CN101955772B - Fluorescent material and preparation method thereof - Google Patents
Fluorescent material and preparation method thereof Download PDFInfo
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- CN101955772B CN101955772B CN200910160716.7A CN200910160716A CN101955772B CN 101955772 B CN101955772 B CN 101955772B CN 200910160716 A CN200910160716 A CN 200910160716A CN 101955772 B CN101955772 B CN 101955772B
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- magnesium silicate
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Abstract
The invention relates to a fluorescent material and a preparation method thereof. The invention discloses a fluorescent material capable of emitting three primary colors of red, green and blue, which is alkali-earth silicate mainly taking manganese (Mn2+) and europium (Eu2+) as luminescence centers. A chemical formula of the fluorescent material is Sr(3+/-a)-x-yMg1.5+/-bSi1.5+/-cOz:Eux, Mny. Through the generation of a main phase Sr3MgSi2O8 and an auxiliary phase Sr2SiO4 and the energy transfer effect between manganese and europium of the luminescence centers, the three primary colors of red, green and blue can be emitted and blended in the region of an Coherent Infrared Energy (CIE) coordinate where white light is positioned under the excitation of ultraviolet light. Besides, the material has the advantages of simple and rapid preparation method, easy mass production and industrial application value.
Description
Technical field
The invention relates to a kind of fluorescent material and preparation method thereof.
Background technology
Japanese Ya chemical company in 1996, development with InGaN (InGaN) blue light-emitting diode collocation Yellow light-emitting low temperature with cerium (Ce
3+) be yttrium aluminium garnet fluorescent powder (the Ce-doped YttriumAluminum Garnet of luminescence center; YAG:Ce), become first white light emitting diode.White light LEDs has advantages of energy-conservation long with the life-span compared with conventional light source, meet the development trend of global various countries carbon reduction, white light LEDs has been regarded as 21 century lighting source at present, suitable manpower and development costs are all bet by the advanced countries such as America and Europe and Japan, in the future several years, can generally substitute conventional illumination device, the industrial value that it is derivative and energy environment protection effect will be promising.
But the color rendering of the white light LEDs of blue-ray LED cooperation YAG:Ce fluorescent material is lower, and can utilize UV-light to there is higher luminous efficiency and color rendering as the white light LEDs of red, the green and blue three-color phosphor combination of ultraviolet light-emitting diodes (UV-LED) collocation of excitaton source.But be applicable to red, the green and blue three-color phosphor of ultraviolet excitation, in actual package process, because of need, to consider that the efficiency of multiple different powders, powder are mixed difficulty higher, still waits to break through considering of practical aspect.
At present taking alkaline-earth silicate (Alkaline-earth silicates) compound as main material, and be applicable to the fluorescent material of blue light or ultraviolet excitation, the dealer of existing quite a lot of family drops into.In people such as Audesse in 1971 in United States Patent (USP) the 3rd, 732, No. 416 disclosed Ca
1.5sr
1.5mgSi
2o
8: Eu
0.04, for using the earliest the fluorescent material of alkaline-earth silicate compound, only this document is only used for conventional lamp, the unexposed LED that can be applicable to by fluorescent material; Then the people such as Ma is in Applied Physics Letters, and 93,144101,2008, one of disclosed Sr
2.78mgSi
2o
8: 0.02Eu
2+, 0.2Mn
2+, can pass through divalent europium (Eu
2+) deliver power to manganese (Mn
2+), emit blue light and ruddiness simultaneously.
Summary of the invention
The invention discloses a kind of fluorescent material of launching red green blue tricolor, mainly with manganese (Mn
2+) and europium (Eu
2+) be the alkaline-earth silicate class of luminescence center.This fluorescent material chemical formula is Sr
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
y.By producing principal phase Sr
3mgSi
2o
8and parafacies Sr
2siO
4, and transmission ofenergy effect between luminescence center manganese and europium, can be under ultraviolet excitation, send red green blue tricolor light and blend together the white light field that is arranged in CIE coordinate.In addition material disclosed in this invention, its preparation method is simple and easy rapidly, easily a large amount of production, therefore have industry using value.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction of the prepared fluorescent material sample of embodiments of the invention.
Fig. 2 is the prepared optical excitation of fluorescent material sample of embodiments of the invention and the spectrogram of transmitting.
Fig. 3 is the cie color coordinate diagram with program conversion gained by the emmission spectrum of figure bis-fluorescent material samples.
Embodiment
In view of above-mentioned document and patent, contain in the alkaline-earth silicate of strontium (Sr) with divalent europium (Eu
2+) in the luminescence components such as LED, play the part of the role of important blue-light source for the fluorescent material of luminescence center, and previous literature is only mentioned and is contained two kinds of phases or divalent europium (Eu simultaneously
2+) and manganese (Mn
2+) energy transformation, cause powder to mix the main cause that difficulty promotes because not being all in view of the efficiency of multiple powder, the disclosed fluorescent material of this institute can be produced the spectrum of RGB three-wavelength under ultraviolet excitation, its CIE coordinate is seated white light field, therefore can obtain more quantum jump in the application of practical aspect.
In embodiments of the invention, alkaline-earth silicate class fluorescent material and preparation method thereof is described below.The present invention discloses Sr
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
yas fluorescent material, wherein 0≤a, b, c≤0.3, x compositing range can be 0 < x≤0.02, y compositing range can be 0 < y≤0.3, and z compositing range can be 7 < z≤9, selects a=0, b=0, c=0, x=0.01, y=0.2 and 7 its making methods of < z≤9 as follows in the present embodiment:
One, first get respectively according to stoichiometric ratio the first reactant that contains strontium (Sr), as SrCO
3, the second reactant that contains silicon (Si), as SiO
2, the 3rd reactant that contains magnesium (Mg), as MgO, the 4th reactant that contains europium (Eu), as Eu
2o
3, and the 5th reactant that contains manganese (Mn), as MnO
2, and after above-mentioned reactant weighs, add the fusing assistant NH of all reactant gross weights 5%
4cl, its synthetic method is utilized solid state reaction.
Two, grind after fully mixing with mortar, mixture is placed in to alumina crucible, then alumina crucible is inserted to block furnace, in H
2/ N
2under the reducing atmosphere of (5%/95%), be heated to react 4 hours at 1300 DEG C with the temperature rise rate of 5 DEG C/min, be then cooled to room temperature with the rate of temperature fall of 5 DEG C/min again, take out and grind, obtain alkaline-earth silicate compounds fluorescent material Sr
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
y, wherein a=0, b=0, c=0, x=0.01, y=0.2 and 7 < z≤9.
Above-mentioned each reactant, for example SrCO
3, MgO, SiO
2, Eu
2o
3and MnO
2, can directly obtain in commercial goods.
According to the prepared Sr of the embodiment of the present invention
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
y, wherein a=0, b=0, c=0, x=0.01, y=0.2 and z=7-9 sample, its X light powder diffraction collection of illustrative plates as shown in figure mono-, in figure with Sr
3mgSi
2o
8for the solid circles of principal phase and sign is Sr
2siO
4parafacies two-phase forms alkaline-earth silicate compounds.
The exciting of this sample (excitation) and emission spectrum (emission) as shown in Figure 2, comprise Sr by known this of exciting light spectrogram
3mgSi
2o
8for principal phase and Sr
2siO
4the two-phase fluorescent material of parafacies is applicable to UV-light and excites.In addition, can obtain red, green and Lan Sanse radiation wavelength by radiating light spectrogram and be respectively 684nm, 542nm and 458nm, and the light color rendering that this compound collocation UV-light forms excites YAG yellow fluorescent powder for high compared with blue chip.
By the data of emission spectrum with 1931 by (the CommissionInternational de l ' Eclairage of International Commission on Illumination, CIE) formula of the tristimulus coordinates figure (Chromaticity diagram) formulating is converted into the tristimulus coordinates of each fluor representative, is shown in figure tri-.Figure mid point x is by figure bis-Sr
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
y, the position that wherein emission spectrum of a=0, b=0, c=0, x=0.01, y=0.2 and 7 < z≤9 is simulated in tristimulus coordinates with program conversion gained.
In the present invention, by comprising Sr
3mgSi
2o
8for principal phase and Sr
2siO
4the two-phase fluorescent material of parafacies and manganese (Mn
2+) and europium (Eu
2+) two luminescence center, blue light source is by Sr
3mgSi
2o
8: Eu
2+send, gold-tinted light source is by Sr
2siO
4: Eu
2+send, and red-light source is by Sr
3mgSi
2o
8middle Eu
2+energy transformation is to Mn
2+and send.By gold-tinted light source is moved toward Exocarpium Citri Rubrum light, can obtain warm white (warm white).Also can, by increasing the content of manganese (Mn), make europium (Eu in addition
2+) can be by energy transformation to manganese Mn
2+, and can enter warm white (warm white) region.
Above-described embodiment is only explanation technological thought of the present invention and feature, its object is making in technical field that the present invention belongs to technician can understand content of the present invention and implement according to this, can not limit the scope of the claims of the present invention with it, all equalizations of doing according to spirit disclosed in this invention change or modify, and must be included in the scope of the claims of the present invention.
Claims (9)
1. a strontium magnesium silicate compounds fluorescent material, this fluorescent material general formula is Sr
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
ywherein a=0, b=0, c=0,0 < x≤0.02,0 < y≤0.3 and 7 < z≤9, under ultraviolet excitation, this fluorescent material can produce red, green and blue three coloured light spectrums, and this fluorescent material can produce Sr simultaneously
3mgSi
2o
8and Sr
2siO
4two-phase.
2. strontium magnesium silicate compounds fluorescent material as claimed in claim 1, wherein a=0, b=0, c=0, x=0.01, y=0.2 and 7 < z≤9.
3. strontium magnesium silicate compounds fluorescent material as claimed in claim 1, this fluorescent material is mainly with divalent europium (Eu
2+) and bivalent manganese (Mn
2+) be luminescence center, and this divalent europium (Eu wherein
2+) can be by transmission ofenergy to bivalent manganese (Mn
2+) mode and send ruddiness.
4. strontium magnesium silicate compounds fluorescent material as claimed in claim 1, wherein this UV-light can be by photodiode or plasma generation.
5. strontium magnesium silicate compounds fluorescent material as claimed in claim 1, wherein this red, green and blue three color light spectrum is warm white.
6. a preparation method for strontium magnesium silicate compounds fluorescent material, comprises:
The first reactant that contains strontium, the second reactant that contains silicon, the 3rd reactant that contains magnesium, the 4th reactant that contains europium (Eu) and the 5th reactant that contains manganese (Mn) are mixed into mixture; And
This mixture is added to thermosetting strontium magnesium silicate compounds fluorescent material in reducing atmosphere, and this fluorescent material general formula is Sr
(3 ± a)-x-ymg
1.5 ± bsi
1.5 ± co
z: Eu
x, Mn
ywherein a=0, b=0, c=0,0 < x≤0.02,0 < y≤0.3 and 7 < z≤9, under ultraviolet excitation, this fluorescent material can produce red, green and blue three coloured light spectrums, and this fluorescent material can produce Sr simultaneously
3mgSi
2o
8and Sr
2siO
4two-phase.
7. the preparation method of strontium magnesium silicate compounds fluorescent material as claimed in claim 6, can add NH
4cl is as fusing assistant, and wherein this fusing assistant is 5% of reactant gross weight.
8. the preparation method of strontium magnesium silicate compounds fluorescent material as claimed in claim 6, wherein this preparation method is solid state reaction.
9. the preparation method of strontium magnesium silicate compounds fluorescent material as claimed in claim 6, wherein this reducing atmosphere comprises hydrogen and nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910160716.7A CN101955772B (en) | 2009-07-17 | 2009-07-17 | Fluorescent material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910160716.7A CN101955772B (en) | 2009-07-17 | 2009-07-17 | Fluorescent material and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101955772A CN101955772A (en) | 2011-01-26 |
| CN101955772B true CN101955772B (en) | 2014-07-16 |
Family
ID=43483366
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|---|---|---|---|
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5857234B2 (en) | 2012-11-20 | 2016-02-10 | パナソニックＩｐマネジメント株式会社 | Phosphor, light emitting device, imaging device, liquid crystal display device, lighting device, and vehicle |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7791261B2 (en) * | 2003-06-11 | 2010-09-07 | Sumitomo Chemical Company, Limited | Ultraviolet excited light-emitting device |
| US7026755B2 (en) * | 2003-08-07 | 2006-04-11 | General Electric Company | Deep red phosphor for general illumination applications |
-
2009
- 2009-07-17 CN CN200910160716.7A patent/CN101955772B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Sr2MgSiO5:(Eu2+, Mn2+)单一基质白光荧光粉的发光性质;杨志平等;《硅酸盐学报》;20061031;第34卷(第10期);第1195-1198页 * |
| 杨志平等.Sr2MgSiO5:(Eu2+ Mn2+)单一基质白光荧光粉的发光性质.《硅酸盐学报》.2006 |
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| Publication number | Publication date |
|---|---|
| CN101955772A (en) | 2011-01-26 |
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