is Cs5V3-3xM3xO10, wherein M is B<3+>, P<5+>, W<5+>, Mo<6+>, Zr<4+>, Ti<4+>, Nb<5+> or Ta<5+>, x is the mol percentage of M which is doped and substituted for V<5+>, and 0<=x<=0.1. The invention adopts a solid-phase sintering method to obtain the vanadate fluorescent powder, wherein calcination is carried out in an air atmosphere at 600-800 DEG C for 4-9 hours. The fluorescent powder can emit bright green fluorescence under the excitation of near-ultraviolet light, and can be used for near-ultraviolet-excited white light LEDs (light-emitting diodes). The fluorescent powder provided by the invention has the advantages of high luminescence efficiency, wide excitation wavelength, simple preparation method, low sintering temperature, no pollution and the like.
Description
Technical field
The present invention relates to a kind of inorganic fluorescent material, particularly a kind of under near ultraviolet excitation, the preparation method of the fluorescent material of transmitting green fluorescence and application thereof, belong to fluorescent material technical field.
Background technology
In recent years, because light-emitting diode (LED) has the advantages such as high-luminous-efficiency, long-life, low energy consumption and environmentally safe, became a kind of New Solid illuminating device developing rapidly.The countries in the world a large amount of manpower and financial resources of numerous and confused input is carried out research and the application of white light LEDs.Fluorescent material is as the important component part of white light LEDs, has great importance for improving the performance index such as the luminous efficiency, useful life, colour temperature, color rendering index of LED.At present, the technology of preparing of white light LEDs mainly contains two kinds: the one, by three kinds of monochromatic LED combination results white lights of red, green, blue, can arbitrarily adjust color, but power supply is complicated, and cost is higher; The 2nd, excite other luminescent material to be mixed to form white light with LED, coordinate the fluorescent material of Yellow light-emitting low temperature with blue-ray LED, blue-ray LED coordinates and glows and the fluorescent material of green glow or excite three kinds of fluorescent material of red, green, blue with near ultraviolet LED, the method is no matter be to be all better than first method aspect feasibility, practicality or commercialization, and can obtain higher color developing, colour temperature can be mated arbitrarily within 2500～10000 K scopes, therefore become more popular research direction, there is application prospect more extensively.
At present, can be used for the green emitting phosphor that near ultraviolet (360～410 nanometer) type white light LEDs uses also few, studying more is aluminate-base green emitting phosphor, mainly taking high temperature solid-state method as main, and vanadic acid alkali green emitting phosphor research less.For example, green emitting phosphor (Ce
0.67, Tb
0.33) MgAl
11o
19(CMAT) as a kind of good green powder of aluminate three primary colors, at present, the main application fields of this fluorescent material is at fluorescent lamp (FL) and emission display equipment, as electroluminescence panel (EL), plasma display (PDP) and Field Emission Display (FED) etc.Along with making constant progress of science and technology, the continuous enhancing of people's environmental consciousness, light source and emerging display apparatus etc. to the demand of efficient, energy-conservation fluorescent material also in sustainable growth, luminous intensity and the luminous efficiency of commercial green emitting phosphor can not satisfy the demands preferably, sintering temperature is higher, and uses rare earth element price comparison costliness.Such fluorescent material need to be at H in addition
2+ N
2, synthetic among the reducing atmosphere such as CO, H in building-up process
2+ N
2can not be penetrated into for a full due among synthetic fluorescent material powder with reducing gass such as CO, badly influence the luminous of fluorescent material; The CO gas also using due to reduction has murder by poisoning, H
2+ N
2reducing gas has danger, and misoperation can set off an explosion, and therefore, its production has been subject to certain restriction.
Vanadate has good chemical stability and thermal stability as inorganic fluorescent material, also be the fluorescence synthetic material with high-luminous-efficiency simultaneously, higher crystallinity and visible light permeability, be a kind of better luminescent material, can be applied to preferably near ultraviolet type phosphor for white light LED.Chinese invention patent CN102517008A discloses a kind of alkaline earth metal pyrovanadate blue-green fluorescent powder, and this blue-green fluorescent powder is the alkaline earth pyrovanadate of europium doping, and its chemical expression is M
2-xv
2o
7: Eu
2+x, in formula, M is expressed as the combination of one or both ions in alkaline-earth metal, 0.005≤x≤0.2.The alkaline earth pyrovanadate blue-green fluorescent powder of this invention can be excited by 250～350 nano-ultraviolet lights, sends efficient main emission peak adjustable blue-green fluorescence in 480～520 nanometer range.
To sum up, the present invention adopts vanadate matrix, utilizes solid sintering technology synthesize white light LED green emitting phosphor to have application prospect potentially, and preparation condition safety, environmental protection, and tool is of great significance.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of novel green emitting phosphor luminescent material, preparation method and application thereof are provided, and it is high that the product providing has degree of crystallinity, and luminous mass is good, the feature that cost is low, and preparation technology is simple, safe, pollution-free.
For reaching above object, the technical solution used in the present invention is to provide a kind of vanadate phosphor, and its chemical formula is Cs
5v
3-3xm
3xo
10, wherein M is ion B
3+, P
5+, W
5+, Mo
6+, Zr
4+, Ti
4+, Nb
5+and Ta
5+in one, x is M doped and substituted V
5+molar percentage coefficient, 0≤x≤0.1; It launches the green fluorescence of centre wavelength in 495～570 nanometers under near ultraviolet excitation.
A preparation method for vanadate phosphor as above, comprises the steps:
1, with the compound that contains M, contain cesium ion Cs
+compound, contain vanadium ion V
5+compound be raw material, by chemical formula Cs
5v
3-3xm
3xo
10the mol ratio of middle element takes raw material, grinds and mixes; Described M is ion B
3+, P
5+, W
5+, Mo
6+, Zr
4+, Ti
4+, Nb
5+and Ta
5+in one, x is M doped and substituted V
5+molar percentage coefficient, 0≤x≤0.1;
2, by the mixture obtaining presintering under air atmosphere, sintering temperature is 200～600 DEG C, and sintering time is 2～8 hours, presintering 1～2 time;
3, the mixture after presintering is naturally cooling, grind and mix, be to calcine under the condition of 600～800 DEG C in temperature, calcination time is 4～9 hours, obtains a kind of vanadate phosphor.
In technical solution of the present invention, contain boron ion B
3+compound be the one in diboron trioxide, boric acid; Contain phosphonium ion P
5+compound be the one in phosphorus pentoxide, phosphoric acid; Contain tungsten ion W
5+, molybdenum ion Mo
6+compound be respectively the one in their ammonium salt, oxide, contain Zr
4+, Ti
4+, Nb
5+and Ta
5+compound be respectively the one in their oxide, carbonate, hydroxide, nitrate.
The described vanadium ion V that contains
5+compound be the one in vanadic oxide, metavanadic acid ammonia.The described cesium ion Cs that contains
+compound be the one in cesium oxide, cesium hydroxide, cesium carbonate, cesium nitrate.
Sintering temperature described in preparation method's step 2 is 250～550 DEG C, and sintering time is 4～7 hours.Calcining heat described in step 3 is 650～750 DEG C, and calcination time is 5～8 hours.The calcination atmosphere of step 3 is the mixture of air, oxygen and nitrogen, or one in the mixture of oxygen and inert gas.
Technical solution of the present invention also comprises the application of vanadate phosphor, is coordinated appropriate blueness and red fluorescence powder, applies and is packaged in outside InGaN diode, prepares White-light LED illumination device.
Compared with prior art, the advantage of technical solution of the present invention is:
1, the vanadate that prepared by the present invention has good chemical stability and thermal stability, and meanwhile, fluorescence synthetic material luminous efficiency is high, has higher crystallinity and visible light permeability.The prepared atmosphere of fluorescent material is the one of the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and preparation condition safety, can save the energy, reduces costs, and is conducive to promote produce.
2, the excitation wavelength of fluorescent material provided by the invention is mainly in the black light region of 300～400 nanometers, under near ultraviolet excitated, launch green glow, mate the radiation wavelength of near ultraviolet InGaN chip completely, it can coordinate appropriate blueness and red fluorescence powder, apply and be packaged in outside InGaN diode, can prepare White-light LED illumination equipment, meet preferably the application of near ultraviolet type white light LEDs.
3, host material of the present invention has been broken through the restriction of traditional rare earth doped luminescent material, has avoided the higher problem of cost that uses in a large number the thuliums such as Ce, Eu, Y, Gd to bring because of need.Meanwhile, the preparation process of luminescent material of the present invention is simple, easy operating, and product easily collecting, pollution-free, without waste water and gas discharge, environmental friendliness, is especially applicable to serialization and produces.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 is prepared sample Cs
5v
3o
10x-ray powder diffraction collection of illustrative plates;
Fig. 2 is that the embodiment of the present invention 1 is prepared sample Cs
5v
3o
10the exciting light spectrogram near ultraviolet region obtaining in monitoring wavelength 500 nanometers;
Fig. 3 is that the embodiment of the present invention 1 is prepared sample Cs
5v
3o
10the luminescent spectrum obtaining under black light 360 nanometers excite;
Fig. 4 is that the embodiment of the present invention 1 is prepared sample Cs
5v
3o
10the decay of luminescence curve chart obtaining in monitoring wavelength 500 nanometers;
Fig. 5 is that the embodiment of the present invention 2 is prepared sample Cs
5v
2.7ti
0.3o
10the exciting light spectrogram near ultraviolet region obtaining in monitoring wavelength 480 nanometers;
Fig. 6 is that the embodiment of the present invention 2 is prepared sample Cs
5v
2.7ti
0.3o
10the luminescent spectrum obtaining under black light 350 nanometers excite;
Fig. 7 is that the embodiment of the present invention 2 is prepared sample Cs
5v
2.7ti
0.3o
10the decay of luminescence curve chart obtaining in monitoring wavelength 480 nanometers;
Fig. 8 is that the embodiment of the present invention 3 is prepared sample Cs
5v
2.85mo
0.15o
10the exciting light spectrogram near ultraviolet region obtaining in monitoring wavelength 440 nanometers;
Fig. 9 is that the embodiment of the present invention 3 is prepared sample Cs
5v
2.85mo
0.15o
10the luminescent spectrum obtaining under black light 320 nanometers excite;
Figure 10 is that the embodiment of the present invention 3 is prepared sample Cs
5v
2.85mo
0.15o
10the decay of luminescence curve chart obtaining in monitoring wavelength 440 nanometers.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
Embodiment 1
Preparation Cs
5v
3o
10: take 1.629 grams of cesium carbonate (Cs
2cO
3), 0.71 gram of ammonium metavanadate (NH
4vO
3), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 350 DEG C, calcination time is 5 hours, presintering 2 times; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 690 DEG C, and calcination time is 5 hours, obtains a kind of vanadate phosphor.
Referring to accompanying drawing 1, it is the X-ray powder diffraction collection of illustrative plates of the sample prepared by the present embodiment technical scheme, and with the comparison of standard card PDF#50-0027, XRD test result shows, prepared sample Cs
5v
3o
10for monophase materials.
Referring to accompanying drawing 2, it is the exciting light spectrogram near ultraviolet region that the sample prepared by the present embodiment technical scheme obtains in monitoring wavelength 500 nanometers, is shown by Fig. 2, and this fluorescent material can mate near ultraviolet LED chip well.
Referring to accompanying drawing 3, it is the luminescent spectrum that the sample prepared by the present embodiment technical scheme obtains under black light 360 nanometers excite, as seen from Figure 3, the main center emission wavelength of this material is the green emitting wave band of approximately 525 nanometers, calculate through CIE simultaneously, the coordinate of learning it is x=0.306, and y=0.419 shows green light.It can finely be applicable to the white light LEDs taking black light as excitation source, and its luminous quantum efficiency is higher.
Referring to accompanying drawing 4, it is the decay of luminescence curve that the sample prepared by the present embodiment technical scheme obtains under monitoring wavelength 500 nanometers excite, and this curve presents single index decay, and luminescent lifetime is 11 μ s.
Embodiment 2
Preparation Cs
5v
2.7ti
0.3o
10: take 1.87 grams of cesium hydroxides (CsOH), 0.79 gram of ammonium metavanadate (NH
4vO
3), 0.06 gram of titanium dioxide (TiO
2), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 250 DEG C, calcination time is 4 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 650 DEG C, and calcination time is 6 hours, obtains a kind of vanadate phosphor.
Referring to accompanying drawing 5, it is the exciting light spectrogram near ultraviolet region that the sample prepared by the present embodiment technical scheme obtains in monitoring wavelength 480 nanometers, is shown by Fig. 5, and this fluorescent material can mate near ultraviolet LED chip well.
Referring to accompanying drawing 6, it is the luminescent spectrum that the sample prepared by the present embodiment technical scheme obtains under black light 350 nanometers excite, as seen from Figure 6, the main center emission wavelength of this material is the green emitting wave band of approximately 525 nanometers, calculate through CIE simultaneously, the coordinate of learning it is x=0.306, and y=0.419 shows green light.It can finely be applicable to the white light LEDs that black light is excitation source, and its luminous quantum efficiency is higher.
Referring to accompanying drawing 7, it is the decay of luminescence curve that the sample prepared by the present embodiment technical scheme obtains under exciting light 480 nanometers excite, and this curve presents single index decay, and luminescent lifetime is 11 μ s.
Embodiment 3
Preparation Cs
5v
2.85mo
0.15o
10: take 1.76 grams of cesium oxide (Cs
2o), 0.65 gram of vanadic oxide (V
2o
5), 0.067 gram of ammonium molybdate ((NH
4)
6mo
7o
24-4H
2o), after grinding and mixing, under air atmosphere, calcine in agate mortar, calcining heat is 280 DEG C, and calcination time is 6 hours, presintering 2 times; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 700 DEG C, and calcination time is 7 hours, obtains a kind of vanadate phosphor.
Referring to accompanying drawing 8, it is the exciting light spectrogram near ultraviolet region that the sample prepared by the present embodiment technical scheme obtains in monitoring wavelength 440 nanometers, is shown by Fig. 8, and this fluorescent material can mate near ultraviolet LED chip well.
Referring to accompanying drawing 9, it is the luminescent spectrum that the sample prepared by the present embodiment technical scheme obtains under black light 320 nanometers excite, as seen from Figure 9, the main center emission wavelength of this material is the green emitting wave band of approximately 525 nanometers, calculate through CIE simultaneously, the coordinate of learning it is x=0.306, and y=0.419 shows green light.It can finely be applicable to the white light LEDs that black light is excitation source, and its luminous quantum efficiency is higher.
Referring to accompanying drawing 10, it is the decay of luminescence curve that the sample prepared by the present embodiment technical scheme obtains under monitoring wavelength 440 nanometers excite, and this curve presents single index decay, and luminescent lifetime is 11 μ s.
Embodiment 4
Preparation Cs
5v
2.82b
0.18o
10: take 2.44 grams of cesium nitrate (CsNO
3), 0.64 gram of vanadic oxide (V
2o
5), 0.016 gram of boron oxide (B
2o
3), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 300 DEG C, calcination time is 7 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 750 DEG C, and calcination time is 8 hours, obtains a kind of vanadate phosphor.Its main structural behaviour, excitation spectrum, luminescent spectrum and decay of luminescence are similar to embodiment 1.
Embodiment 5
Preparation Cs
5v
2.73p
0.27o
10: take 2.04 grams of cesium carbonate (Cs
2cO
3), 0.8 gram of ammonium metavanadate (NH
4vO
3), 0.07 gram of phosphoric acid (H
3pO
4), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 400 DEG C, calcination time is 5 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 720 DEG C, and calcination time is 7 hours, obtains a kind of vanadate phosphor.Its main structural behaviour, excitation spectrum, luminescent spectrum and decay of luminescence are similar to embodiment 1.
Embodiment 6
Preparation Cs
5v
2.94zr
0.06o
10: take 2.04 grams of cesium oxide (Cs
2o), 0.15 gram of ammonium metavanadate (NH
4vO
3), 0.032 gram of zirconium hydroxide (ZrO (OH)
2-nH
2o), after grinding and mixing, under air atmosphere, calcine in agate mortar, calcining heat is 360 DEG C, and calcination time is 4 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 680 DEG C, and calcination time is 7 hours, obtains a kind of vanadate phosphor.Its main structural behaviour, excitation spectrum, luminescent spectrum and decay of luminescence are similar to embodiment 1.
Embodiment 7
Preparation Cs
5v
2.9997w
0.0003o
10: take 2.04 grams of cesium carbonate (Cs
2cO
3), 0.88 gram of ammonium metavanadate (NH
4vO
3), 0.0002 gram of tungsten pentoxide (W
2o
5), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 380 DEG C, calcination time is 5 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 730 DEG C, and calcination time is 6 hours, obtains a kind of vanadate phosphor.Its main structural behaviour, excitation spectrum, luminescent spectrum and decay of luminescence are similar to embodiment 1.
Embodiment 8
Preparation Cs
5v
2.76nb
0.24o
10: take 1.76 grams of cesium oxide (Cs
2o), 0.63 gram of vanadic oxide (V
2o
5), 0.08 gram of niobium pentaoxide (Nb
2o
5), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 390 DEG C, calcination time is 6 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 740 DEG C, and calcination time is 8 hours, obtains a kind of vanadate phosphor.Its main structural behaviour, excitation spectrum, luminescent spectrum and decay of luminescence are similar to embodiment 1.
Embodiment 9
Preparation Cs
5v
2.88ta
0.12o
10: take 2.44 grams of cesium nitrate (CsNO
3), 0.66 gram of vanadic oxide (V
2o
5), 0.07 gram of tantalum pentoxide (Ta
2o
5), after grinding in agate mortar and mixing, under air atmosphere, to calcine, calcining heat is 420 DEG C, calcination time is 4 hours; Be cooled to room temperature, take out sample; After it is fully ground again, be placed in Muffle furnace, in air atmosphere, calcine, calcining heat is 670 DEG C, and calcination time is 5 hours, obtains a kind of vanadate phosphor.Its main structural behaviour, excitation spectrum, luminescent spectrum and decay of luminescence are similar to embodiment 1.
Claims (9)
1. a vanadate phosphor, is characterized in that: its chemical formula is Cs
5v
3-3xm
3xo
10, wherein M is ion B
3+, P
5+, W
5+, Mo
6+, Zr
4+, Ti
4+, Nb
5+and Ta
5+in one, x is M doped and substituted V
5+molar percentage coefficient, 0 < x≤0.1; It launches the green fluorescence of centre wavelength in 495～570 nanometers under near ultraviolet excitation.
2. a preparation method for vanadate phosphor as claimed in claim 1, is characterized in that comprising the steps:
(1) with the compound that contains M, contain cesium ion Cs
+compound, contain vanadium ion V
5+compound be raw material, by chemical formula Cs
5v
3-3xm
3xo
10the mol ratio of middle element takes raw material, grinds and mixes; Described M is ion B
3+, P
5+, W
5+, Mo
6+, Zr
4+, Ti
4+, Nb
5+and Ta
5+in one, x is M doped and substituted V
5+molar percentage coefficient, 0 < x≤0.1;
(2) by the mixture obtaining presintering under air atmosphere, sintering temperature is 200～600 DEG C, and sintering time is 2～8 hours, presintering 1～2 time;
(3) mixture after presintering is naturally cooling, grind and mix, be to calcine under the condition of 600～800 DEG C in temperature, calcination time is 4～9 hours, obtains a kind of vanadate phosphor.
3. the preparation method of a kind of vanadate phosphor according to claim 2, is characterized in that: contain boron ion B
3+compound be the one in diboron trioxide, boric acid; Contain phosphonium ion P
5+compound be the one in phosphorus pentoxide, phosphoric acid; Contain tungsten ion W
5+, molybdenum ion Mo
6+compound be respectively the one in their ammonium salt, oxide, contain Zr
4+, Ti
4+, Nb
5+and Ta
5+compound be respectively the one in their oxide, carbonate, hydroxide, nitrate.
4. the preparation method of a kind of vanadate phosphor according to claim 2, is characterized in that: the described vanadium ion V that contains
5+compound be the one in vanadic oxide, metavanadic acid ammonia.
5. the preparation method of a kind of vanadate phosphor according to claim 2, is characterized in that: the described cesium ion Cs that contains
+compound be the one in cesium oxide, cesium hydroxide, cesium carbonate, cesium nitrate.
6. the preparation method of a kind of vanadate phosphor according to claim 2, is characterized in that: the described sintering temperature of step (2) is 250～550 DEG C, and sintering time is 4～7 hours.
7. the preparation method of a kind of vanadate phosphor according to claim 2, is characterized in that: the described calcining heat of step (3) is 650～750 DEG C, and calcination time is 5～8 hours.
8. the preparation method of a kind of vanadate phosphor according to claim 2, is characterized in that: the calcination atmosphere of step (3) is the mixture of air, oxygen and nitrogen, or one in the mixture of oxygen and inert gas.
9. an application for vanadate phosphor as claimed in claim 1, is characterized in that: coordinated appropriate blueness and red fluorescence powder, apply and be packaged in outside InGaN diode, prepare White-light LED illumination device.
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