CN103074057A - Rare earth-doped aluminate fluorescent powder and preparation method thereof - Google Patents
Rare earth-doped aluminate fluorescent powder and preparation method thereof Download PDFInfo
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- CN103074057A CN103074057A CN2012105754576A CN201210575457A CN103074057A CN 103074057 A CN103074057 A CN 103074057A CN 2012105754576 A CN2012105754576 A CN 2012105754576A CN 201210575457 A CN201210575457 A CN 201210575457A CN 103074057 A CN103074057 A CN 103074057A
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- fluorescent powder
- aluminate fluorescent
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- earth
- doped aluminate
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Abstract
The invention discloses rare earth-doped aluminate fluorescent powder and a preparation method thereof. The chemical formula of the aluminate fluorescent powder is Cal-x-yAl2B2O8: xRE, yR, wherein B is a combination of Si and Ge; Re is Eu; x is not less than 0.001 and not more than 0.02; R is Mn; and y is not less than 0.01 and not more than 0.35. Raw materials are sintered with fluxing agent under the condition of protective atmosphere after being weighed according to the chemical formula; and a product obtained through sintering is taken out for grinding and washing after being cooled to obtain the aluminate fluorescent powder. The aluminate fluorescent powder and the preparation method solve the problems of mixed preparation of the fluorescent powder, color reabsorption and the like, so that the luminous efficiency, the color stability and the indication index are largely improved.
Description
Technical field
The invention belongs to LED fluorescent material, relate to a kind of rear-earth-doped aluminate fluorescent powder and preparation method thereof.
Background technology
White light LEDs has the advantages such as environmental protection, volume is little, the life-span is long, speed of response is fast, and has overcome the shortcoming such as many, the frangible and gurry mercury pollution of power consumption that conventional incandescent and luminescent lamp exist.Demonstrate huge application prospect at aspects such as special lighting, liquid-crystal display and general lightings.
Light conversion hysteria white light LEDs is the easiest realization industrialization at present, and wherein the most general method is: excite YAG:Ce by blue chip
3+Yellow fluorescent powder utilizes gold-tinted and blue light to obtain white light.But the glow color of such white light LEDs is easy to be subjected to the impact of received current and fluorescent coating thickness, and YAG:Ce
3+Luminous intensity influenced by ambient temperature also very large.For overcoming the above problems, this field turns to employing ultraviolet-near-ultraviolet radiation InGaN chip excitated fluorescent powder to realize white light LEDs attention gradually.
Because the existence of the problems such as fluorescent material mixing preparation and color absorb again, so that luminous efficiency and color stability, demonstration index etc. have larger impact, developing in recent years near ultraviolet excitated panchromatic single white phosphors becomes a study hotspot.
Summary of the invention
The problem that the present invention solves is to provide a kind of rear-earth-doped aluminate fluorescent powder and preparation method thereof, overcomes fluorescent material mixing preparation and color and absorbs, so that luminous efficiency and color stability, demonstration index etc. are greatly improved.
The present invention is achieved through the following technical solutions:
A kind of rear-earth-doped aluminate fluorescent powder, the chemical general formula of this aluminate fluorescent powder are Ca
1-x-yAl
2B
2O
8: xRE, yR; Wherein B is the combination of Si and Ge, and RE is Eu, 0.001≤x≤0.02, and R is Mn, 0.01≤y≤0.35.
The mol ratio of described Si:Ge is 1.5～1.95:0.05～0.5.
Described x=0.01.
Described y is 0.0.15≤y≤0.35.
A kind of preparation method of rear-earth-doped aluminate fluorescent powder may further comprise the steps:
1) according to chemical general formula Ca
1-x-yAl
2B
2O
8: xRE, the mol ratio of Ca, Al, B, RE, R takes by weighing oxide compound or the carbonate that contains Ca, Al, B, RE, R element among the yR, and with its grinding, be mixed to get mixture; Wherein, B is the combination of Si and Ge, and RE is Eu, 0.001≤x≤0.05, and R is Mn, 0.01≤y≤0.35;
2) in the prepared mixture of step 1), add the fusing assistant that accounts for mixture total mass 2～5t%, under the protective atmosphere condition, carry out sintering;
3) with step 2) the rear taking-up of sintering products therefrom cooling is ground, washing, obtains aluminate fluorescent powder Ca
1-x-yAl
2B
2O
8: xRE, yR.
Described fusing assistant is H
3BO
3Or fluorochemical, described fluorochemical is one or more in the fluorochemical of Ca, B.
Described sintering is under protective atmosphere, and sintering temperature is at 1300 ℃-1550 ℃, sintering time 〉=5 hour.
Described protective atmosphere is H
2, N
2/ H
2, NH
3In one or more.
Described protective atmosphere is N
2And H
2Mixing, its volume ratio is N
2: H
2=3:1～99:1.
The NH that described protective atmosphere is
3And H
2Mixing, its volume ratio is NH
3: H
2=3:1～99:1.
Compared with prior art, the present invention has following useful technique effect:
Rear-earth-doped aluminate fluorescent powder provided by the invention and preparation method thereof, adopting common cheap compound is starting material synthetics Physicochemical stable in properties, luminescent properties white light emission aluminate fluorescent powder good, single-matrix, synthetic fluorescent material can excite lower emission white light at ultraviolet-near ultraviolet chip; Overcome the existence of the problems such as fluorescent material mixing preparation and color absorb again, so that luminous efficiency and color stability, demonstration index etc. are greatly improved.
Rear-earth-doped aluminate fluorescent powder provided by the invention and preparation method thereof, workable, cost of material is cheap, and process window is wide, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is prepared Ca
0.99-xAl
2Si
1.95Ge
0.05O
8: 0.01Eu
2+, xMn
2+(x=0.15-0.35) chromaticity coordinates and correlated(color)temperature;
Fig. 2 is not for adding the emmission spectrum of fluorescent material corresponding among the blue colour fluorescent powder of Mn active ions and Fig. 1.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, and the explanation of the invention is not limited.
Embodiment 1
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.84Al
2Si
1.95Ge
0.05O
8: 0.01Eu, the 0.15Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant H of 3wt%
3BO
3After mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas N
2: H
2With 1550 ℃ of temperature sintering 12 hours, be cooled to afterwards room temperature and take out among=the 3:1, grind and sieve by washed with isopropyl alcohol, drying, namely obtain pearl opal fluorescent material Ca
0.84Al
2Si
1.95Ge
0.05O
8: 0.01Eu, 0.15Mn.
Embodiment 2
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.79Al
2Si
1.95Ge
0.05O
8: 0.01Eu, the 0.20Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant NaF of 2wt% is after mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas N
2: H
2With 1450 ℃ of temperature sintering 5 hours, be cooled to afterwards room temperature and take out among=the 9:1, grind and sieve by washed with isopropyl alcohol, drying, namely obtain pearl opal fluorescent material Ca
0.79Al
2Si
1.95Ge
0.05O
8: 0.01Eu, 0.20Mn.
Embodiment 3
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.74Al
2Si
1.95Ge
0.05O
8: 0.01Eu, the 0.25Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant CaF of 4wt%
2After mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas N
2: H
2With 1350 ℃ of temperature sintering 7 hours, be cooled to afterwards room temperature among the=95:5, take out to grind and sieve by washed with isopropyl alcohol, drying; Namely obtain white fluorescent powder Ca
0.74Al
2Si
1.95Ge
0.05O
8: 0.01Eu, 0.25Mn.
Embodiment 4
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.69Al
2Si
1.95Ge
0.05O
8: 0.01Eu, the 0.30Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant BaF of 5wt%
2After mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas NH
3In with 1500 ℃ of temperature sintering 10 hours, be cooled to afterwards room temperature and take out, grind and sieve by washed with isopropyl alcohol, drying, namely obtain white fluorescent powder Ca
0.69Al
2Si
1.95Ge
0.05O
8: 0.01Eu, 0.30Mn.
Embodiment 5
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.64Al
2Si
1.95Ge
0.05O
8: 0.01Eu, the 0.35Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant SrF of 3wt%
2After mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas NH
3In with 1440 ℃ of temperature sintering 8 hours, be cooled to afterwards room temperature and take out, grind and sieve by washed with isopropyl alcohol, drying, namely obtain white fluorescent powder Ca
0.64Al
2Si
1.95Ge
0.05O
8: 0.01Eu, 0.35Mn.
Embodiment 6
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.82Al
2Si
1.9Ge
0.1O
8: 0.01Eu, the 0.17Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant SrF of 3wt%
2After mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas NH
3In with 1430 ℃ of temperature sintering 4 hours, be cooled to afterwards room temperature and take out; Grinding is sieved by washed with isopropyl alcohol, drying, namely obtains pearl opal fluorescent material Ca
0.82Al
2Si
1.9Ge
0.1O
8: 0.01Eu, 0.17Mn.
Embodiment 7
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.77Al
2Si
1.8Ge
0.2O
8: 0.01Eu, the 0.22Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant SrF of 3wt%
2After mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas NH
3In with 1500 ℃ of temperature sintering 7 hours, be cooled to afterwards room temperature and take out, grind and sieve by washed with isopropyl alcohol, drying, namely obtain white fluorescent powder Ca
0.77Al
2Si
1.8Ge
0.2O
8: 0.01Eu, 0.22Mn.
Embodiment 8
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.68Al
2Si
1.6Ge
0.4O
8: 0.01Eu, the 0.31Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant SrF of 1wt%
2After mixing, fully grinding, be put in the alumina crucible, crucible placed tube furnace, at shielding gas NH
3: H
2With 1480 ℃ of temperature sintering 8 hours, be cooled to afterwards room temperature and take out among=the 90:10, grind and sieve by washed with isopropyl alcohol, drying, namely obtain white fluorescent powder Ca
0.68Al
2Si
1.6Ge
0.4O
8: 0.01Eu, 0.31Mn.
Embodiment 9
Rear-earth-doped aluminate fluorescent powder and preparation method thereof may further comprise the steps:
According to Ca
0.75Al
2Si
1.5Ge
0.5O
8: 0.01Eu, the 0.24Mn stoichiometric ratio takes by weighing CaCO
3, SiO
2, GeO
2, Al
2O
3, Eu
2O
3, MnCO
3And the fusing assistant NaF of 4wt% is after mixing, fully grinding; Be put in the alumina crucible, crucible is placed tube furnace, at shielding gas NH
3In with 1460 ℃ of temperature sintering 6.5 hours, be cooled to afterwards room temperature and take out, grind and sieve by namely obtaining white fluorescent powder Ca after washed with isopropyl alcohol, the drying
0.75Al
2Si
1.5Ge
0.5O
8: 0.01Eu, 0.24Mn.
Referring to Fig. 1, Fig. 2, be depicted as chromaticity coordinates and the correlated(color)temperature of the prepared fluorescent material of embodiment 1～5, with and with the emmission spectrum of the fluorescent material of Mn active ions not, the result shows, prepared aluminate fluorescent powder has overcome the existence that fluorescent material mixing preparation and color such as absorb again at the problem, so that luminous efficiency and color stability, demonstration index etc. are greatly improved.
Claims (10)
1. a rear-earth-doped aluminate fluorescent powder is characterized in that, the chemical general formula of this aluminate fluorescent powder is Ca
1-x-yAl
2B
2O
8: xRE, yR; Wherein B is the combination of Si and Ge, and RE is Eu, 0.001≤x≤0.02, and R is Mn, 0.01≤y≤0.35.
2. rear-earth-doped aluminate fluorescent powder as claimed in claim 1 is characterized in that, the mol ratio of Si:Ge is 1.5～1.95:0.05～0.5.
3. rear-earth-doped aluminate fluorescent powder as claimed in claim 1 is characterized in that, described x=0.01.
4. rear-earth-doped aluminate fluorescent powder as claimed in claim 1 is characterized in that, described y is 0.0.15≤y≤0.35.
5. the preparation method of a rear-earth-doped aluminate fluorescent powder is characterized in that, may further comprise the steps:
1) according to chemical general formula Ca
1-x-yAl
2B
2O
8: xRE, the mol ratio of Ca, Al, B, RE, R takes by weighing oxide compound or the carbonate that contains Ca, Al, B, RE, R element among the yR, and with its grinding, be mixed to get mixture; Wherein, B is the combination of Si and Ge, and RE is Eu, 0.001≤x≤0.05, and R is Mn, 0.01≤y≤0.35;
2) in the prepared mixture of step 1), add the fusing assistant that accounts for mixture total mass 2～5t%, under the protective atmosphere condition, carry out sintering;
3) with step 2) the rear taking-up of sintering products therefrom cooling is ground, washing, obtains aluminate fluorescent powder Ca
1-x-yAl
2B
2O
8: xRE, yR.
6. the preparation method of rear-earth-doped aluminate fluorescent powder as claimed in claim 5 is characterized in that described fusing assistant is H
3BO
3Or fluorochemical.
7. the preparation method of rear-earth-doped aluminate fluorescent powder as claimed in claim 5 is characterized in that described sintering is under protective atmosphere, and sintering temperature is at 1300 ℃～1550 ℃, sintering time 〉=5 hour.
8. the preparation method of rear-earth-doped aluminate fluorescent powder as claimed in claim 7 is characterized in that described protective atmosphere is H
2, N
2/ H
2, NH
3In one or more.
9. the preparation method of rear-earth-doped aluminate fluorescent powder as claimed in claim 8 is characterized in that described protective atmosphere is N
2And H
2Mixing, its volume ratio is N
2: H
2=3:1～99:1.
10. the preparation method of rear-earth-doped aluminate fluorescent powder as claimed in claim 8 is characterized in that the NH that described protective atmosphere is
3And H
2Mixing, its volume ratio is NH
3: H
2=3:1～99:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312529A (en) * | 2017-07-05 | 2017-11-03 | 河北利福光电技术有限公司 | A kind of narrow half-peak breadth green silicate fluorescent powder and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1900790A1 (en) * | 2005-04-08 | 2008-03-19 | National Institute of Advanced Industrial Science and Technology | Stress luminescent material, process for producing the same, composite material containing the stress luminescent material, and matrix structure of the stress luminescent material |
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2012
- 2012-12-26 CN CN2012105754576A patent/CN103074057A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1900790A1 (en) * | 2005-04-08 | 2008-03-19 | National Institute of Advanced Industrial Science and Technology | Stress luminescent material, process for producing the same, composite material containing the stress luminescent material, and matrix structure of the stress luminescent material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312529A (en) * | 2017-07-05 | 2017-11-03 | 河北利福光电技术有限公司 | A kind of narrow half-peak breadth green silicate fluorescent powder and preparation method thereof |
| CN107312529B (en) * | 2017-07-05 | 2020-12-08 | 河北利福光电技术有限公司 | Narrow half-peak-width green silicate fluorescent powder and preparation method thereof |
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Application publication date: 20130501 |