CN102161887A - Yellow silicate fluorescent powder excited by blue light and preparation method thereof - Google Patents
Yellow silicate fluorescent powder excited by blue light and preparation method thereof Download PDFInfo
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- CN102161887A CN102161887A CN2011100605886A CN201110060588A CN102161887A CN 102161887 A CN102161887 A CN 102161887A CN 2011100605886 A CN2011100605886 A CN 2011100605886A CN 201110060588 A CN201110060588 A CN 201110060588A CN 102161887 A CN102161887 A CN 102161887A
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Abstract
The invention relates to a silicate fluorescent powder suitable for exciting a yellow light by a blue light and a preparation method thereof. The chemical expression formula of the yellow silicate fluorescent powder is L24-xCa(SiO4)3O:xCe<3+>, wherein x is equal to 0.0010-0.10. The preparation method comprises the following steps: adding a flux in a mixture of carbonates, oxides and the like of elements in the expression formula, grinding and evenly mixing; then at the reduction atmosphere, sintering for 3-7 hours at the temperature of 1200-1300 DEG C so as to obtain the yellow fluorescent powder for a light-emitting diode (LED); and exciting with the blue light of 420-80nm so as to obtain the yellow fluorescent powder with an emission peak range of 550-560nm. The fluorescent powder has the advantages of good dispersity, even granularity, high luminous intensity and good chemical stability. The excitation bands of the fluorescent powder are overlapped with the emission peaks of blue light gallium nitride LED. The fluorescent powder can be effectively excited, and white light LED with high brightness can be prepared.
Description
Technical field
The present invention relates to a kind of preparation method of silicate yellow fluorescent powder; Be particularly related to a kind of fluorescent material that is fit to blue-light excited jaundice light and preparation method thereof.
Background technology
White light LEDs is a kind of solid-state semiconductor device that converts electrical energy into white light, claim semiconductor lighting again, have the efficient height, plurality of advantages such as volume is little, the life-span is long, safety, low voltage, energy-saving and environmental protection, by people regard as after incandescent light, luminescent lamp, high-voltage gas discharging light the 4th generation lighting source, be the main product on the following illumination market.
What realize at present that white light LEDs generally adopts is that apply on blue-light LED chip efficiently can be by the blue-light excited and fluorescent material emission gold-tinted, its principle is that the blue-ray LED excitation fluorescent material produces and blue light complementary gold-tinted, utilizing lens principle that blue light, gold-tinted are mixed, making human eye produce the vision of white light.This kind fluorescent material mainly is that its chemical formula is Y by cerium activated YAG yttrium aluminum garnet at present
3Al
5O
12: Ce
3+(United States Patent (USP) 5,998,925 and European patent 862,794), excitation spectrum can effectively absorb the blue light of gan GaN photodiode near 460 ~ 470nm, the fluorescent material of garnet structure have that chemical property is stable, brightness is high, the life-span is long and luminous efficiency height etc. specific.The white light LEDs that this fluorescent material is made has very high luminous efficiency, but owing to less its colour rendering index that makes of the ruddiness composition of its emmission spectrum is on the low side.
In recent years, the yellow fluorescent powder of some other systems is developed.With Eu
2+Activated alkaline-earth metal oxynitride and silicate fluorescent powder are as Ca-α-SiAlON(Rong-Jun Xie, Naoto Hirosaki, Ken Sakuma, Yoshinobu Yamamoto, and Mamoru Mitomo, Appl. Phys. Lett. 84,5404 (2004)), CaSi
2O
2N
2(Y. Q. Li, A. C. A. Delsing, G. de With, and H. T. Hintzen, Chem. Mater. 17,3242 (2005)), and Sr
2SiO
4(J. K. Park, M. A. Lim, C. H. Kim, H. D. Park, J. T. Park, and S. Y. Choi, Appl. Phys. Lett. 82,683 (2003)).In the yellow fluorescent powder of these reports, nitric oxide fluorescent powder Ca-α-SiAlON:Eu
2+And CaSi
2O
2N
2: Eu
2+Generally need high-temperature and high-pressure conditions, synthesis condition is had relatively high expectations, silicate fluorescent powder Sr
2SiO
4: Eu
2+Best excitation peak is in the purple light zone, and the luminous efficiency of the white light LEDs of making is lower.With Ce
3+Activated aluminate and silicate fluorescent powder are as LaSr
2AlO
5(M. P. Saradhi and U. V. Varadaraju, Chem. Mater. 18,5267 (2006)), Sr
3SiO
5(H. S. Jang and D. Y. Jeo, Appl. Phys. Lett. 90,041906 (2007)) and (Ca
3-xLu
x) (Sc
2-zMg
z) Si
3O
12+ δ(application number: 200910066988.0), aluminate fluorescent powder LaSr
2AlO
5: Ce
3+Need higher synthesis temperature, silicate fluorescent powder Sr
3SiO
5: Ce
3+, Li
+Best excitation peak is at purple light zone, (Ca
3-xLu
x) (Sc
2-zMg
z) Si
3O
12+ δ: Ce
3+In used the comparatively expensive Sc of price
2O
3
Ce
3+Be the active ions that can produce d → f transition broadband emission in the trivalent rare earth ions under the room temperature, its 5d electronics is not owing to be subjected to 5s
25p
6Screening of nucleus, the radial wave function extends to the space, just produces strong disturbance under the effect of matrix ligand field, thereby influences the spectral response curve of 5d band.So Ce
3+In different substrate materials, can produce emission from ultraviolet to the ruddiness zone, generally be that crystal field strength of living in is strong, the matrix compounds covalency is strong, and its emission wavelength is shorter.Ce
3+Adulterated Y
3Al
5O
12And some aluminate, silicate etc. have this characteristic.Relative Eu
2+, Ce
3+Emission band wideer, be used for white light LED fluorescent powder, be more suitable for single primary colours white light LEDs.
Summary of the invention
The purpose of this invention is to provide a kind of blue-light excited silicate yellow fluorescent powder and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: its blue-light excited silicate yellow fluorescent powder has following chemical expression formula:
La
4?-xCa(SiO
4)
3O：xCe
3+
In the formula: x is 0.001～0.10.
The preparation method of silicate yellow fluorescent powder of the present invention is characterized in that comprising the steps:
Press chemical formula La
4-xCa (SiO
4)
3O:xCe
3+Stoichiometric ratio take by weighing corresponding raw material, described raw material is respectively lanthanum trioxide, lime carbonate, silicon-dioxide and cerium oxide, wherein x is 0.001～0.10; The back adds fusing assistant grinding mixing and obtains mixture; With this mixture crucible of packing into, in High Temperature Furnaces Heating Apparatus under reducing atmosphere and 1200～1300 ℃ of conditions sintering 3～7 hours, postcooling obtains described silicate yellow fluorescent powder to room temperature.
Further, fusing assistant of the present invention is a Sodium Fluoride, and the quality of described Sodium Fluoride is 0.01～10:100 with the ratio of the total mass of all described raw materials.
Further, reducing atmosphere of the present invention is nitrogen and hydrogen mixture or CO atmosphere.
Compared with prior art, the invention has the beneficial effects as follows:
(1) fluorescent material of the present invention is substrate material with silicate, and silicate fluorescent powder has good chemical stability and thermostability, and the high-purity silicon dioxide raw material inexpensive, be easy to get, maturing temperature is than aluminates system (as: Y
3Al
5O
12: Ce
3+) and oxynitride system (Ca-α-SiAlON:Eu
2+And CaSi
2O
2N
2: Eu
2+) characteristics such as low.Compare other silicate yellow fluorescent powders (as (Ca
3-xLu
x) (Sc
2-zMg
z) Si
3O
12+ δ: Ce
3+), the present invention has avoided using the comparatively Sc of costliness of price
2O
3And Lu
2O
3Deng rare earth oxide.
(2) the present invention is with Ce
3+For activator has prepared a kind of yellow fluorescent powder, compare Eu
2+The activated yellow fluorescent powder, Ce
3+Emission band wideer, be used for white light LED fluorescent powder, be more suitable for single primary colours white light LEDs; The emission peak of the excitation band of this fluorescent material and gan GaN photodiode is overlapping better in addition, can effectively be excited the generation yellow emission by gallium nitride diode.
(3) the present invention adds an amount of fusing assistant in raw material, reduced the sintering temperature of powder, avoid introducing impurity from reactor because calcining temperature is high, especially add Sodium Fluoride as fusing assistant after, synthetic powder granule degree is between 3 ~ 10 μ m, uniform granularity has good dispersiveness, can use without subsequent techniques such as ball millings.
Description of drawings
Fig. 1 is fluorescent powder X-ray powder diffraction (XRD) figure of the embodiment of the invention 1 preparation.
Fig. 2 is fluorescent powder scanning electron microscope (SEM) figure of the embodiment of the invention 1 preparation.
Fig. 3 is that the fluorescent powder of the embodiment of the invention 1 preparation excites and emmission spectrum, and the supervisory wavelength of excitation spectrum is 550nm, and the excitation wavelength of emmission spectrum is 465nm.
Fig. 4 is fluorescent powder X-ray powder diffraction (XRD) figure of the embodiment of the invention 4 preparations.
Fig. 5 is fluorescent powder scanning electron microscope (SEM) figure of the embodiment of the invention 4 preparations.
Fig. 6 is fluorescent powder X-ray powder diffraction (XRD) figure of the embodiment of the invention 5 preparations.
Fig. 7 is fluorescent powder scanning electron microscope (SEM) figure of the embodiment of the invention 5 preparations.
Fig. 8 is fluorescent powder X-ray powder diffraction (XRD) figure of the embodiment of the invention 6 preparations.
Fig. 9 is fluorescent powder scanning electron microscope (SEM) figure of the embodiment of the invention 6 preparations.
Embodiment
Embodiment 1: according to La
3.95Ca (SiO
4)
3O:0.05Ce
3+Take by weighing La
2O
36.9020g, CaCO
31.0725g, SiO
21.9931g, and CeO
20.0923g, add 0.01g NaF, fully ground and mixed evenly after, place in the corundum crucible, put into again High Temperature Furnaces Heating Apparatus under CO atmosphere 1200 ℃ of roastings 5 hours, postcooling obtains being fit to blue-light excited yellow fluorescent powder to room temperature.As shown in Figure 1, X-ray powder diffraction (XRD) figure shows d value and the relative intensity variation tendency and the La of product
4Ca (SiO
4)
3The standard card unanimity shows that present embodiment synthetic fluorescent material powder purity is higher.As shown in Figure 2, the granular size of present embodiment synthetic fluorescent material is 3 ~ 10 μ m, and uniform granularity has good dispersiveness.As shown in Figure 3, exciting down at blue light 465nm, emission wavelength is the gold-tinted of 555nm, as can be seen from Figure 3, fluorescent material excitation spectrum of the present invention is a wide range, covered purple light and blue light region, excitation peak is positioned near the 465nm, overlaps fine with the emission peak of gan GaN photodiode, and the spectrum peak height illustrates that fluorescent material of the present invention can effectively be excited by the blue light gallium nitride diode.When the excitation wavelength of emmission spectrum is 465nm, as can be seen from Figure 3, fluorescent material of the present invention be emitted as cerous broadband yellow emission, emission peak is positioned near the 555nm, illustrates that fluorescent material of the present invention is fit to do blue-light excited yellow fluorescent powder.
Embodiment 2: according to La
3.999Ca (SiO
4)
3O:0.001Ce
3+Take by weighing La
2O
36.9911g, CaCO
31.0730g, SiO
21.9341g, and CeO
20.0018g, add 1g NaF, after abundant ground and mixed is even, place in the corundum crucible, put into High Temperature Furnaces Heating Apparatus again in 5%H
2+ 95%N
21200 ℃ of roastings 7 hours, postcooling obtained being fit to blue-light excited yellow fluorescent powder to room temperature under the nitrogen and hydrogen mixture atmosphere of (volume ratio).The d value and relative intensity variation tendency and the La that show product by X-ray powder diffraction (XRD) figure of fluorescent powder
4Ca (SiO
4)
3The standard card unanimity shows that present embodiment synthetic fluorescent powder purity is higher.And the granular size of fluorescent material is 3 ~ 10 μ m, and uniform granularity has good dispersiveness.Present embodiment synthetic fluorescent powder excites down at blue light 465nm, and emission wavelength is the gold-tinted of 550nm.
Embodiment 3: according to La
3.9Ca (SiO
4)
3O:0.1Ce
3+Take by weighing La
2O
36.8113g, CaCO
31.0720g, SiO
21.9322 g, and CeO
20.1845 g adds 0.001g NaF, after abundant ground and mixed is even, places in the corundum crucible, puts into High Temperature Furnaces Heating Apparatus again in 5%H
2+ 95%N
21300 ℃ of roastings 3 hours, postcooling obtained being fit to blue-light excited yellow fluorescent powder to room temperature under the nitrogen and hydrogen mixture atmosphere of (volume ratio).Figure shows by resulting fluorescent material X-ray powder diffraction (XRD), the d value of this fluorescent powder product and relative intensity variation tendency and La
4Ca (SiO
4)
3The standard card unanimity shows that synthetic powder purity is higher.And the granular size of fluorescent material is 3 ~ 10 μ m, and uniform granularity has good dispersiveness.In addition, present embodiment synthetic fluorescent powder emission wavelength under blue light 465nm excites is the gold-tinted of 560nm.
Embodiment 4: according to La
3.99Ca (SiO
4)
3O:0.01Ce
3+Take by weighing La
2O
36.9773 g, CaCO
31.0738g, SiO
21.9340 g, and CeO
20.0183 g adds 0.05g H
3BO
3, fully ground and mixed evenly after, place in the corundum crucible, put into again High Temperature Furnaces Heating Apparatus under CO atmosphere 1250 ℃ of roastings 5 hours, postcooling obtains a kind of blue-light excited yellow fluorescent powder that is fit to room temperature.As shown in Figure 4, X-ray powder diffraction (XRD) figure shows d value and the relative intensity variation tendency and the La of fluorescent powder product
4Ca (SiO
4)
3The standard card unanimity shows that synthetic powder purity is higher.As shown in Figure 5, the granular size of fluorescent material is 1 ~ 20 μ m.In addition, the fluorescent powder that obtains of present embodiment excites down at blue light 465nm that emission wavelength is the gold-tinted of 555nm.
Embodiment 5: according to La
3.98Ca (SiO
4)
3O:0.02Ce
3+Take by weighing La
2O
36.9557 g, CaCO
31.0737g, SiO
21.9338 g, and CeO
20.0367 g adds 0.02g NH
3F after abundant ground and mixed is even, places in the corundum crucible, puts into High Temperature Furnaces Heating Apparatus again in 5%H
2+ 95%N
21250 ℃ of roastings 7 hours, postcooling obtained a kind of blue-light excited yellow fluorescent powder that is fit to room temperature under the nitrogen and hydrogen mixture atmosphere of (volume ratio).As shown in Figure 6, X-ray powder diffraction (XRD) figure shows d value and the relative intensity variation tendency and the La of the fluorescent powder product of present embodiment
4Ca (SiO
4)
3The standard card unanimity shows that synthetic powder purity is higher.As shown in Figure 7, the granular size of the fluorescent material that obtains of present embodiment is 1 ~ 20 μ m.And the fluorescent material that present embodiment obtains emission wavelength under blue light 465nm excites is the gold-tinted of 555nm.
Embodiment 6: according to La
3.995Ca (SiO
4)
3O:0.005 Ce
3+Take by weighing La
2O
36.9829g, CaCO
31.0739g, SiO
21.9340 g, and CeO
20.092 g adds 0.005g NH
3Cl after abundant ground and mixed is even, places in the corundum crucible, puts into High Temperature Furnaces Heating Apparatus again in 5%H
2+ 95%N
21300 ℃ of roastings 4 hours, postcooling obtained a kind of blue-light excited yellow fluorescent powder that is fit to room temperature under the nitrogen and hydrogen mixture atmosphere of (volume ratio).As shown in Figure 8, X-ray powder diffraction (XRD) figure shows d value and the relative intensity variation tendency and the La of the fluorescent powder product of present embodiment
4Ca (SiO
4)
3The standard card unanimity shows that synthetic powder purity is higher.As shown in Figure 9, the granular size of the fluorescent material that obtains of present embodiment is 1 ~ 25 μ m.And the fluorescent material that present embodiment obtains emission wavelength under blue light 465nm excites is the gold-tinted of 550nm.
Claims (4)
1. a blue-light excited silicate yellow fluorescent powder is characterized in that, this fluorescent material has following chemical expression formula:
La
4?-xCa(SiO
4)
3O：xCe
3+
In the formula: x is 0.001～0.10.
2. the preparation method of the described silicate yellow fluorescent powder of claim 1 is characterized in that comprising the steps:
Press chemical formula La
4-xCa (SiO
4)
3O:xCe
3+Stoichiometric ratio take by weighing corresponding raw material, described raw material is respectively lanthanum trioxide, lime carbonate, silicon-dioxide and cerium oxide, wherein x is 0.001～0.10; The back adds fusing assistant grinding mixing and obtains mixture; With this mixture crucible of packing into, in High Temperature Furnaces Heating Apparatus under reducing atmosphere and 1200～1300 ℃ of conditions sintering 3～7 hours, postcooling obtains described silicate yellow fluorescent powder to room temperature.
3. the preparation method of silicate yellow fluorescent powder as claimed in claim 2, it is characterized in that: described fusing assistant is a Sodium Fluoride, the quality of described Sodium Fluoride is 0.01～10:100 with the ratio of the total mass of all described raw materials.
4. as the preparation method of claim 2 or 3 described silicate yellow fluorescent powders, it is characterized in that: described reducing atmosphere is nitrogen and hydrogen mixture or CO atmosphere.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108646456A (en) * | 2018-04-28 | 2018-10-12 | 厦门天马微电子有限公司 | Display module and display device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800301A (en) * | 2004-12-31 | 2006-07-12 | 吕宗昕 | Fluorescent material |
| CN101012375A (en) * | 2007-02-06 | 2007-08-08 | 江苏苏博特新材料股份有限公司 | Rare earth red fluorescent powder and preparing method thereof |
| CN101298385A (en) * | 2007-03-29 | 2008-11-05 | Tdk株式会社 | Manufacturing methods of dielectric ceramic composition and electronic component |
-
2011
- 2011-03-14 CN CN2011100605886A patent/CN102161887B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800301A (en) * | 2004-12-31 | 2006-07-12 | 吕宗昕 | Fluorescent material |
| CN101012375A (en) * | 2007-02-06 | 2007-08-08 | 江苏苏博特新材料股份有限公司 | Rare earth red fluorescent powder and preparing method thereof |
| CN101298385A (en) * | 2007-03-29 | 2008-11-05 | Tdk株式会社 | Manufacturing methods of dielectric ceramic composition and electronic component |
Non-Patent Citations (1)
| Title |
|---|
| 翟永清 等: "白光LED用硅酸盐荧光粉的研究进展", 《河北化工》, vol. 32, no. 6, 30 June 2009 (2009-06-30), pages 2 - 4 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108646456A (en) * | 2018-04-28 | 2018-10-12 | 厦门天马微电子有限公司 | Display module and display device |
| CN108646456B (en) * | 2018-04-28 | 2021-04-30 | 厦门天马微电子有限公司 | Display module and display device |
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| CN102161887B (en) | 2013-02-13 |
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