CN101759362A - Rare earth doped luminescent glass and preparation method thereof - Google Patents
Rare earth doped luminescent glass and preparation method thereof Download PDFInfo
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- CN101759362A CN101759362A CN201010022968A CN201010022968A CN101759362A CN 101759362 A CN101759362 A CN 101759362A CN 201010022968 A CN201010022968 A CN 201010022968A CN 201010022968 A CN201010022968 A CN 201010022968A CN 101759362 A CN101759362 A CN 101759362A
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Abstract
The invention discloses rare earth doped luminescent glass and a preparation method thereof, and the rare earth doped luminescent glass is mainly used as luminescent material in the fields of photoelectron, illumination engineering science and technology and the like. In the invention, rare earth ions of Dy<3+> and Eu<3+> are used as main components and are singly doped or together doped in a phosphate glass matrix. Under the excitation of ultraviolet light with the wavelength of 360 nm, the rare earth ions can emit respective characteristic light, and transmission of energy from Dy<3+> to Eu<3+> exists. The preparation method comprises the steps of (a) selecting raw materials, (b) preparing and mixing glass batch, (c) melting glass and (d) processing samples. Ultraviolet-visible excitation and emission spectrum test are carried out on the processed glass, a result shows that the rare earth ion doped luminescent glass has excellent performance, and can be effectively excited by ultraviolet light. In addition, Eu<3+> can be effectively sensitized by Dy<3+> so that the luminescent efficiency is improved.
Description
Technical field
The present invention relates to emitting electron, illuminating engineering sciemtifec and technical sphere luminescent material and preparation method thereof, especially relate to white light LEDs with rare earth ion doped fluorescent glass.
Background technology
Lighting system is the important component part of human lives's energy consumption.The main product of traditional lighting is incandescent light and luminescent lamp.The incandescent light light efficiency is low, the life-span short, and luminescent lamp (containing fluorescent lamp, electricity-saving lamp) easily causes mercury pollution to environment, exhausted day by day and environmental pollution increasing today in global resources, human society is badly in need of a kind of efficient, energy-conservation, long lifetime of searching, pollution-free green light source.White light LEDs has the advantages that volume is little, the life-span is long, luminous efficiency is high.Compare with incandescent light, white light LEDs is a kind of cold light source, and radiation mainly concentrates on visible region, produces heat hardly, has also eliminated the harm of non-visible light district hertzian wave to the people.Compare with luminescent lamp, the manufacturing of white light LEDs and use can not be introduced the pollution of mercury, and the continuous spectrum of white light LEDs is more near natural light.From energy-conservation prospect, the energy consumption of white light LEDs only is 1/8 of an incandescent light, 1/2 of luminescent lamp, and its life-span can reach 100,000 hours, is 50～100 times of conventional fluorescent.Simultaneously, semiconductor lamp has the characteristics of safety, no stroboscopic, for domestic lighting, is " the green lighting source " of putting things right once and for all.Scientific circles and industrial community expert prophesy, replace electron tube as transistor, semiconductor lighting will replace traditional incandescent light and luminescent lamp, become after IT another growth rapidly, use one of the emerging high-tech sector of wide, tool development prospect and industry.At present, substantial contribution is all dropped into to the research and development of LED lighting engineering in the U.S., European Union, Japan and China a lot of countries and regions such as (comprising Taiwan), and the novel material in relevant this field, the report of new technology also emerge in an endless stream.Along with succeeding in developing of 360-400nm ultraviolet LED (UV-LED), then become current research focus with the compound white light of UV-LED/ three primary colors fluorescent powder.Yet high-power, the high brightness and the high-color rendering light-source angle that are used for general lighting from development consider that there is the wretched insufficiency of aspects such as efficient, stability, colourity, encapsulation in existing fluorescent material/Resins, epoxy white light pattern.It is abundant that rare earth ion doped fluorescent glass combines rare earth luminescence, the stable and good physics of glass, chemistry and thermostability, controlling cost, simplify Production Flow Chart, aspect such as environmental protection has outstanding advantage more, becomes white light LEDs another selectable approach with luminescent material.
The luminous 4f electronics based on them of rare earth compound is within the f-f configuration or the transition between the f-d configuration.Have the rare earth ion or the atom of the 4f shell of underfilling, its spectrum has covered the visible region of 390-760nm.Rare earth luminous bright in luster, light absorpting ability is strong, the efficiency of conversion height, and emission wavelength range of distribution field width, fluorescence lifetime reaches 6 orders of magnitude from crossing millisecond nanosecond.Glass then has physics and stable chemical performance, and is high temperature resistant, can bear the multiple advantages such as effect of great-power electronic bundle, high-energy radiation and strong UV-light.Therefore, rear-earth-doped fluorescent glass has becomes the possibility of white light LEDs with luminescent material, has very high researching value.In recent years, the transmission ofenergy between the doping with rare-earth ions is paid attention to by more and more people as the common method of effective raising luminous efficiency.
The present invention has developed doping with rare-earth ions Dy
3+And Eu
3+The barium phosphate glass, systematic research its luminescent properties and Dy
3+And Eu
3+Between transmission ofenergy.This fluorescent glass can have stable luminous under the exciting of UV-light.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of rare earth doped luminescent glass and preparation method thereof, with the candidate material of using as the White-light LED illumination except fluorescent material.The present invention has studied Dy especially
3+And Eu
3+Between transmission ofenergy, find Eu
3+Can be effectively by Dy
3+Sensitization improves luminous efficiency.
The preparation method of rare earth doped luminescent glass of the present invention comprises the steps:
A) raw material chooses
Barium phosphate glass raw material sources are in analytically pure phosphoric acid salt and carbonate.Rare earth ion is selected the oxide compound of purity 99.99% for use.
B) outfit of glass batch and mixing
In the weighing room of room temperature and high cleaning,, sample is ground in the ceramic grinding of cleaning evenly according to molar percentage rapid weighing sample on analytical balance.Afterwards well-mixed admixtion is poured in the clean corundum crucible of previously prepd standby.
C) glass smelting
The corundum crucible of placing admixtion is put in the electric furnace that is put in 1250 ℃ in temperature 400-450 ℃ the retort furnace after preheating 1-2 hour and founded 1-2 hour.Subsequently glass metal is poured in the stainless steel mould of 400-500 ℃ of following preheating and poured into the rectangular parallelepiped glass block, process is as quickly as possible to avoid the generation of bubble and striped.Glass block is placed on the good refractory brick of preheating then, put into retort furnace and anneal, annealing temperature is 400～450 ℃, is incubated 2-3 hour, cools to room temperature with the furnace.
D) processing of sample
Block glass is through being cut into the thick sheet glass of 2mm, and through corase grind, fine grinding and polishing become the transparence sheet glass in order to test.
Embodiment
Embodiment 1
Formulating of recipe:
Adopt NH
4H
2PO
4, BaCO
3, Eu
2O
3And Dy
2O
3Be main raw material, according to molar percentage, composition as shown in table 1 takes by weighing admixtion 30g
The glass mole of table 1 embodiment 1 is formed (%)
Admixtion is chosen and is prepared:
Adopt analytically pure NH respectively
4H
2PO
4, BaCO
3Raw material for glass matrix; The rare earth compound Dy of high purity (99.99%)
2O
3And Eu
2O
3Raw material carries out formula calculation according to the mole composition shown in the table 1.
The mixing of admixtion and founding
Admixtion is placed in the clean ceramic grinding grinds evenly, pour in the clean corundum crucible of previously prepd standby.Corundum crucible was put in 450 ℃ of stoves of temperature preheating 1 hour, is put in afterwards in 1250 ℃ the electric furnace and founded 2 hours.Glass metal is poured in the stainless steel mould of 450 ℃ of following preheatings and poured into the rectangular parallelepiped glass block, place then on the good refractory brick of preheating, put into retort furnace and anneal, annealing temperature is 450 ℃, is incubated 3 hours, cools to room temperature with the furnace, promptly gets embodiment 1 sample.
Experimental result
Resulting glass specimen is done ultraviolet-visible and is excited, the emmission spectrum test, and the result shows that the 360nm UV-light can excite doping with rare-earth ions Dy effectively
3+And Eu
3+Sample under the exciting of 360nm UV-light, Dy
3+Emission wavelength be 483nm and 572nm, Eu
3+Emission wavelength be 592nm and 611nm.For Dy
3+, mix luminous in the sample altogether and compare obvious reduction with singly mixing, and for Eu
3+, mix luminous in the sample altogether and compare obvious enhancing with singly mixing, show Dy
3+Can effectively transmit energy and give Eu
3+
Embodiment 2 and example 3
Formulating of recipe:
Adopt NH
4H
2PO
4, BaCO
3, Eu
2O
3And Dy
2O
3Be main raw material, according to molar percentage, composition takes by weighing admixtion 30g shown in table 2 and table 3
The glass mole of table 2 embodiment 2 is formed (%)
The glass mole of table 3 embodiment 3 is formed (%)
Admixtion is chosen identical with embodiment 1 with preparation
Experimental result
Resulting glass specimen keeps Dy under the exciting of 360nm UV-light
3+Volumetric molar concentration be that 1.5 (%) are constant, along with Eu
3+The increase of volumetric molar concentration, Dy
3+Luminous intensity reduce Eu successively
3+Luminous intensity increase successively.Keep Eu
3+Volumetric molar concentration be that 0.25 (%) is constant, along with Dy
3+The increase of volumetric molar concentration, Eu
3+Luminous intensity increase Dy successively
3+Luminous intensity increase successively.The result fully proves Dy
3+And Eu
3+Between have transmission ofenergy, Dy
3+Can effectively transmit energy and give Eu
3+
Dy
3+And Eu
3+Between the existence of transmission ofenergy for the development of white light LEDs important meaning is arranged.
Claims (3)
1. a rare earth doped luminescent glass is mixed Eu altogether by barium phosphoric acid salt
3+And Dy
3+, it consists of (mol%):
65-75P
2O
5·25-35BaO:xDy
2O
3·yEu
2O
3
x＝0.25-0.75；y＝0.125-0.5
2. rare earth doped luminescent glass according to claim 1 is characterized in that the UV-light of 360-380nm is the excitation rare-earth ion effectively, and has Dy
3+To Eu
3+Transmission ofenergy.
3. according to the preparation method of claim 1 and 2 described rare earth doped luminescent glass, it is characterized in that may further comprise the steps:
A) raw material chooses
Barium phosphate glass raw material sources are in analytically pure phosphoric acid salt and carbonate.Rare earth ion is selected the oxide compound of purity 99.99% for use.
B) outfit of glass batch and mixing
In the weighing room of room temperature and high cleaning,, sample is ground in the ceramic grinding of cleaning evenly according to molar percentage rapid weighing sample on analytical balance.Afterwards well-mixed admixtion is poured in the clean corundum crucible of previously prepd standby.
C) glass smelting
The corundum crucible of placing admixtion is put in the electric furnace that is put in 1250 ℃ in temperature 400-450 ℃ the retort furnace after preheating 1-2 hour and founded 1-2 hour.Subsequently glass metal is poured in the stainless steel mould of 400-500 ℃ of following preheating and poured into the rectangular parallelepiped glass block, process is as quickly as possible to avoid the generation of bubble and striped.Glass block is placed on the good refractory brick of preheating then, put into retort furnace and anneal, annealing temperature is 400～450 ℃, is incubated 2-3 hour, cools to room temperature with the furnace.
D) processing of sample
Block glass is through being cut into the thick sheet glass of 2mm, and through corase grind, fine grinding and polishing become the transparence sheet glass in order to test.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010022968A CN101759362A (en) | 2010-01-19 | 2010-01-19 | Rare earth doped luminescent glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010022968A CN101759362A (en) | 2010-01-19 | 2010-01-19 | Rare earth doped luminescent glass and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101759362A true CN101759362A (en) | 2010-06-30 |
Family
ID=42490767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010022968A Pending CN101759362A (en) | 2010-01-19 | 2010-01-19 | Rare earth doped luminescent glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101759362A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923947A (en) * | 2012-11-06 | 2013-02-13 | 华东理工大学 | Novel white light glass and preparation method thereof |
| CN103415482A (en) * | 2011-03-02 | 2013-11-27 | 皇家飞利浦有限公司 | Tin phosphate glass containing embedded luminescent material particles |
| CN114835395A (en) * | 2022-04-12 | 2022-08-02 | 南京工业大学 | Fluorescent glass for W-LED illumination and preparation method thereof |
-
2010
- 2010-01-19 CN CN201010022968A patent/CN101759362A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103415482A (en) * | 2011-03-02 | 2013-11-27 | 皇家飞利浦有限公司 | Tin phosphate glass containing embedded luminescent material particles |
| CN102923947A (en) * | 2012-11-06 | 2013-02-13 | 华东理工大学 | Novel white light glass and preparation method thereof |
| CN114835395A (en) * | 2022-04-12 | 2022-08-02 | 南京工业大学 | Fluorescent glass for W-LED illumination and preparation method thereof |
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Application publication date: 20100630 |