CN103395997B - A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof - Google Patents
A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof Download PDFInfo
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- CN103395997B CN103395997B CN201310312850.0A CN201310312850A CN103395997B CN 103395997 B CN103395997 B CN 103395997B CN 201310312850 A CN201310312850 A CN 201310312850A CN 103395997 B CN103395997 B CN 103395997B
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Abstract
The invention discloses a kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof.With rare earth ion Dy
3+, Tm
3+, Tb
3+and Eu
3+for luminescence center, it singly mixed or mixes altogether in borosilicate glass ceramic forerunner, under burst of ultraviolel, sending warm white.Its preparation method comprises: choosing of (a) raw material, the mixing that (b) prepares burden, and (c) glass-ceramic founds three steps.Under burst of ultraviolel, singly mix Dy
3+time, devitrified glass presents white light emission.By doping Tm
3+, Tb
3+and Eu
3+, achieve and finally arrive ruddiness color adaptation by blue light to white light.
Description
Technical field
The present invention relates to rare earth material synthesis technical field, particularly relate to a kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof.
Background technology
LED is the solid state light emitter of a kind of high-level efficiency, stable performance, low cost, can be widely used on various set lights, wide market.White light LEDs is expected to become the new lighting source of forth generation, realizes the green illumination of energy-conserving and environment-protective.White light LEDs realizes there is a variety of mode, and what current business-like most of White-light LED illumination device adopted is the fluorescent material that the associating of blue light InGaNLED chip can launch gold-tinted, green glow, orange light.This kind of light-emitting phosphor efficiency is higher, but because of red light emitting intensity deficiency, therefore colour rendering index is on the low side, and colour temperature is higher, and white light easily drifts about, and cannot meet the demand of high performance device.For meeting its service requirements, the monomer material that the direct transmitting white of a kind of energy is prepared in doping is imperative.
Summary of the invention
Goal of the invention: disclose a kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof, in this, as the candidate material of the white light LEDs except fluorescent material.:
Technical scheme, prepares the rear-earth-doped crystallite fluorescent glass of white light LEDs, and each component and molar percentage (mol%) thereof are: SiO
2: 25%, B
2o
3: 10%, Na
2o:9%, SrF
2: 4%, GdF
32%, Re
3+: x%, a certain amount of B
2o
3introducing can change glass network structure, strengthen covalency, and then change the luminous intensity of rare earth ion; SrF
2and GdF
3introducing, make to grow GdSr in this glass
2f
2crystallite.
Tb
3+luminescence be mainly positioned at the green wavelength of 542nm, Eu
3+ion mainly produces the emitting red light of 612nm, Dy
3+the luminescence of ion is mainly positioned at Huang, blue light region, therefore singly mixes Dy
3+time, jointly regulate transmitting white by doping content and matrix precursor.Rare earth ion easily produces concentration quenching effect when high density, requires that the doping content of rare earth ion is within a suitable scope, therefore works as Dy
3+during=0.1-0.5mol%, the luminosity of glass-ceramic and emmission spectrum can meet ultraviolet 380-420nm and excite, and send white light.During codoped, the conveniently adjustment of emissive porwer ratio, fixing Dy
3+concentration be 0.3mol%, only change Tm
3+, Tb
3+and Eu
3+concentration, reach and regulate the object of chromaticity coordinates, realize by the adjustment of blue light, white light, green glow, ruddiness.
The preparation method of the transparent glass ceramics that the present invention relates to comprises the following steps:
Choosing of (a) raw material
Glass-ceramic raw material is mainly analytically pure oxide compound and fluorochemical, and rare earth ion selects purity to be the fluorochemical of 99.99%.
The mixing of (b) glass-ceramic admixtion
Take raw material accurately according to proportioning, put into mortar and add dehydrated alcohol and fully grind 0.5 hour.
C () glass-ceramic is founded
What glass smelting adopted is corundum crucible, and through founding, glass melting temperature is 1400 DEG C, 40 minutes time, has then carried out thermal treatment.Annealed again, annealing temperature is 640 DEG C, and the time is 8 hours.
Beneficial effect:
(1) preparation method of the present invention is easy, is applicable to industrial mass manufacture.
(2) glass-ceramic that the present invention obtains has good thermostability and chemical stability compared with fluorescent material.
(3) glass-ceramic of the present invention not only achieves white light emission, meanwhile, can realize blue light, white light, green glow, the adjustment of ruddiness wideband district.
(4) this transparent glass ceramics does not need, by epoxy encapsulation, to avoid illumination easily this shortcoming aging.
(5) the present invention has prepared and has singly mixed (Dy
3+), mix (Dy altogether
3+, Tm
3+, Dy
3+, Tb
3+, Dy
3+, Eu
3+) transparent glass ceramics.This glass-ceramic has the luminescence of efficient stable, has good absorption in ultraviolet.
Accompanying drawing explanation
Fig. 1 is the emmission spectrum of sample under 354nm excites of embodiment 1-5.
Fig. 2 is the emmission spectrum of sample under 354nm excites of embodiment 6-10.
Fig. 3 is the emmission spectrum of sample under 382nm excites of embodiment 11-15.
Fig. 4 is the emmission spectrum of sample under 382nm excites of embodiment 16-20.
Embodiment:
Embodiment 1-20 prepares white light LEDs rare earth doping transparent glass-ceramic as follows:
Choosing of (a) raw material
Glass-ceramic raw material is mainly analytically pure oxide compound and fluorochemical, and rare earth ion selects purity to be the fluorochemical of 99.99%.
The mixing of (b) glass-ceramic admixtion
Take raw material accurately according to proportioning, put into mortar and add dehydrated alcohol and fully grind 0.5 hour.
C () glass-ceramic is founded
What glass smelting adopted is corundum crucible, and through founding, glass melting temperature is 1400 DEG C, 40 minutes time, has then carried out thermal treatment.Annealed again, annealing temperature is 640 DEG C, and the time is 8 hours.
Embodiment 1-5
The oxide compound that substrate material Analysis about Selection is pure and fluorochemical, rare earth ion select concentration be 99.99% fluorochemical be main raw material, according to SiO
2: 25%, B
2o
3: 10%, Na
2o:9%, SrF
2: 4%, GdF
3: 2%, Dy
3+: x, x=0.1, the ratio of 0.2,0.3,0.4,0.5mol% takes raw material 5g altogether, and each raw materials quality is as shown in table 1.
The glass composition of table 1 embodiment 1-5
Embodiment 6-10
The oxide compound that substrate material Analysis about Selection is pure and fluorochemical, rare earth ion select concentration be 99.99% fluorochemical be main raw material, according to SiO
2: 25%, B
2o
3: 10%, Na
2o:9%, SrF
2: 4%, GdF
3: 2%:0.3Dy
3+xTm
3+, the ratio of x=0.15,0.3,0.45,0.6,0.75mol% takes raw material 5g altogether, and each raw materials quality such as table 2 shows.
The glass composition of table 2 embodiment 6-10
Embodiment 11-15
The oxide compound that substrate material Analysis about Selection is pure and fluorochemical, rare earth ion select concentration be 99.99% fluorochemical be main raw material, according to SiO
2: 25%, B
2o
3: 10%, Na
2o:9%, SrF
2: 4%, GdF
3: 2%:0.3Dy
3+xEu3
+, the ratio of x=0.5,1.0,1.5,2.0,2.5mol% takes raw material 5g altogether, and each raw materials quality is as table 3.
The glass composition of table 3 embodiment 11-15
Embodiment 16-20
The oxide compound that substrate material Analysis about Selection is pure and fluorochemical, rare earth ion select concentration be 99.99% fluorochemical be main raw material, according to SiO
2: 25%, B
2o
3: 10%, Na
2o:9%, SrF
2: 4%, GdF
3: 2%:0.3Dy
3+xTb3+, x=0.5, the ratio of 1.0,1.5,2.0,2.5mol% takes raw material 5g altogether, and each raw materials quality is as table 4.
The glass composition of table 4 embodiment 16-20
Claims (5)
1. a white light LEDs rare earth doping transparent glass-ceramic its consist of:
Each component and mol ratio thereof are: SiO
2: B
2o
3: Na
2o:SrF
2: GdF
3: Dy
3+=25:10:9:4:2:x, x=0.1 or 0.2 or 0.3 or 0.4 or 0.5.
2. a white light LEDs rare earth doping transparent glass-ceramic its consist of:
Each component and mol ratio thereof are: SiO
2: B
2o
3: Na
2o:SrF
2: GdF
3: Dy
3+: Re
3+=25:10:9:4:2:0.3:x,
Wherein Re
3+for Tm
3+or Eu
3+or Tb
3+,
Work as Re
3+=Tm
3+time, x=0.15 or 0.3 or 0.45 or 0.6 or 0.75;
Work as Re
3+=Eu
3+or Tb
3+time, x=0.5 or 1.0 or 1.5 or 2.0 or 2.5.
3. a rare earth doping transparent glass-ceramic preparation method as claimed in claim 1 or 2, is characterized in that, comprise following step:
Choosing of (a) raw material
Glass-ceramic raw material is analytically pure oxide compound and fluorochemical, and rare earth ion selects purity to be the fluorochemical of 99.99%;
The mixing of (b) glass-ceramic admixtion
Accurately take raw material according to proportioning, put into mortar and add dehydrated alcohol and fully grind 0.5 hour;
C () glass-ceramic is founded
What glass-ceramic founded employing is corundum crucible, high temperature melting for some time, is then cooled to glass-ceramic rapidly, more annealed, increases the degree of crystallinity of crystallite.
4. rare earth doping transparent glass-ceramic preparation method according to claim 3, is characterized in that, in step (c), glass melting temperature is 1400 DEG C, 40 minutes time.
5. rare earth doping transparent glass-ceramic preparation method according to claim 3, is characterized in that, in step (c), annealing temperature is 640 DEG C, and the time is 8 hours.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103771714A (en) * | 2014-01-21 | 2014-05-07 | 华南理工大学 | Tm<3+> single-doped three-photon infrared quantum cutting microcrystalline glass as well as preparation method and application thereof |
| CN104163572A (en) * | 2014-07-15 | 2014-11-26 | 南昌大学 | Transparent glass ceramic having high efficiency white light emission and preparation method thereof |
| CN104355545A (en) * | 2014-09-24 | 2015-02-18 | 南京邮电大学 | Transparent glass ceramic having double-frequency light absorption and conversion capability and preparation method for transparent glass ceramic |
| CN104313689B (en) * | 2014-10-15 | 2017-03-29 | 宁波大学 | For the Tb of white light LEDs3+/Eu3+/Tm3+Three doped alpha NaYF4Monocrystal and preparation method thereof |
| CN107311458B (en) * | 2017-06-13 | 2020-02-21 | 南京邮电大学 | Rare earth doped transparent glass ceramic with white light emission and light temperature sensing functions and preparation method thereof |
| CN108275882B (en) * | 2018-01-10 | 2020-11-06 | 南京邮电大学 | Ultraviolet light excited multicolor light emitting glass and preparation method thereof |
| CN108863087A (en) * | 2018-07-30 | 2018-11-23 | 吉林工程技术师范学院 | A kind of rear-earth-doped niobates transparent glass ceramics and preparation method thereof |
| CN111153594B (en) * | 2020-01-09 | 2022-06-07 | 温州大学 | YAG-Ce glass ceramic and preparation method and application thereof |
| CN114538769B (en) * | 2020-11-27 | 2023-12-01 | 天津工业大学 | Rare earth element Dy doped anti-radiation borosilicate luminescent glass and preparation method thereof |
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| CN101723593A (en) * | 2009-11-30 | 2010-06-09 | 浙江大学 | Luminous glass ceramic used for LED white-light illumination and preparation method thereof |
| CN102603194A (en) * | 2011-12-22 | 2012-07-25 | 中国计量学院 | Rare earth doped microcrystalline glass of precipitated beta-NaGdF4 nanocrystalline and preparation method thereof |
| CN102838279A (en) * | 2012-10-26 | 2012-12-26 | 沈阳化工大学 | Preparation method for Eu<3+> ion doped oxyfluoride borosilicate microcrystal glass |
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| DE102006027306B4 (en) * | 2006-06-06 | 2013-10-17 | Schott Ag | Process for the preparation of a glass ceramic with a garnet phase and use of the glass ceramic produced thereafter |
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| CN101723593A (en) * | 2009-11-30 | 2010-06-09 | 浙江大学 | Luminous glass ceramic used for LED white-light illumination and preparation method thereof |
| CN102603194A (en) * | 2011-12-22 | 2012-07-25 | 中国计量学院 | Rare earth doped microcrystalline glass of precipitated beta-NaGdF4 nanocrystalline and preparation method thereof |
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Application publication date: 20131120 Assignee: Jiangsu Nanyou IOT Technology Park Ltd. Assignor: NANJING University OF POSTS AND TELECOMMUNICATIONS Contract record no.: 2016320000210 Denomination of invention: Rare earth doped transparent glass ceramic for white-light LED (Light-emitting Diode) and preparation method thereof Granted publication date: 20151202 License type: Common License Record date: 20161114 |
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Assignee: Jiangsu Nanyou IOT Technology Park Ltd. Assignor: NANJING University OF POSTS AND TELECOMMUNICATIONS Contract record no.: 2016320000210 Date of cancellation: 20180116 |
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