CN101565620A - Single-phase white-emitting phosphor based on near ultraviolet excitation and preparation method thereof - Google Patents
Single-phase white-emitting phosphor based on near ultraviolet excitation and preparation method thereof Download PDFInfo
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- CN101565620A CN101565620A CNA2009100670765A CN200910067076A CN101565620A CN 101565620 A CN101565620 A CN 101565620A CN A2009100670765 A CNA2009100670765 A CN A2009100670765A CN 200910067076 A CN200910067076 A CN 200910067076A CN 101565620 A CN101565620 A CN 101565620A
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- near ultraviolet
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Abstract
The invention relates to phosphor applicable to preparing a light emitting[white-emitting] LED, in particular to single-phase white-emitting phosphor based on near ultraviolet excitation and a preparation method thereof; the chemical formula of the phosphor is as follows: Sr5-m-nZn<n>(SiO4)2Cl2:Eu<2+>m, wherein m is more than or equal to 0.10 but less than or equal to 0.15, n is more than or equal to 0 but less than or equal to 0.20; the phosphor emits single-phase white light after being excited by 360nm-410nm near ultraviolet light. The preparation method comprises the steps of taking SiO2, Eu2O3, SrCO3, ZnO and SrCl2.6H2O as raw materials, mixing and grinding the raw materials, and then baking the raw materials at the temperature of 1000 DEG C to 1200 DEG C for 3h to 5h, and grinding the raw materials after being cooled naturally, thereby obtaining the single-phase white-emitting phosphor. The phosphor can be combined with near ultraviolet tube core to prepare the light emitting LED, thus overcoming the defects of tricolor (red, green and blue) mixed phosphor that the problems of re-absorption and proportioning regulation affect the lumen efficiency and color rendition.
Description
Technical field
The present invention relates to be applicable to the fluorescent material of preparation white light LEDs, particularly relate to a kind of under near ultraviolet excitation and fluorescent material of emission single-phase white and preparation method thereof.
Background technology
The successful research and development of high brightness GaN blue LED and the white light LEDs of realizing thus have been described as maximum light source revolution since Edison's invention incandescent light that continues.Compare with traditional incandescent light, luminescent lamp, White-light LED illumination is energy-efficient owing to having, the life-span long, do not have advantages such as (Hg, Pb) pollutes, operating voltage is low, not fragile receives much concern.The LED industry increases progressively with the speed more than 20% every year in recent years.
Blue (purple) light LED phosphor combination is the important channel of realizing white light LEDs.At present, white light LEDs practical on the market is the rear-earth-doped YAG:Ce gold-tinted fluorescent material of blue light tube core excitation, because the blue light of LED is participated in the synthetic of white light directly, so the glow color of device changes with the coat-thickness and the driving voltage of fluorescent material, color rendition power is relatively poor, and colour rendering index is on the low side.For addressing the above problem, adopt near-ultraviolet light (370-410nm) tube core to excite three primary colors fluorescent powder to realize that white light LEDs becomes the focus of research and development.Because human eye is insensitive to near-ultraviolet light, this method realizes the color of white light LEDs only by the three primary colors fluorescent powder decision, so color stable, and reproduction power is strong, and the colour rendering index height is the direction of white light LEDs development.
Reported single-phase white-emitting phosphor has: 2004, its composition of Korean's development was respectively Sr
3MgSi
2O
8: Eu
2+And Sr
3MgSi
2O
8: Eu
2+, Mn
2+Two kinds of single-phase white-emitting phosphor (JongSu Kim, Pyung Eun Jeon, Yun Hyung Park, Jun chul Choi, and Hong LeeParka, Gwang Chul Kim, TaeWhan Kim, Appl.Phys.Lett. Applied Physics wall bulletin, 85 volume (17) phases, 3696 pages, 2004).2006, Changchun Institute of Optics, Fine Mechanics and Physics, CAS development consist of Eu
XySr
Y-xyMgSi
zO
2z+y+1Single-phase white-emitting phosphor (patent of invention, contriver Zhang Jiahua, Sun Xiaoyuan, Wang Xiaojun, Zhang Xia, the patent No. 200510016743.9, publication number CN1850940A).
Summary of the invention
The objective of the invention is to propose a kind of single-phase white-emitting phosphor based near ultraviolet excitation, this fluorescent material sends single-phase white under near ultraviolet excitation, can with near-ultraviolet light tube core combined preparation white light LEDs, to overcome present red, green, blue three primary colours mixed fluorescent powder because of absorbing again of existing with proportioning is regulated and control the defective that problem influences luminous efficiency and color rendition performance.
The present invention is based on the single-phase white-emitting phosphor of near ultraviolet excitation, is the compound with following chemical formula: Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ m, wherein, 0.10≤m≤0.15; 0≤n≤0.20.
Described x, y preferred value are: m=0.12, n=0.10; M=0.15, n=0.10.
Because rare earth ion Eu
2+The d electronic energy level structure be subjected to matrix and lattice site environmental influence very big, just can regulate and control different cases by adjusting matrix components than, activator concentration, regulate and control different luminescent spectrum distributions.Fluorescent material of the present invention is launched single-phase white under the 360-410nm near ultraviolet excitation.
The preparation method of fluorescent material of the present invention may further comprise the steps:
A. with SiO
2, Eu
2O
3, SrCO
3, ZnO, SrCl
2.6H
2O makes raw material, takes by weighing above-mentioned each raw material by the stoichiometric ratio of each material in the above-mentioned chemical formula, carries out ground and mixed;
B. above-mentioned compound is inserted in the corundum crucible, at CO or H
2Roast under the reducing atmosphere, roast temperature are that the roast time is 3 one 5 hours in 1000 ℃ one 1200 ℃, grind behind the naturally cooling and promptly get described single-phase white-emitting phosphor.
Because SrCl
2.6H
2The fusing point of O lower (873 ℃), easy scaling loss when roast, so SrCl in the described mixing raw material of step a
2.6H
2The proportional quantity of O is for the 110%-120% by the stoichiometric ratio calculated amount, to compensate its scaling loss in roast.
Single-phase white-emitting phosphor of the present invention, under the 360-410nm near ultraviolet excitation, launch single-phase white, with near-ultraviolet light tube core combined preparation white light LEDs, overcome three primary colors fluorescent powder and weakened problem, also avoided the red, green, blue three primary colours to absorb problem again because of irregular colour weighing apparatus, the luminous intensity that heterogeneous mixing produces.
Description of drawings
Fig. 1 is single-phase white-emitting phosphor Sr of the present invention
4.75Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.15Emmission spectrum (λ
Ex=400nm) and the exciting light spectrogram;
Fig. 2 is single-phase white-emitting phosphor Sr of the present invention
4.78Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.12Emmission spectrum (λ
Ex=400nm) and the exciting light spectrogram.
Embodiment
By following examples the present invention is described in further detail.
Use spectroscopically pure SiO
2, the pure Eu of top grade
2O
3, analytical pure SrCO
3, ZnO, SrCl
2.6H
2O makes raw material, prepares fluorescent material of the present invention.
Embodiment 1
Preparation Sr
4.90(SiO
4)
2Cl
2.0: Eu
2+ 0.10(promptly work as Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ mMiddle m=0.10 is during n=0.00) fluorescent material.
Take by weighing SrCO by stoichiometric ratio
32.8782 gram, SrCl
2.6H
2O1.5972 gram (because SrCl
2.6H
2O fusing point lower (873 ℃) is by calculated amount excessive 20%), SiO
20.6008 gram, Eu
2O
30.0880 gram is put into the agate mortar mixed grinding; Put into corundum crucible, add a cover, place in the High Temperature Furnaces Heating Apparatus, at CO or H
2Under the reducing atmosphere, under 1100-1200 ℃ of temperature roast 3-5 hour; Grind behind the naturally cooling, promptly obtaining chemical formula is 8r
4.90(SiO
4)
2Cl
2.0: Eu
0.10Single-phase white-emitting phosphor.Its chromaticity coordinates is x=0.3262, y=0.4386; Colour temperature is T
c=5710K; Colour rendering index is Ra=56.0.
Preparation Sr
4.70Zn
0.20(SiO
4)
2Cl
2: Eu
0.10 2+(promptly work as Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ mMiddle m=0.10 is during n=0.20) fluorescent material.
Take by weighing SrCO by stoichiometric ratio
32.7306 gram, SrCl
2.6H
2O 1.4641 grams (by calculated amount excessive 10%), ZnO0.0814, SiO
20.6008 gram, Eu
2O
30.0880 gram is put into the agate mortar mixed grinding; Put into corundum crucible, add a cover, place in the High Temperature Furnaces Heating Apparatus, at CO or H
2Under the reducing atmosphere, under 1100-1200 ℃ of temperature roast 3-5 hour; Grind behind the naturally cooling, promptly obtaining chemical formula is Sr
4.70Zn
0.20(SiO
4)
2Cl
2: Eu
0.10 2+Single-phase white-emitting phosphor.Its chromaticity coordinates is x=0.3293, y=0.4061; Colour temperature is T
c=5829K; Colour rendering index is Ra=64.0.。
Embodiment 3
Preparation Sr
4.88(SiO
4)
2Cl
2.:Eu
2+ 0.12(promptly work as Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ mMiddle m=0.12 is during n=0.00) fluorescent material.
Take by weighing SrCO by stoichiometric ratio
32.8634 gram, SrCl
2.6H
2O 1.5972 grams (by calculated amount excessive 20%), SiO
20.6008 gram, Eu
2O
30.1056 gram is put into the agate mortar mixed grinding; Put into corundum crucible, add a cover, place in the High Temperature Furnaces Heating Apparatus, under CO or H2 reducing atmosphere, under 1100-1200 ℃ of temperature roast 3-5 hour; Grind behind the naturally cooling, promptly obtaining chemical formula is Sr
4.88(SiO
4)
2Cl
2.:Eu
2+ 0.12Single-phase white-emitting phosphor.Its chromaticity coordinates is x=0.3370, y=0.4074; Colour temperature is T
c=6067K; Colour rendering index is Ra=61.7.
Embodiment 4
Preparation Sr
4.78Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.12(promptly work as Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ mMiddle m=0.12 is during n=0.10) fluorescent material.
Take by weighing SrCO by stoichiometric ratio
32.7896, SrCl
2.6H
2O1.4641 gram (by calculated amount excessive 10%), SiO
20.6008 gram, ZnO0.0407, Eu
2O
30.1056 gram is put into the agate mortar thorough mixing and is ground; Put into corundum crucible, add a cover, place in the High Temperature Furnaces Heating Apparatus, at CO or H
2Under the reducing atmosphere, under 1000-1200 ℃ of temperature roast 3-5 hour; Naturally grind cold back, and promptly obtaining chemical formula is Sr
4.78Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.12Single-phase white-emitting phosphor.
As shown in Figure 2, be this Sr
4.78Zn
0.12(SiO
4)
2Cl
2: Eu
0.10 2+Emmission spectrum (the λ of fluorescent material
Ex=400nm) and excitation spectrum (λ
Em=445nm; λ
Em=548nm).Its chromaticity coordinates is x=0.3268, y=0.3866; Colour temperature is T
c=5837K; Colour rendering index is Ra=66.6
Embodiment 5
Preparation Sr
4.85(SiO
4)
2Cl
2: Eu
2+ 0.15(promptly work as Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ mMiddle m=0.15 is during n=0.00) fluorescent material.
Take by weighing SrCO by stoichiometric ratio
32.8413 gram, SrCl
2.6H
2O1.5972 gram (by calculated amount excessive 20%), SiO
20.6008 gram, Eu
2O
30.1320 gram is put into the agate mortar mixed grinding; Put into corundum crucible, add a cover, place in the High Temperature Furnaces Heating Apparatus, under CO or H2 reducing atmosphere, under 1000-1200 ℃ of temperature roast 3-5 hour; Grind behind the naturally cooling, promptly obtaining chemical formula is Sr
4.85(SiO
4)
2Cl
2.0: Eu
2+ 0.15Single-phase white-emitting phosphor.Its chromaticity coordinates is x=0.3101, y=0.4041; Colour temperature is T
c=6315K; Colour rendering index is Ra=60.0.
Embodiment 6
Preparation Sr
4.75Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.15(promptly work as Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ mMiddle m=0.15 is during n=0.10) fluorescent material.
Take by weighing SrCO by stoichiometric ratio
32.7675 gram, SrCl
2.6H
2O1.4641 gram (by calculated amount excessive 10%), SiO
20.6008 gram, ZnO0.0407, Eu
2O
30.1320 gram is put into the agate mortar mixed grinding; Put into corundum crucible, add a cover. place in the High Temperature Furnaces Heating Apparatus, at CO or H
2Under the reducing atmosphere, under 1000-1200 ℃ of temperature roast 3-5 hour; Grind behind the naturally cooling, promptly obtaining chemical formula is Sr
4.75Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.15Single-phase white-emitting phosphor.
As shown in Figure 1, be this Sr
4.75Zn
0.10(SiO
4)
2Cl
2: Eu
2+ 0.15Emmission spectrum (the λ of fluorescent material
Ex=400nm) and excitation spectrum (λ
Em=445nm; λ
Em=546nm), its chromaticity coordinates is x=0.3146, y=0.3747; Colour temperature is T
c=6265K; Colour rendering index is Ra=69.6.
More than the excitation spectrum of the prepared fluorescent material of each embodiment show, be effectively in the 360-410nm ultraviolet region and excite; Emmission spectrum shows that blue-light-emitting band and yellow-green colour luminous zone can synthesize white lights.
Claims (5)
1. the single-phase white-emitting phosphor based near ultraviolet excitation is characterized in that the chemical formula of described fluorescent material is: Sr
5-m-nZn
n(SiO
4)
2Cl
2: Eu
2+ m, wherein, 0.10≤m≤0.15; 0≤n≤0.20.
2. the single-phase white-emitting phosphor based near ultraviolet excitation according to claim 1 is characterized in that mole number m, the n in the described chemical formula is: m=0.12, n=0.10.
3. the single-phase white-emitting phosphor based near ultraviolet excitation according to claim 1 is characterized in that mole number m, the n in the described chemical formula is: m=0.15, n=0.10.
4. the preparation method of the described white emitting fluorescent powder of claim 1 is characterized in that may further comprise the steps:
A. with SiO
2, Eu
2O
3, SrCO
3, ZnO, SrCl
2.6H
2O makes raw material, takes by weighing above-mentioned each raw material by the stoichiometric ratio of each material in the described chemical formula of claim 1, carries out ground and mixed;
B. above-mentioned compound is inserted in the corundum crucible, at CO or H
2Roast under the reducing atmosphere, roast temperature are 1000 ℃-1200 ℃, and the roast time is 3-5 hour, grind behind the naturally cooling and promptly get described single-phase white-emitting phosphor.
5. the preparation method of white emitting fluorescent powder according to claim 4 is characterized in that SrCl in the described mixing raw material of step a
2.6H
2The proportional quantity of O is for the 110%-120% by the stoichiometric ratio calculated amount, to compensate its scaling loss in roast.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660262A (en) * | 2012-05-04 | 2012-09-12 | 苏州大学 | Eu<2+> activated chloride calcium silicate fluorescent powder, preparation method and application |
| CN107611240A (en) * | 2017-09-22 | 2018-01-19 | 苏州轻光材料科技有限公司 | A kind of white light LEDs lamp bead preparation method of burst of ultraviolel perovskite fluorescent material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260321C (en) * | 2003-06-18 | 2006-06-21 | 北京有色金属研究总院 | Luminscent-powder in use for LED of white light, preparing method and electric light source produced |
| CN100404639C (en) * | 2005-04-22 | 2008-07-23 | 中国科学院长春光学精密机械与物理研究所 | Single-phase whitelight fluorescent powder for ultraviolet light excitation |
| CN100554373C (en) * | 2006-12-21 | 2009-10-28 | 温州大学 | A kind of LED lamp single component white light fluorescent powder and preparation method thereof |
| CN100551998C (en) * | 2007-11-15 | 2009-10-21 | 上海交通大学 | The preparation method of ultraviolet light excitated single phase white radiation fluorescent powder |
-
2009
- 2009-06-05 CN CN2009100670765A patent/CN101565620B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660262A (en) * | 2012-05-04 | 2012-09-12 | 苏州大学 | Eu<2+> activated chloride calcium silicate fluorescent powder, preparation method and application |
| CN107611240A (en) * | 2017-09-22 | 2018-01-19 | 苏州轻光材料科技有限公司 | A kind of white light LEDs lamp bead preparation method of burst of ultraviolel perovskite fluorescent material |
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Granted publication date: 20120411 Termination date: 20140605 |