CN103980898A - Red fluorescent powder with tungstate as matrix and preparation method thereof - Google Patents
Red fluorescent powder with tungstate as matrix and preparation method thereof Download PDFInfo
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- CN103980898A CN103980898A CN201410216461.2A CN201410216461A CN103980898A CN 103980898 A CN103980898 A CN 103980898A CN 201410216461 A CN201410216461 A CN 201410216461A CN 103980898 A CN103980898 A CN 103980898A
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- red fluorescence
- tungstate
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Abstract
The invention discloses red fluorescent powder with tungstate as the matrix and a preparation method thereof. The chemical general formula of the red fluorescent powder is K2Ba<1-x>(WO4)2:xEu, wherein x is not less than 0.05 and not more than 0.8. The red fluorescent powder can be effectively excited by near ultraviolet or blue light to emit red light with high color purity. The red fluorescent powder is prepared based on a solid-phase synthesis method. The preparation method is simple, is low in calcination temperature, good in reproducibility and short in preparation cycle, is used for preparing the red fluorescent powder in the air atmosphere, avoids pollution discharge, is environment-friendly, is easy to operate and easily achieves industrial production.
Description
Technical field
The invention belongs to LED fluorescent material technical field, relate to a kind of red fluorescence powder taking tungstate as matrix and preparation method thereof.
Background technology
Photodiode (Light Emitting Diode, LED) be acknowledged as the new light sources of 21st century, there is the plurality of advantages such as energy-conservation, response is fast, environmental protection, the life-span is long, volume is little, luminous efficiency is high, have huge application prospect in illumination and demonstration field.
At present, obtain the illumination form of white light LEDs and mainly contain three kinds: the first, by red-green-blue LED chip combination package generation by a certain percentage white light; The second, on blue-light LED chip, apply YAG fluorescent material, chip sends blue-light excited fluorescent material, produces gold-tinted, and gold-tinted and residue blue light, form white light; The 3rd, near ultraviolet LED chip, apply redgreenblue fluorescent material, combine and generation white light with near ultraviolet excitation blueness, green, red fluorescence powder formation blue light, green glow, ruddiness.
The red fluorescence powder that current business is used is mainly Y
2o
2s:Eu
3+, but red fluorescence powder Y
2o
2s:Eu
3+its luminous intensity is approximately blue colour fluorescent powder BaM
gal
l0o
17: Eu
2+with green emitting phosphor ZnS:(Cu
+, A1
3+) 1/8th.And, red fluorescence powder Y
2o
2s:Eu
3+easily decompose and produce harmful gas.So the red fluorescent powder for white radiation LED that exploitation can effectively be excited by near-ultraviolet light and blue light has actual application value.
Summary of the invention
The object of the invention is to the problem existing for above-mentioned white light LEDs technology, a kind of red fluorescence powder taking tungstate as matrix and preparation method thereof is provided, adopt solid phase method to prepare, its technique is simple, strong operability, and favorable reproducibility, preparation cycle is short.
The present invention is achieved through the following technical solutions:
A red fluorescence powder taking tungstate as matrix, the chemical general formula of this red fluorescence powder is K
2ba
1-x(WO
4)
2: xEu, wherein 0.05≤x≤0.8.
The excitation spectrum of this red fluorescence powder is at 350～550nm, and two main excitation peaks are near 394nm and 465nm, and its emmission spectrum is at 580～630nm, and main peak is near 617nm.
Described red fluorescence powder can near ultraviolet or blue-light excited under send ruddiness.
A preparation method for red fluorescence powder taking tungstate as matrix, comprises the following steps:
(1) according to the chemical structural formula K of red fluorescence powder
2ba
1-x(WO
4)
2: mole proportional quantity of xEu, take respectively the compound that contains K, Ba, W, Eu element as raw material, the raw material taking is fully ground and mixed;
(2) by uniform raw material under air atmosphere, at 700～1100 DEG C, calcine 3～8 hours;
(3) after having calcined, take out after being cooled to room temperature, fully grind, obtain mixing the tungstate red fluorescent powder K of europium
2ba
1-x(WO
4)
2: xEu, wherein 0.05≤x≤0.8.
The described compound that contains K, Ba, W, Eu element, is respectively its carbonate or oxide compound.
The described compound that contains K, Ba, W, Eu element, is respectively K
2cO
3, BaCO
3, WO
3, Eu
2o
3.
Described in the time of calcining, be to rise to 700～1100 DEG C with the temperature rise rate of 3～10 DEG C/min.
Its milling time of grinding after grinding, the calcining of described raw material is 20～60min.
Compared with prior art, the present invention has following useful technique effect:
Red fluorescence powder taking tungstate as matrix provided by the invention, WO wherein
4 2-w-O key in group has stronger covalent linkage effect, and the oxonium ion in polyhedron is subject to the polarized action of contiguous high valence state tungsten, and the Fluorescence quenching effect of rare earth activation ion is reduced, thereby the doping content of active ions is improved.By doping active ions Eu
3+, can excite lower acquisition main peak to be positioned near the ruddiness that 617nm, luminous intensity is strong, purity of color is higher near ultraviolet (394nm) and blue light (465nm).The CIE chromaticity coordinates of this red fluorescence powder and NTSC reference colour coordinate fit like a glove, and mate with the photodiode of near ultraviolet chip and blue chip, can be as red fluorescent powder for white radiation LED.
The preparation method of the red fluorescence powder taking tungstate as matrix provided by the invention, its preparation method is prepared based on solid-phase synthesis, strong operability, calcining temperature is low, under air atmosphere, prepares, and temperature-rise period is simple, preparation method is simple, favorable reproducibility, and preparation cycle is short.
Brief description of the drawings
Fig. 1 is K
2ba
0.8(WO
4)
2: the X ray diffracting spectrum of 0.2Eu red fluorescence powder and K
2ba (WO
4)
2standard card (PDF#51-0083) comparison diagram.
Fig. 2 is K
2ba
0.8(WO
4)
2: the excitation spectrum of 0.2Eu red fluorescence powder and emmission spectrum.
Fig. 3 is K
2ba
0.4(WO
4)
2: the CIE chromaticity coordinates figure of 0.6Eu red fluorescence powder.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
Embodiment 1
Press chemical formula K
2ba
0.95(WO
4)
2: the stoichiometric of 0.05Eu, utilizes electronic balance accurately to take respectively raw material K
2cO
3, BaCO
3, WO
3, Eu
2o
3, the purity of its middle rare earth is 99.99%, all the other are analytical pure.By above-mentioned raw materials carry out ground and mixed evenly after, pack corundum crucible into, be placed in the resistance furnace that is rapidly heated, rise to 800 DEG C at air atmosphere with the temperature rise rate of 5 DEG C/min, be incubated 7 hours, then furnace cooling, treats that sample is cooled to room temperature.Take out sample and again grind, obtain mixing the tungstate red fluorescent powder of europium.
Embodiment 2
Press chemical formula K
2ba
0.8(WO
4)
2: the stoichiometric of 0.2Eu, utilizes electronic balance accurately to take respectively raw material K
2cO
3, BaCO
3, WO
3, Eu
2o
3, the purity of its middle rare earth is 99.99%, all the other are analytical pure.By above-mentioned raw materials carry out ground and mixed evenly after, pack corundum crucible into, be placed in the resistance furnace that is rapidly heated, rise to 800 DEG C at air atmosphere with the temperature rise rate of 5 DEG C/min, be incubated 5 hours, then furnace cooling, treats that sample is cooled to room temperature.Take out sample and again grind, obtain mixing the tungstate red fluorescent powder of europium.
Fig. 1 is K prepared by the present embodiment 2
2ba
0.8(WO
4)
2: the X ray diffracting spectrum of 0.2Eu red fluorescence powder and K
2ba (WO
4)
2standard card (PDF#51-0083) comparison diagram.As can be seen from Figure, thing phase purity is high, better crystallinity degree.
Fig. 2 is K prepared by the present embodiment 2
2ba
0.8(WO
4)
2: the excitation spectrum of 0.2Eu red fluorescence powder and emmission spectrum.Main emission peak is positioned near 617nm, and two main excitation peaks lay respectively near 394nm and near 465nm.As can be seen here, this fluorescent material can effectively be excited and send ruddiness by near-ultraviolet light and blue light, can be applicable to white light LEDs.
Embodiment 3
Press chemical formula K
2ba
0.6(WO
4)
2: the stoichiometric of 0.4Eu, utilizes electronic balance accurately to take respectively raw material K
2cO
3, BaCO
3, WO
3, Eu
2o
3, the purity of its middle rare earth is 99.99%, all the other are analytical pure.By above-mentioned raw materials carry out ground and mixed evenly after, pack corundum crucible into, be placed in the resistance furnace that is rapidly heated, rise to 900 DEG C at air atmosphere with the temperature rise rate of 5 DEG C/min, be incubated 5 hours, then furnace cooling, treats that sample is cooled to room temperature.Take out sample and again grind, obtain mixing the tungstate red fluorescent powder of europium.
Embodiment 4
Press chemical formula K
2ba
0.5(WO
4)
2: the stoichiometric of 0.6Eu, utilizes electronic balance accurately to take respectively raw material K
2cO
3, BaCO
3, WO
3, Eu
2o
3, the purity of its middle rare earth is 99.99%, all the other are analytical pure.By above-mentioned raw materials carry out ground and mixed evenly after, pack corundum crucible into, be placed in the resistance furnace that is rapidly heated, rise to 800 DEG C at air atmosphere with the temperature rise rate of 5 DEG C/min, be incubated 5 hours, then furnace cooling, treats that sample is cooled to room temperature.Take out sample and again grind, obtain mixing the tungstate red fluorescent powder of europium.
Fig. 3 is the prepared K of the present embodiment 4
2ba
0.4(WO
4)
2: the CIE chromaticity coordinates figure of 0.6Eu red fluorescence powder.As can be seen from Figure, the CIE chromaticity coordinates of this red fluorescence powder is (x=0.670, y=0.330), fits like a glove with NTSC reference colour coordinate (x=0.670, y=0.330).
Embodiment 5
Press chemical formula K
2ba
0.3(WO
4)
2: the stoichiometric of 0.7Eu, utilizes electronic balance accurately to take respectively raw material K
2cO
3, BaCO
3, WO
3, Eu
2o
3, the purity of its middle rare earth is 99.99%, all the other are analytical pure.By above-mentioned raw materials carry out ground and mixed evenly after, pack corundum crucible into, be placed in the resistance furnace that is rapidly heated, rise to 900 DEG C at air atmosphere with the temperature rise rate of 10 DEG C/min, be incubated 3 hours, then furnace cooling, treats that sample is cooled to room temperature.Take out sample and again grind, obtain mixing the tungstate red fluorescent powder of europium.
Claims (8)
1. the red fluorescence powder taking tungstate as matrix, is characterized in that, the chemical general formula of this red fluorescence powder is K
2ba
1-x(WO
4)
2: xEu, wherein 0.05≤x≤0.8.
2. the red fluorescence powder taking tungstate as matrix as claimed in claim 1, it is characterized in that, the excitation spectrum of this red fluorescence powder is at 350～550nm, and two main excitation peaks are near 394nm and 465nm, its emmission spectrum is at 580～630nm, and main peak is near 617nm.
3. the red fluorescence powder taking tungstate as matrix as claimed in claim 2, is characterized in that, described red fluorescence powder can near ultraviolet or blue-light excited under send ruddiness.
4. a preparation method for the red fluorescence powder taking tungstate as matrix, is characterized in that, comprises the following steps:
(1) according to the chemical structural formula K of red fluorescence powder
2ba
1-x(WO
4)
2: mole proportional quantity of xEu, take respectively the compound that contains K, Ba, W, Eu element as raw material, the raw material taking is fully ground and mixed;
(2) by uniform raw material under air atmosphere, at 700～1100 DEG C, calcine 3～8 hours;
(3) after having calcined, take out after being cooled to room temperature, fully grind, obtain mixing the tungstate red fluorescent powder K of europium
2ba
1-x(WO
4)
2: xEu, wherein 0.05≤x≤0.8.
5. the preparation method of the red fluorescence powder taking tungstate as matrix as claimed in claim 4, is characterized in that, the described compound that contains K, Ba, W, Eu element, is respectively its carbonate or oxide compound.
6. the preparation method of the red fluorescence powder taking tungstate as matrix as claimed in claim 5, is characterized in that, the described compound that contains K, Ba, W, Eu element, is respectively K
2cO
3, BaCO
3, WO
3, Eu
2o
3.
7. the preparation method of the red fluorescence powder taking tungstate as matrix as claimed in claim 4, is characterized in that, described in the time of calcining, is to rise to 700～1100 DEG C with the temperature rise rate of 3～10 DEG C/min.
8. the preparation method of the red fluorescence powder taking tungstate as matrix as claimed in claim 4, is characterized in that, its milling time of grinding after grinding, the calcining of described raw material is 20～60min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357051A (en) * | 2014-11-10 | 2015-02-18 | 朝克夫 | Fluorescent material, preparation method thereof and light-emitting device |
| CN105586037A (en) * | 2016-01-05 | 2016-05-18 | 重庆理工大学 | Red potassium tungstate phosphor and preparation method |
| CN105670623A (en) * | 2015-12-31 | 2016-06-15 | 中南大学 | Blue-white light conversion fluorescent powder on the basis of UV light excitation and preparation thereof |
| CN106753374A (en) * | 2017-02-15 | 2017-05-31 | 江苏师范大学 | A kind of europium ion-doped tungsten barium tantalate and its preparation method and application |
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| CN101338194A (en) * | 2008-05-15 | 2009-01-07 | 沈阳化工学院 | Rare-earth red fluorescent material and method for preparing same |
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2014
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Patent Citations (3)
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| KR20030033864A (en) * | 2001-10-25 | 2003-05-01 | 한국화학연구원 | Red phosphor for UV LED and active matrix LCD |
| KR100764634B1 (en) * | 2006-03-08 | 2007-10-08 | 재단법인서울대학교산학협력재단 | New wo4-based phosphor for white led and synthetic method |
| CN101338194A (en) * | 2008-05-15 | 2009-01-07 | 沈阳化工学院 | Rare-earth red fluorescent material and method for preparing same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357051A (en) * | 2014-11-10 | 2015-02-18 | 朝克夫 | Fluorescent material, preparation method thereof and light-emitting device |
| CN105670623A (en) * | 2015-12-31 | 2016-06-15 | 中南大学 | Blue-white light conversion fluorescent powder on the basis of UV light excitation and preparation thereof |
| CN105670623B (en) * | 2015-12-31 | 2017-09-26 | 中南大学 | One kind is based on blue white light conversion phosphor and its preparation under ultraviolet excitation |
| CN105586037A (en) * | 2016-01-05 | 2016-05-18 | 重庆理工大学 | Red potassium tungstate phosphor and preparation method |
| CN106753374A (en) * | 2017-02-15 | 2017-05-31 | 江苏师范大学 | A kind of europium ion-doped tungsten barium tantalate and its preparation method and application |
| CN106753374B (en) * | 2017-02-15 | 2019-03-15 | 江苏师范大学 | A kind of europium ion-doped tungsten barium tantalate and its preparation method and application |
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Application publication date: 20140813 |