CN103395997A - Rare earth doped transparent glass ceramic for white-light LED (Light-emitting Diode) and preparation method thereof - Google Patents
Rare earth doped transparent glass ceramic for white-light LED (Light-emitting Diode) and preparation method thereof Download PDFInfo
- Publication number
- CN103395997A CN103395997A CN2013103128500A CN201310312850A CN103395997A CN 103395997 A CN103395997 A CN 103395997A CN 2013103128500 A CN2013103128500 A CN 2013103128500A CN 201310312850 A CN201310312850 A CN 201310312850A CN 103395997 A CN103395997 A CN 103395997A
- Authority
- CN
- China
- Prior art keywords
- glass
- ceramic
- rare earth
- light
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a rare earth doped transparent glass ceramic for white-light LED (Light-emitting Diode) and a preparation method thereof. The rare earth ions Dy<3+>, Tm<3+>, Tb<3+> and Eu<3+> which are used as luminescence centers are subjected to single doping or codoping in a borosilicate glass ceramic precursor, and warm white light is emitted under the ultraviolet excitation. The preparation method comprises three steps of: (a) selecting ingredients; (b) mixing the ingredients; and (c) melting glass ceramics. Under the ultraviolet excitation, when Dy<3+> is singly doped, the microlite glass emits white light. Through doping the Tm<3+>, Tb<3+> and Eu<3+>, the color adjustment from blue light to white light and finally to red light can be realized.
Description
Technical field
The present invention relates to the rare earth material synthesis technical field, relate in particular to a kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof.
Background technology
LED is a kind of high-level efficiency, stable performance, solid state light emitter cheaply, can be widely used on various set lights, and market outlook are wide.White light LEDs be expected to become the 4th generation new lighting source, realize the green illumination of energy-conserving and environment-protective.White light LEDs realizes having a variety of modes, and what present business-like most of White-light LED illumination device adopted is the fluorescent material that the associating of blue light InGaN LED chip can be launched gold-tinted, green glow, orange light.This class light-emitting phosphor efficiency is higher, but because of the red emission undercapacity, so colour rendering index is on the low side, and colour temperature is higher, and white light easily drifts about, and can't meet the demand of high performance device.For meeting its service requirements, it is imperative that the monomer material of the direct transmitting white of a kind of energy is prepared in doping.
Summary of the invention
Goal of the invention: disclose a kind of white light LEDs with rare earth doping transparent glass-ceramic and preparation method thereof, usingd this candidate material as the white light LEDs except fluorescent material.:
Technical scheme, prepare white light LEDs with rear-earth-doped crystallite fluorescent glass, and each component and molar percentage thereof (mol%) 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 the glass network structure, strengthen covalency, and then change the luminous intensity of rare earth ion; SrF
2And GdF
3Introducing, make in this glass and grow GdSr
2F
2Crystallite.
Tb
3+The luminous green glow zone that mainly is positioned at 542nm, Eu
3+Ion mainly produces the emitting red light of 612nm, Dy
3+Luminous Huang, the blue light region of mainly being positioned at of ion, therefore singly mix Dy
3+The time, by doping content and matrix presoma, jointly regulate transmitting white.Rare earth ion easily produces the concentration quenching effect when high density, require the doping content of rare earth ion 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, in order to facilitate the adjusting of emissive porwer ratio, fixedly Dy
3+Concentration be 0.3mol%, only change Tm
3+, Tb
3+And Eu
3+Concentration, reach the purpose of regulating chromaticity coordinates, realize the adjusting by 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:
(a) raw material chooses
The glass-ceramic raw material is mainly analytically pure oxide compound and fluorochemical, and rare earth ion selection purity is 99.99% fluorochemical.
(b) mixing of glass-ceramic admixtion
According to proportioning, take accurately raw material, put into mortar and add dehydrated alcohol and fully ground 0.5 hour.
(c) glass-ceramic is founded
What glass smelting adopted is corundum crucible, and through founding, glass melting temperature is 1400 ℃, 40 minutes time, has then carried out thermal treatment.Annealed again, annealing temperature is 640 ℃, and the time is 8 hours.
Beneficial effect:
(1) preparation method of the present invention is easy, is suitable for industrial mass manufacture.
(2) glass-ceramic that makes of the present invention has good thermostability and chemical stability than fluorescent material.
(3) glass-ceramic of the present invention has not only realized white light emission, simultaneously, can realize that blue light, white light, green glow, ruddiness wideband district regulate.
(4) this transparent glass ceramics does not need to use epoxy encapsulation, has avoided easily aging this shortcoming of illumination.
(5) the present invention has prepared singly and has mixed (Dy
3+), mix altogether (Dy
3+, Tm
3+, Dy
3+, Tb
3+, Dy
3+, Eu
3+) transparent glass ceramics.This glass-ceramic has the luminous of efficient stable, in ultraviolet, has good absorption.
The 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:
(a) raw material chooses
The glass-ceramic raw material is mainly analytically pure oxide compound and fluorochemical, and rare earth ion selection purity is 99.99% fluorochemical.
(b) mixing of glass-ceramic admixtion
According to proportioning, take accurately raw material, put into mortar and add dehydrated alcohol and fully ground 0.5 hour.
(c) glass-ceramic is founded
What glass smelting adopted is corundum crucible, and through founding, glass melting temperature is 1400 ℃, 40 minutes time, has then carried out thermal treatment.Annealed again, annealing temperature is 640 ℃, and the time is 8 hours.
Embodiment 1-5
It is that 99.99% fluorochemical is main raw material that the oxide compound that the substrate material Analysis about Selection is pure and fluorochemical, rare earth ion are selected concentration, 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 of table 1 embodiment 1-5 forms
Embodiment 6-10
It is that 99.99% fluorochemical is main raw material that the oxide compound that the substrate material Analysis about Selection is pure and fluorochemical, rare earth ion are selected concentration, according to SiO
2: 25%, B
2O
3: 10%, Na
2O:9%, SrF
2: 4%, GdF
3: 2%:0.3Dy
3+X Tm
3+, x=0.15, the ratio of 0.3,0.45,0.6,0.75mol% takes raw material 5g altogether, and each raw materials quality such as table 2 show.
The glass of table 2 embodiment 6-10 forms
Embodiment 11-15
It is that 99.99% fluorochemical is main raw material that the oxide compound that the substrate material Analysis about Selection is pure and fluorochemical, rare earth ion are selected concentration, according to SiO
2: 25%, B
2O
3: 10%, Na
2O:9%, SrF
2: 4%, GdF
3: 2%:0.3Dy
3+XEu3
+, x=0.5, the ratio of 1.0,1.5,2.0,2.5mol% takes raw material 5g altogether, each raw materials quality such as table 3.
The glass of table 3 embodiment 11-15 forms
Embodiment 16-20
It is that 99.99% fluorochemical is main raw material that the oxide compound that the substrate material Analysis about Selection is pure and fluorochemical, rare earth ion are selected concentration, 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, each raw materials quality such as table 4.
The glass of table 4 embodiment 16-20 forms
Claims (6)
1. it consists of a white light LEDs with the rare earth doping transparent glass-ceramic:
Each component and molar percentage thereof (mol%) are: SiO
2: 25%, B
2O
3: 10%, Na
2O:9%, SrF
2: 4%, GdF
32%, Re
3+: x%, Re
3+=Dy
3+, Tm
3+, Tb
3+, Eu
3+, can singly mix, also can two-pack mix altogether x=0.05-0.75mol%.
2. white light LEDs rare earth doping transparent glass-ceramic according to claim 1, is characterized in that Re
3+For Dy
3+, Tm
3+, Tb
3+, Eu
3+In one or both combinations.
3. white light LEDs rare earth doping transparent glass-ceramic according to claim 1, is characterized in that Dy
3+Molar percentage (mol%) is 0.3mol%.
4. rare earth doping transparent glass-ceramic as claimed in claim 2, its preparation method comprises following step:
(a) raw material chooses
The glass-ceramic raw material is mainly analytically pure oxide compound and fluorochemical, and rare earth ion selection purity is 99.99% fluorochemical.
(b) mixing of glass-ceramic admixtion
Accurately according to proportioning, take raw material, put into mortar and add dehydrated alcohol and fully ground 0.5 hour.
(c) glass-ceramic is founded
What glass-ceramic was founded employing is corundum crucible, high temperature melting temperature for some time, then be cooled to rapidly glass-ceramic, more annealed, the degree of crystallinity of increase crystallite.
5. preparation method according to claim 4, is characterized in that, in step (c), glass melting temperature is 1400 ℃, 40 minutes time.
6. preparation method according to claim 4, is characterized in that, in step (c), annealing temperature is 640 ℃, and the time is 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310312850.0A CN103395997B (en) | 2013-07-23 | 2013-07-23 | A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310312850.0A CN103395997B (en) | 2013-07-23 | 2013-07-23 | A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103395997A true CN103395997A (en) | 2013-11-20 |
| CN103395997B CN103395997B (en) | 2015-12-02 |
Family
ID=49559791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310312850.0A Expired - Fee Related CN103395997B (en) | 2013-07-23 | 2013-07-23 | A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103395997B (en) |
Cited By (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 |
| CN104313689A (en) * | 2014-10-15 | 2015-01-28 | 宁波大学 | Tb<3+>/Eu<3+>/Tm<3+>-doped alpha-NaYF4 single crystal for white LED (light emitting diode) 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 |
| CN107311458A (en) * | 2017-06-13 | 2017-11-03 | 南京邮电大学 | It is a kind of to sense difunctional rare earth doping transparent glass ceramics and preparation method thereof with white light emission and light temperature |
| CN108275882A (en) * | 2018-01-10 | 2018-07-13 | 南京邮电大学 | A kind of polychrome light emitting glass of ultraviolet excitation 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 |
| CN111153594A (en) * | 2020-01-09 | 2020-05-15 | 温州大学 | YAG-Ce glass ceramic and preparation method and application thereof |
| CN114538769A (en) * | 2020-11-27 | 2022-05-27 | 天津工业大学 | Rare earth element Dy-doped anti-irradiation borosilicate luminescent glass and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080041106A1 (en) * | 2006-06-06 | 2008-02-21 | Karine Seneschal-Merz | Method for producing a glass ceramic having a garnet phase |
| 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 |
-
2013
- 2013-07-23 CN CN201310312850.0A patent/CN103395997B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080041106A1 (en) * | 2006-06-06 | 2008-02-21 | Karine Seneschal-Merz | Method for producing a glass ceramic having a garnet phase |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| FENGXIA XIN，ET AL: "Structure and luminescence properties of Eu/Tb codoped oxyfluoride glass ceramics containing Sr2GdF7 nanocrystals", 《OPTICAL MATERIALS》, no. 34, 17 August 2011 (2011-08-17), pages 85 - 88 * |
Cited By (13)
| 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 |
| CN104313689A (en) * | 2014-10-15 | 2015-01-28 | 宁波大学 | Tb<3+>/Eu<3+>/Tm<3+>-doped alpha-NaYF4 single crystal for white LED (light emitting diode) 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 |
| CN107311458A (en) * | 2017-06-13 | 2017-11-03 | 南京邮电大学 | It is a kind of to sense difunctional rare earth doping transparent glass ceramics and preparation method thereof with white light emission and light temperature |
| 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 |
| CN108275882A (en) * | 2018-01-10 | 2018-07-13 | 南京邮电大学 | A kind of polychrome light emitting glass of ultraviolet excitation 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 |
| CN111153594A (en) * | 2020-01-09 | 2020-05-15 | 温州大学 | YAG-Ce glass ceramic and preparation method and application thereof |
| CN111153594B (en) * | 2020-01-09 | 2022-06-07 | 温州大学 | YAG-Ce glass ceramic and preparation method and application thereof |
| CN114538769A (en) * | 2020-11-27 | 2022-05-27 | 天津工业大学 | Rare earth element Dy-doped anti-irradiation borosilicate luminescent glass and preparation method 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103395997B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103395997B (en) | A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof | |
| CN103803797B (en) | A kind of LED fluorescent glass and preparation method thereof | |
| CN101824321B (en) | Blue light excitation-based fluorescent powder for white light LED and preparation method thereof | |
| CN101314519A (en) | Rare earth doping luminescent glass for white radiation LED and producing thereof | |
| CN104726101A (en) | Single-host white-light emitting fluorophosphate fluorescent powder for white-light LED and preparation method of fluorophosphate fluorescent powder | |
| CN106479500A (en) | A kind of luminescent glass ceramic and its preparation method and the application in LED illumination device | |
| CN110316963B (en) | Fluorescent glass ceramic material and light-emitting device containing same | |
| KR20190013977A (en) | Fluorescent powder, a method for producing the same, and a light emitting element having the same | |
| CN105236750A (en) | Rare earth-doped white-light fluorescent phosphate glass ceramics material and preparation method thereof | |
| CN108998025A (en) | A kind of LED silicate-base red fluorescence powder and preparation method thereof | |
| CN103468264A (en) | Manufacture method of polycrystalline Ce:YAG fluorophor | |
| CN107098582B (en) | White light luminescent glass with high thermal stability and borate matrix for LED and preparation method thereof | |
| CN106634997A (en) | Composite phosphate fluorophor and application thereof | |
| CN104087300B (en) | A kind of thiophosphate fluorophor and its application | |
| CN105131953A (en) | Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder | |
| CN102584015A (en) | White light-emitting glass and preparation method thereof | |
| CN103980902A (en) | Ga-Bi doped aluminate green phosphor and preparation method thereof | |
| CN104163572A (en) | Transparent glass ceramic having high efficiency white light emission and preparation method thereof | |
| CN101935165A (en) | Inorganic silicate fluorescent glass and preparation method thereof | |
| CN114574206B (en) | Fluorescent powder for white light-emitting diode and synthesis method and application thereof | |
| CN106634996A (en) | Fluorophor and application method thereof | |
| CN107163943B (en) | Spectrum-adjustable fluorescent powder suitable for near ultraviolet excitation and preparation method thereof | |
| CN106967429B (en) | A kind of red fluorescence powder and preparation method thereof of fluorescence thermal stability enhancing | |
| CN109054835A (en) | A kind of light activated long lad phosphor of indigo plant and preparation method thereof | |
| CN108793733A (en) | A kind of high-melting-point LED fluorescent glass and discharge plasma sintering preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Jiangsu Nanyou IOT Technology Park Ltd. Assignor: NANJING University OF POSTS AND TELECOMMUNICATIONS Contract record no.: 2016320000210 Date of cancellation: 20180116 |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 Termination date: 20210723 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |