CN103589429A - Vanadate fluorescent material and white light emitting device - Google Patents
Vanadate fluorescent material and white light emitting device Download PDFInfo
- Publication number
- CN103589429A CN103589429A CN201310508472.3A CN201310508472A CN103589429A CN 103589429 A CN103589429 A CN 103589429A CN 201310508472 A CN201310508472 A CN 201310508472A CN 103589429 A CN103589429 A CN 103589429A
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- China
- Prior art keywords
- luminescent material
- photoexcitation
- vanadate
- euca
- illustrative plates
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- 239000000463 material Substances 0.000 title claims abstract description 88
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 230000005855 radiation Effects 0.000 claims description 43
- 230000005284 excitation Effects 0.000 claims description 11
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- 230000001443 photoexcitation Effects 0.000 description 42
- 238000010586 diagram Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- 238000002156 mixing Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000005245 sintering Methods 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical class O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical class [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical class [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
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- 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
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- Luminescent Compositions (AREA)
Abstract
The invention provides a vanadate fluorescent material with the structural formula: Eu[1-x] Ca9(VO4)7:Max. Ma is Sm<3+>, Bi<3+>, Tb<3+>, La<3+> or Y<3+>, and 0<=x<=0.15. The vanadate fluorescent material can emit visible light after being excited by ultraviolet light or blue light and can be made into a white light emitting device after being combined with various other applicative fluorescent materials.
Description
The application is that the application number of submitting on December 12nd, 2008 is 200810188103.X, and what denomination of invention was the application for a patent for invention of " vanadate luminescent material and white light emitting device " divides an application.
Technical field
The present invention relates to a kind of vanadic acid salt fluorescent material, relates more specifically to this kind of material in the application of white light emitting device.
Background technology
The luminous efficiency of photodiode (LED) is high, and has energy-conservation and characteristic environmental protection, can be used to replace the vehement lamp of traditional heat and luminescent lamp.In white light LEDs, the most important thing is the composition of fluorescent material, this will have influence on the characteristics such as luminous efficiency, stability, color rendering, colour temperature, work-ing life.
The excitation light source of traditional fluorescent material mostly be short wavelength UV (as 147,172,185 or 254nm), this kind of fluorescent material is high in absorption and the light conversion efficiency of the UV of this wave band.Compare, application long wavelength UV is more rare to the fluorescent material that visible ray (350-470nm) excites.
In known technology, the material of main part of fluor mostly is the oxide compound of sulfide, nitride or silicate or aluminate class.The light conversion efficiency of sulphide phosphor is high, but shortcoming is poor stability, is subject to aqueous vapor or oxygen is deteriorated; The good stability of nitride phosphor, but it is synthetic difficult, often needs High Temperature High Pressure preparation process, and not only danger also raises the cost.
Summary of the invention
The object of the present invention is to provide a kind of preparation temperature low and there is the vanadate luminescent material of high optics and chemical stability.
The invention provides a kind of vanadate luminescent material, there is structural formula as follows: Eu
1-xca
9-y(VO
4)
7: Ma
x, Mb
y; Wherein Ma is Sm
3+, Bi
3+, La
3+or Y
3+, Mb is Sr
2+, Ba
2+or Zn
2+; And 0<x≤0.15,0<y≤1.
The present invention also provides a kind of vanadate luminescent material, has structural formula as follows: EuCa
9-y(VO
4)
7: Mb
y; Wherein Mb is Sr
2+, Ba
2+or Zn
2+; And 0<y≤1.
The present invention also provides a kind of vanadate luminescent material, has structural formula as follows: Eu
1-xca
9(VO
4)
7: Ma
x; Wherein Ma is Sm
3+, Bi
3+, La
3+or Y
3+, and 0<x≤0.15.
The present invention also provides a kind of white light emitting device, comprises above-mentioned vanadic acid fluorescent material and excitation light source, and the wavelength of excitation light source is the UV-light of 200nm to 400nm or the blue light of 400nm to 470nm.
Compared with prior art, the advantage of vanadate luminescent material of the present invention is: preparation process temperature is low, have the characteristics such as high optics and chemical stability.Vanadic acid salt fluorescent material provided by the present invention, if collocation can be sent blue light or ultraviolet photodiode or laser diode, can radiate visible ray.If the of all kinds fluorescence material combination applicable with other, can make white light emitting device again.
Accompanying drawing explanation
Fig. 1 is vanadate luminescent material Eu
0.9ca
9(VO
4)
7: Sm
3+ 0.1photoexcitation collection of illustrative plates;
Fig. 2 is vanadate luminescent material Eu
0.9ca
9(VO
4)
7: Sm
3+ 0.1photic radiation collection of illustrative plates;
Fig. 3 is vanadate luminescent material EuCa
8.5(VO
4)
7: Zn
2+ 0.5photoexcitation collection of illustrative plates;
Fig. 4 is vanadate luminescent material EuCa
8.5(VO
4)
7: Zn
2+ 0.5photic radiation collection of illustrative plates;
Fig. 5 is vanadate luminescent material Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5photoexcitation collection of illustrative plates;
Fig. 6 is vanadate luminescent material Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5photic radiation collection of illustrative plates;
Fig. 7 is vanadate luminescent material Eu
0.9ca
9(VO
4)
7: Sm
3+ 0.1the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Fig. 8 is vanadate luminescent material EuCa
8.5(VO
4)
7: Zn
2+ 0.5the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Fig. 9 is vanadate luminescent material Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 10 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: Sm
3+ 0.15photoexcitation collection of illustrative plates;
Figure 11 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: Sm
3+ 0.15photic radiation collection of illustrative plates;
Figure 12 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: Sm
3+ 0.15the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 13 is vanadate luminescent material EuCa
8(VO
4)
7: Zn
2+photoexcitation collection of illustrative plates;
Figure 14 is vanadate luminescent material EuCa
8(VO
4)
7: Zn
2+photic radiation collection of illustrative plates;
Figure 15 is vanadate luminescent material EuCa
8(VO
4)
7: Zn
2+the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 16 is vanadate luminescent material Eu
0.85ca
8(VO
4)
7: Sm
3+ 0.15, Zn
2+photoexcitation collection of illustrative plates;
Figure 17 is vanadate luminescent material Eu
0.85ca
8(VO
4)
7: Sm
3+ 0.15, Zn
2+photic radiation collection of illustrative plates;
Figure 18 is vanadate luminescent material Eu
0.85ca
8(VO
4)
7: Sm
3+ 0.15, Zn
2+the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 19 is vanadate luminescent material EuCa
9(VO
4)
7photoexcitation collection of illustrative plates;
Figure 20 is vanadate luminescent material EuCa
9(VO
4)
7photic radiation collection of illustrative plates;
Figure 21 is vanadate luminescent material EuCa
9(VO
4)
7the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 22 is vanadate luminescent material EuCa
9(VO
4)
7with vanadate luminescent material Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5the luminous comparison diagram of photoexcitation;
Figure 23 is vanadate luminescent material Eu
0.95ca
9(VO
4)
7: Bi
3+ 0.05photoexcitation collection of illustrative plates;
Figure 24 is vanadate luminescent material Eu
0.95ca
9(VO
4)
7: Bi
3+ 0.05photic radiation collection of illustrative plates;
Figure 25 is vanadate luminescent material Eu
0.95ca
9(VO
4)
7: Tb
3+ 0.05photoexcitation collection of illustrative plates;
Figure 26 is vanadate luminescent material Eu
0.95ca
9(VO
4)
7: Tb
3+ 0.05photic radiation collection of illustrative plates;
Figure 27 is vanadate luminescent material EuCa
8.5(VO
4)
7: Sr
2+ 0.5photoexcitation collection of illustrative plates;
Figure 28 is vanadate luminescent material EuCa
8.5(VO
4)
7: Sr
2+ 0.5photic radiation collection of illustrative plates;
Figure 29 is vanadate luminescent material EuCa
8.5(VO
4)
7: Sr
2+ 0.5the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 30 is vanadate luminescent material EuCa
8(VO
4)
7: Sr
2+photoexcitation collection of illustrative plates;
Figure 31 is vanadate luminescent material EuCa
8(VO
4)
7: Sr
2+photic radiation collection of illustrative plates;
Figure 32 is vanadate luminescent material EuCa
8(VO
4)
7: Sr
2+the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 33 is vanadate luminescent material EuCa
8.5(VO
4)
7: Ba
2+ 0.5photoexcitation collection of illustrative plates;
Figure 34 is vanadate luminescent material EuCa
8.5(VO
4)
7: Ba
2+ 0.5photic radiation collection of illustrative plates;
Figure 35 is vanadate luminescent material EuCa
8.5(VO
4)
7: Ba
2+ 0.5the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 36 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: Y
3+ 0.15photoexcitation collection of illustrative plates;
Figure 37 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: Y
3+ 0.15photic radiation collection of illustrative plates;
Figure 38 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: Y
3+ 0.15the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681;
Figure 39 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: La
3+ 0.15photoexcitation collection of illustrative plates;
Figure 40 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: La
3+ 0.15photic radiation collection of illustrative plates; And
Figure 41 is vanadate luminescent material Eu
0.85ca
9(VO
4)
7: La
3+ 0.15the luminous comparison diagram of photoexcitation with commercial goods Kasei-KX681.
Embodiment
The invention provides vanadate luminescent material and there is structural formula as Eu
1-xca
9-y(VO
4)
7: Ma
x, Mb
y.Ma is Sm
3+, Bi
3+, Tb
3+, La
3+or Y
3+deng trivalent element, Mb is Sr
2+, Ba
2+or Zn
2+deng dyad.In an embodiment of the present invention, 0<x≤0.15 and 0<y≤1, the structure of vanadate luminescent material can be Eu
1-xca
9-y(VO
4)
7: Sm
x, Zn
y.In another embodiment of the present invention, x=0 and 0<y≤1, the structural formula of vanadate luminescent material is EuCa
9-y(VO
4)
7: Mb
yas EuCa
9-y(VO
4)
7: Zn
y.In another embodiment of the present invention, 0<x≤0.15 and y=0, the structural formula of vanadate luminescent material is Eu
1-xca
9(VO
4)
7: Ma
xas Eu
1-xca
9(VO
4)
7: Sm
x.
In an embodiment of the present invention, doping Sm
3+vanadate at 405nm, have one
6h
5/2→
4k
11/2spectrum of properties.And the Sm that simultaneously adulterates
3+with Zn
2+the excitation spectrum of vanadate between the 394～406nm Sm that adulterates more merely
3+vanadate there is better performance.
After above-mentioned vanadate excites via blue light (400nm to 470nm) or UV-light (200nm to 400nm), can radiate the visible ray of different wave length.Above-mentioned can photodiode or laser diode in order to send that the excitation light source of blue light or UV-light can be.
The forming method of above-mentioned vanadate luminescent material is solid state reaction, first according to stoichiometry, weighs the reagent of suitable mol ratio.Reagent containing Eu can be oxide compound as Eu
2o
3.Reagent containing Ca can be oxide compound (CaO) or carbonic acid thing (CaCO
3).Containing Sm
3+, Bi
3+, Tb
3+, La
3+, Y
3+, Sr
2+, Ba
2+, Zn
2+reagent can be oxide compound as Sm
2o
3, Y
2o
3, Bi
2o
3or ZnO, carbonic acid thing is as SrCO
3or BaCO
3.Vanadic acid source can be containing vanadium reagents as Vanadium Pentoxide in FLAKES (V
2o
5) or ammonium meta-vanadate (NH
4vO
3).The mentioned reagent of getting equivalence ratio is ground after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus after then putting into crucible, in 700-1100 ℃ of sintering after a few hours, and the vanadate luminescent material that gets final product above-mentionedly.
In an embodiment of the present invention, vanadate luminescent material radiates ruddiness after blue light or ultraviolet excitation.In this embodiment, can be by above-mentioned vanadate luminescent material, the green glow fluorescent material that the blue-light fluorescent material that combination ultraviolet ray can excite and ultraviolet ray or blue light can excite, and photodiode or the laser diode equal excitation source of arranging in pairs or groups and can send near-ultraviolet ray, to make white light emitting diode or white light laser diode light source.Wherein blue-light fluorescent material comprises BaMgAl
10o
17: Eu
2+, (Ba, Sr, Ca)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, 2SrO*0.84P
2o
5* 0.16B
2o
3: Eu
2+, Sr
2si
3o
8* 2SrCl
2: Eu
2+(Mg, Ca, Sr, Ba, Zn)
3b
2o
6: Eu
2+, or other suitable blue-light fluorescent material; Green glow fluorescent material can be BaMgAl
10o
17: Eu
2+, Mn
2+, SrGa
2s
4: Eu
2+, (Ca, Sr, Ba) Al
2o
4: Eu
2+, Mn
2+, (Ca, Sr, Ba)
4al
14o
25: Eu
2+, Ca
8mg (SiO
4)
4cl
2: Eu
2+, Mn
2+or other suitable green light material.If the blue light and the green glow fluorescent material that use ultraviolet ray to excite are the application mode of " directly the exciting " in ultraviolet photodiode or laser diode equal excitation source; If what use is the green glow fluorescent material that blue light can excite, belong to the application mode of blue light that blue-light fluorescent material sends " indirectly exciting ".And ruddiness, blue light, with the combination of green glow fluorescent material, also respectively have its different optimum formulas or ratio.
The white light devices such as aforesaid photodiode or white light laser diode, can be by above-mentioned various indigo plant/green/red fluor that waits according to optimum formula or ratio, evenly blending dispersion is after transparent optical cement, is packaged in can send the chip of the photodiode of near-ultraviolet ray or laser diode etc. and make.But it should be noted that with UV-light and do excitation light source, in white light emitting device outermost, uv filter should be set or utilize other UV-light to completely cut off mode, human body or eyes are damaged avoiding.
For clearer, point out feature of the present invention, spy is schematically illustrated in following preferred embodiment explanation.
Embodiment 1 (Eu
0.9ca
9(VO
4)
7: Sm
3+ 0.1)
Get 9mol CaCO
3(0.3420g, FW=100.086, Mallinckodt Baker99.95%), 0.9mol Eu
2o
3(0.0601g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2417g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.1mol Sm
2o
3(0.0066g, FW=348.72, FLUKA99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.9ca
9(VO
4)
7: Sm
3+ 0.1.As shown in Figures 1 and 2, it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.65,0.34) to the photoexcitation radiation collection of illustrative plates of above-mentioned product.Above-mentioned product Eu
0.9ca
9(VO
4)
7: Sm
3+ 0.1with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in Figure 7.
Embodiment 2 (EuCa
8.5(VO
4)
7: Zn
2+ 0.5)
Get 8.5mol CaCO
3(0.3199g, FW=100.086, Mallinckodt Baker99.95%), 1mol Eu
2o
3(0.0662g, FW=351.93, STREM99.99%), 0.5mol ZnO (0.0153g, FW=81.39, SHOWA99.0%) and 3.5mol V
2o
5(0.2393g, FW=181.88, KOJUNDO99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the EuCa of pure phase after taking-up
8.5(VO
4)
7: Zn
2+ 0.5.As shown in Figure 3 and Figure 4, it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.65,0.34) to the photoexcitation radiation collection of illustrative plates of above-mentioned product.Above-mentioned product EuCa
8.5(VO
4)
7: Zn
2+ 0.5with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in Figure 8.
Embodiment 3 (Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5)
Get 8.5mol CaCO
3(0.3199g, FW=100.086, Mallinckodt Baker99.95%), 0.9mol Eu
2o
3(0.0595g, FW=351.93, STREM99.99%), 0.5mol ZnO (0.0153g, FW=81.39, SHOWA99.0%), 0.1mol Sm
2o
3(0.0066g, FW=348.72, FLUKA99.9%) and 3.5mol V
2o
5(0.2394g, FW=181.88, KOJUNDO99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Fig. 5 and Fig. 6, and it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.65,0.34).Above-mentioned product Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in Figure 9.
Embodiment 4 (Eu
0.85ca
9(VO
4)
7: Sm
3+ 0.15)
Get 9mol CaCO
3(0.3420g, FW=100.086, Mallinckodt Baker99.95%), 0.85mol Eu
2o
3(0.0568g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2417g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.15mol Sm
2o
3(0.0099g, FW=348.72, FLUKA99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.85ca
9(VO
4)
7: Sm
3+ 0.15.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 10 and Figure 11, and it excites main peak is that 394nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.649,0.343).Above-mentioned product Eu
0.85ca
9(VO
4)
7: Sm
3+ 0.15with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 12.
Embodiment 5 (EuCa
8(VO
4)
7: Zn
2+)
Get 8mol CaCO
3(0.2982g, FW=100.086, Mallinckodt Baker99.95%), 1mol Eu
2o
3(0.0655g, FW=351.93, STREM99.99%), 1mol ZnO (0.0303g, FW=81.39, SHOWA99.0%) and 3.5mol V
2o
5(0.2371g, FW=181.88, KOJUNDO99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the EuCa of pure phase after taking-up
8(VO
4)
7: Zn
2+.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 13 and Figure 14, and it excites main peak is that 394nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.642,0.346).Above-mentioned product EuCa
8(VO
4)
7: Zn
2+with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 15.
Embodiment 6 (Eu
0.85ca
8(VO
4)
7: Sm
3+ 0.15, Zn
2+)
Get 8mol CaCO
3(0.3010g, FW=100.086, Mallinckodt Baker99.95%), 0.85mol Eu
2o
3(0.0576g, FW=351.93, STREM99.99%), 1mol ZnO (0.0306g, FW=81.39, SHOWA99.0%), 0.15mol Sm
2o
3(0.0099g, FW=348.72, FLUKA99.9%) and 3.5mol V
2o
5(0.2394g, FW=181.88, KOJUNDO99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.85ca
8(VO
4)
7: Sm
3+ 0.15, Zn
2+.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 16 and Figure 17, and it excites main peak is that 395nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.652,0.340).Above-mentioned product Eu
0.85ca
8(VO
4)
7: Sm
3+ 0.15, Zn
2+with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 18.
Comparative example (EuCa
9(VO
4)
7)
Get 9mol CaCO
3(0.3419g, FW=100.086, Mallinckodt Baker99.95%), 1mol Eu
2o
3(0.0668g, FW=351.93, STREM99.99%) and 3.5mol V
2o
5(0.2416g, FW=181.88, KOJUNDO99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the EuCa of pure phase after taking-up
9(VO
4)
7.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 19 and Figure 20, and it excites main peak is that 394nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.650,0.343).Above-mentioned product EuCa
9(VO
4)
7with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 21.If by product EuCa
9(VO
4)
7eu with embodiment 3
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5photoexcitation illuminated diagram compare as shown in figure 22, can find to pass through Sm
3+with Zn
2+doping, Eu
0.9ca
8.5(VO
4)
7: Sm
3+ 0.1, Zn
2+ 0.5in 405nm left and right, there is obvious excitation spectrum.
Embodiment 7 (Eu
0.95ca
9(VO
4)
7: Bi
3+ 0.05)
Get 9mol CaCO
3(0.3412g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0633g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2411g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.05mol Bi
2o
3(0.0044g, FW=465.96, Riedel-de Haen99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.85ca
9(VO
4)
7: Bi
3+ 0.15.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 23 and Figure 24, and it excites main peak is that 394nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.646,0.345).
Embodiment 8 (Eu
0.95ca
9(VO
4)
7: Tb
3+ 0.05)
Get 9mol CaCO
3(0.3418g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0634g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2416g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.05mol Tb
4o
7(0.0035g, FW=747.70, STREM CHEMICALS99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.95ca
9(VO
4)
7: Tb
3+ 0.05.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 25 and Figure 26, and it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.650,0.343).
Embodiment 9 (EuCa
8.5(VO
4)
7: Sr
2+ 0.5)
Get 9mol CaCO
3(0.3172g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0656g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2373g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.5mol SrCO
3(0.0275g, FW=147.63, ProChem inc.99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the EuCa of pure phase after taking-up
8.5(VO
4)
7: Sr
2+ 0.5.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 27 and Figure 28, and it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.649,0.344).Above-mentioned product EuCa
8.5(VO
4)
7: Sr
2+ 0.5with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 29.
Embodiment 10 (EuCa
8(VO
4)
7: Sr
2+)
Get 9mol CaCO
3(0.2933g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0645g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2332g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.5mol SrCO
3(0.0541g, FW=147.63, ProChem inc.99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the EuCa of pure phase after taking-up
8(VO
4)
7: Sr
2+.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 30 and Figure 31, and it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.648,0.344).Above-mentioned product EuCa
8(VO
4)
7: Sr
2+with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 shown in figure 32.
Embodiment 11 (EuCa
8.5(VO
4)
7: Ba
2+ 0.5)
Get 9mol CaCO
3(0.3114g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0644g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2330g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.5mol BaCO
3(0.0361g, FW=197.34, Alfa Aesar99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the EuCa of pure phase after taking-up
8.5(VO
4)
7: Ba
2+ 0.5.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 33 and Figure 34, and it excites main peak is that 394nm, radiation main peak are that 613nm and the CIE coordinate that radiates main peak are (0.648,0.344).Above-mentioned product EuCa
8.5(VO
4)
7: Ba
2+ 0.5with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 35.
Embodiment 12 (Eu
0.85ca
9(VO
4)
7: Y
3+ 0.15)
Get 9mol CaCO
3(0.3444g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0572g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2434g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.05mol Y
2o
3(0.0065g, FW=225.81, SHOWA99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.85ca
9(VO
4)
7: Y
3+ 0.15.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 36 and Figure 37, and it excites main peak is that 394nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.649,0.344).Above-mentioned product Eu
0.85ca
9(VO
4)
7: Y
3+ 0.15with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 38.
Embodiment 13 (Eu
0.85ca
9(VO
4)
7: La
3+ 0.15)
Get 9mol CaCO
3(0.3424g, FW=100.086, Mallinckodt Baker99.95%), 0.95mol Eu
2o
3(0.0569g, FW=351.93, STREM99.99%), 3.5mol V
2o
5(0.2420g, FW=181.88, the bright KOJUNDO99.9% of scape) and 0.05mol La
2o
3(0.0093g, FW=225.81, MP Biomedicals, Inc.99.9%), grinds after evenly mixing, and inserts High Temperature Furnaces Heating Apparatus, and under the air of 1100 ℃, sintering is approximately 24 hours, obtains the Eu of pure phase after taking-up
0.85ca
9(VO
4)
7: La
3+ 0.15.The photoexcitation radiation collection of illustrative plates of above-mentioned product is as shown in Figure 39 and Figure 40, and it excites main peak is that 394nm, radiation main peak are that 614nm and the CIE coordinate that radiates main peak are (0.650,0.343).Above-mentioned product Eu
0.85ca
9(VO
4)
7: La
3+ 0.15with the luminous comparison diagram of photoexcitation of commercial goods Kasei-KX681 as shown in figure 41.
Although the present invention with several embodiment openly as above; so it is not in order to limit the present invention; any the technical staff in the technical field; without departing from the spirit and scope of the present invention; when changing arbitrarily and retouching, so protection scope of the present invention is when being as the criterion depending on accompanying claims person of defining.
Claims (7)
1. a vanadate luminescent material, has structural formula as follows:
Eu
1-x?Ca
9(VO
4)
7:Ma
x；
Wherein Ma is Sm
3+, Bi
3+, Tb
3+, La
3+or Y
3+, and 0<x≤0.15.
2. vanadate luminescent material according to claim 1, is Eu
0.9ca
9(VO
4)
7: Sm
3+ 0.1, after the UV-light of 200nm to 400nm or 400nm to 470nm blue-light excited, radiating a ruddiness, the main radiation crest of described ruddiness is 614nm, and the CIE coordinate of described ruddiness is (0.62,0.33).
3. a white light emitting device, comprise vanadate luminescent material and an excitation light source described in claim 1 or 2, and the wavelength of described excitation light source is the UV-light of 200nm to 400nm or the blue light of 400nm to 470nm.
4. white light emitting device according to claim 3, wherein said excitation light source comprises photodiode or laser diode.
5. white light emitting device according to claim 3, more comprises a blue-light fluorescent material and a green glow fluorescent material.
6. white light emitting device according to claim 5, wherein said blue-light fluorescent material is BaMgAl
10o
17: Eu
2+, (Ba, Sr, Ca)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, 2SrO*0.84P
2o
5* 0.16B
2o
3: Eu
2+, Sr
2si
3o
8* 2SrCl
2: Eu
2+or (Mg, Ca, Sr, Ba, Zn)
3b
2o
6: Eu
2+.
7. white light emitting device according to claim 5, wherein said green glow fluorescent material is BaMgAl
10o
17: Eu
2+, Mn
2+, SrGa
2s
4: Eu
2+, (Ca, Sr, Ba) Al
2o
4: Eu
2+, Mn
2+, (Ca, Sr, Ba)
4al
14o
25: Eu
2+, or Ca
8mg (SiO
4)
4cl
2: Eu
2+, Mn
2+.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300475A (en) * | 2018-02-27 | 2018-07-20 | 四川省有色冶金研究院有限公司 | A kind of LED red fluorescence powders and preparation method thereof |
| CN109082273A (en) * | 2018-09-18 | 2018-12-25 | 济南大学 | A kind of white fluorescent powder and preparation method thereof |
| CN109777421A (en) * | 2019-03-15 | 2019-05-21 | 常州工程职业技术学院 | A kind of europium ion Eu3+The red fluorescence powder of activation, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319394A (en) * | 2008-06-23 | 2008-12-10 | 福州大学 | Nonlinear optical crystal lanthanum calcium vanadate and preparation method and application thereof |
-
2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319394A (en) * | 2008-06-23 | 2008-12-10 | 福州大学 | Nonlinear optical crystal lanthanum calcium vanadate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHOUBIN LIN ET AL.: "Growth of a new nonlinear optical crystal YCa9(VO4)7", 《JOURNAL OF CRYSTAL GROWTH》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300475A (en) * | 2018-02-27 | 2018-07-20 | 四川省有色冶金研究院有限公司 | A kind of LED red fluorescence powders and preparation method thereof |
| CN109082273A (en) * | 2018-09-18 | 2018-12-25 | 济南大学 | A kind of white fluorescent powder and preparation method thereof |
| CN109777421A (en) * | 2019-03-15 | 2019-05-21 | 常州工程职业技术学院 | A kind of europium ion Eu3+The red fluorescence powder of activation, preparation method and application |
| CN109777421B (en) * | 2019-03-15 | 2021-04-20 | 常州工程职业技术学院 | Europium ion Eu3+Activated red fluorescent powder, preparation method and application |
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