CN101376566A - Zinc oxide quantum dots sensitized rare earth doping glass ceramics and sol-gel preparation thereof - Google Patents
Zinc oxide quantum dots sensitized rare earth doping glass ceramics and sol-gel preparation thereof Download PDFInfo
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- CN101376566A CN101376566A CNA2007100094329A CN200710009432A CN101376566A CN 101376566 A CN101376566 A CN 101376566A CN A2007100094329 A CNA2007100094329 A CN A2007100094329A CN 200710009432 A CN200710009432 A CN 200710009432A CN 101376566 A CN101376566 A CN 101376566A
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Abstract
The invention discloses a rare-earth doped glass ceramic which is sensitized by zinc oxide quantum dots, and a sol-gel preparation method thereof, and the glass ceramic relates to the field of luminescent materials. The glass ceramic comprises the following chemical components: xSiO2*yZnO*zRe2O3, wherein, x is equal to 20-100 mol percent; y is equal to (100-x-z) mol percent; z is equal to 0-20 mol percent; and Re refers to trivalent actinide rare-earth ions such as Er<3+>, Eu<3+>, Sm<3+>, Tm<3+>, Ho<3+> or Tb<3+>, and the like. The glass ceramic is prepared by adopting the sol-gel method. The zinc oxide semiconductor quantum dots have good sensibilization performance to the rare-earth ions, and the rare-earth luminescent properties can be effectively increased.
Description
Technical field
The present invention relates to field of light emitting materials, especially relate to zinc oxide semi-conductor quantum dot sensitized rare earth doping transparent glass-ceramic luminescent material and process for preparing sol-gel thereof.
Background technology
The transparent glass ceramics that contains semiconductor-quantum-point is that a class evenly is coated on SiO with semiconductor-quantum-point
2The nano composite material of substrate of glass, last century the fifties just begin as filter research and obtain practical application.The electronics of semiconductor material has the intensive transition from the conduction band to the valence band, absorption cross can be up to 10
-15Cm
2, and the level structure of rare earth ion is mainly determined by the Coulomb interactions and the spin of 4f shell electron, parity and spin forbidden effect cause the absorption cross-section of rare earth ion less (as Er
3+The ionic absorption cross is approximately 10
-21Cm
2).Discover that semiconductor-quantum-point can be used as sensitizing agent and transmits energy to contiguous rare earth ion, thereby increases substantially rare earth luminous efficient.Rear-earth-doped contains in the semiconductor-quantum-point glass-ceramic amorphous SiO
2Substrate provides the environment that mixes preferably, rare earth just need not enter in the semiconductor quantum point lattice may and semiconductor-quantum-point between the generate energy transmission, make quantum dot have good sensitization effect (with reference to J.Bang etc., J.Chem.Phys.123 (2005) p.084709) to rare earth.At present in the world the research of this class nano composite material also is in the starting stage, so far, the existing sol-gel method that adopts prepares the rear-earth-doped SnO that contains respectively
2, ZnS and CdS semiconductor-quantum-point glass-ceramic report.The present invention adopts sol-gel method, in conjunction with subsequent heat treatment, has prepared the rear-earth-doped transparent glass ceramics bulk that contains the zinc oxide semi-conductor quantum dot first.Semiconductor-quantum-point in this material is obvious to the rare earth sensibilized, can absorb UV-light and give rare earth ion with transmission ofenergy, thereby significantly improve rare earth luminous performance, has important application prospects in luminous field.
Summary of the invention
The present invention proposes a kind of transparent glass ceramics component rear-earth-doped, that contain the zinc oxide semi-conductor quantum dot and sol-gel preparation technology thereof, purpose is to prepare and can absorbs UV-light (220～380nm) and launch the transparent glass ceramics advanced luminescent material of strong visible light.
The chemical composition of the transparent glass ceramics of the present invention's preparation is: xSiO
2YZnOzRe
2O
3(x=20～100mol%, y=(100-x-z) mol%, z=0～20mol%); Re is Er
3+, Eu
3+, Sm
3+, Tm
3+, Ho
3+Or Tb
3+Etc. the trivalent La rear earth ion
The present invention adopts and is prepared as follows technology: with an amount of zinc acetate, Virahol and the hydrolysis of thanomin mixing post-heating, obtain A solution; An amount of tetraethoxy, dehydrated alcohol, soluble ree compound, hydrolyst and deionized water are mixed, obtain B solution.The A drips of solution is added in the B solution, obtain vitreosol; To obtain xerogel after vitreosol ageing, the drying, then reheat to 300～800 ℃ and be incubated certain hour promptly obtain transparent glass-ceramic bulk.Observe through high-resolution-ration transmission electric-lens, the ZnO quantum dot is uniformly distributed in SiO
2In the noncrystal substrate.
Measure with the FLS920 fluorescence spectrophotometer, the result shows that the glass-ceramic to above design component and preparation technology's acquisition is higher than at energy under the ultraviolet excitation of semiconductor-quantum-point band gap, and rare earth ion sends stronger visible light; And, can only inspire weak rare earth ion visible light in several certain wavelengths to the object of reference sample of oxygen-free zinc component (all the other components and material preparation condition are identical), illustrate that Zinc oxide quantum dot has the intensive sensibilized to rare earth ion in the glass-ceramic.
Glass-ceramic of the present invention has chemical purity height, good uniformity, the controlled advantage of component, and preparation technology is simple, with low cost.At wavelength is under the ultraviolet excitation of 220～380nm, can launch stronger visible light, is a kind of luminescent material with important application prospect.
Description of drawings
Accompanying drawing is mixed europium and (b) is contained zinc oxide semi-conductor Quantum Dot Glass pottery and mix the excitation spectrum (left side) and emission spectrum (the right) of europium sample for (a) pure silicon dioxide.
Embodiment
Example one: 0.009mol zinc acetate, 0.018mol Virahol, 0.009mol thanomin are mixed post-heating to 65 ℃ reaction 3 hours in beaker, obtain clear solution A; With 0.09mol tetraethoxy, 0.36mol dehydrated alcohol, 0.9mol deionized water, 0.001mol acetic acid europium and a spot of nitric acid mix stirring 0.5 hour, obtain settled solution B.After the A drips of solution adds B solution, cover preservative film and stirred 4 hours, obtain the colloidal sol of homogeneous transparent; Colloidal sol is poured in the weighing bottle, after two weeks of room temperature ageing, in baking oven, slowly be heated to 200 ℃ and be incubated a week, obtain transparent xerogel; Xerogel is warming up to 500 ℃ with 2K/min speed in retort furnace, and is incubated 2 hours, obtaining component is 90SiO
29ZnO1Eu
3+Transparent glass ceramics bulk (disk of diameter 5mm, thickness 0.5mm).Transmission electron microscope observing shows, SiO
2A large amount of yardsticks that distributing in the glass basis are about the ZnO semiconductor-quantum-point of 5nm.FLS920 fluorescence spectrophotometer test shows in 220～380nm scope, adopts different wave length to excite, and the Eu rare earth ion all can be launched strong ruddiness, illustrates to have tangible transmission ofenergy phenomenon between ZnO quantum dot and the Eu ion.
Example 2: 0.009mol zinc acetate, 0.018mol Virahol, 0.009mol thanomin are mixed post-heating to 65 ℃ reaction 3 hours in beaker, obtain clear solution (hereinafter to be referred as A solution); With 0.09mol tetraethoxy, 0.36mol dehydrated alcohol, 0.9mol deionized water, 0.0005-0.004mol acetic acid europium and a spot of nitric acid mix stirring 0.5 hour, obtain settled solution (hereinafter to be referred as B solution).After the A drips of solution adds B solution, cover preservative film and stirred 4 hours, obtain the colloidal sol of homogeneous transparent.After the drying and heat treatment process identical, obtain 90SiO with example 1
29ZnOxEu
3+The transparent glass ceramics bulk of (x=0.5,1,2,4) (disk of diameter 5mm, thickness 0.5mm).Measure with the FLS920 fluorescence spectrophotometer, under 320nm laser excitation, the red luminous intensity of Eu improves along with the increase of Eu content.
Example 3: 0-0.018mol zinc acetate, 0.018mol Virahol, 0-0.018mol thanomin are mixed post-heating to 65 ℃ reaction 3 hours in beaker, obtain clear solution (hereinafter to be referred as A solution); 0.1-0.08mol tetraethoxy, 0.36mol dehydrated alcohol, 0.9mol deionized water, 0.002mol acetic acid europium and a spot of nitric acid are mixed stirring 0.5 hour, obtain settled solution (hereinafter to be referred as B solution).After the A drips of solution adds B solution, cover preservative film and stirred 4 hours, obtain the colloidal sol of homogeneous transparent.After the drying and heat treatment process identical, obtain xSiO with example 1
2YZnO2Eu
3+(x=78,83,88,93,98; Y=98-x) transparent glass ceramics bulk (disk of diameter 5mm, thickness 0.5mm).Measure with the FLS920 fluorescence spectrophotometer, under 320nm laser excitation, Eu ion red luminous intensity improves along with increasing of ZnO content, and when ZnO content was 20%, its intensity was that ZnO content is 0 o'clock 10 times.
Claims (4)
1. the rear-earth-doped glass-ceramic of Zinc oxide quantum dot sensitization is characterized in that: its chemical composition is (mol ratio): xSiO2yZnOzRe2O3 (x=20～100mol%, y=(100-x-z) mol%, z=0～20mol%); Re is Er
3+, Eu
3+, Sm
3+, Tm
3+, Ho
3+Or Tb
3+Etc. the trivalent La rear earth ion.
2. the preparation method of the glass-ceramic of a claim 1 is characterized in that: adopt process for preparing sol-gel.
3. method as claimed in claim 2 is characterized in that: with an amount of zinc acetate, Virahol and the hydrolysis of thanomin mixing post-heating, obtain A solution; An amount of tetraethoxy, dehydrated alcohol, soluble ree compound, hydrolyst and deionized water are mixed, obtain B solution.The A drips of solution is added in the B solution, obtain vitreosol; To obtain xerogel after vitreosol ageing, the drying, then reheat to 300～800 ℃ and be incubated certain hour promptly obtain transparent glass-ceramic bulk.
4. the purposes of the glass-ceramic of a claim 1 is characterized in that: the zinc oxide semi-conductor quantum dot strengthens the rare earth luminescence performance as sensitizing agent.
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|---|---|---|---|
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|---|---|---|---|
| CNA2007100094329A CN101376566A (en) | 2007-08-30 | 2007-08-30 | Zinc oxide quantum dots sensitized rare earth doping glass ceramics and sol-gel preparation thereof |
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ID=40420311
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940933A (en) * | 2010-07-30 | 2011-01-12 | 武汉理工大学 | Preparation method for visible light photocatalyst prepared by CdS quantum dot sensitization Zn1-xCdxs and photodecomposition of water into hydrogen |
| CN102050578B (en) * | 2009-11-06 | 2012-03-28 | 海洋王照明科技股份有限公司 | Luminous enhanced terbium-doped nano microcrystalline glass and preparation method thereof |
| CN102515549A (en) * | 2011-12-06 | 2012-06-27 | 中国科学院福建物质结构研究所 | Rare earth doping cerium oxide contained nano-crystal glass ceramic and preparation method thereof |
| CN102992618A (en) * | 2012-12-25 | 2013-03-27 | 河北联合大学 | Rare earth europium-doped nitrogen oxide luminescent glass and preparation method thereof |
| CN103601368A (en) * | 2013-11-13 | 2014-02-26 | 东华大学 | Method of preparing NaYF4-based up-conversion luminescent glass by quick solid phase sintering technology |
-
2007
- 2007-08-30 CN CNA2007100094329A patent/CN101376566A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050578B (en) * | 2009-11-06 | 2012-03-28 | 海洋王照明科技股份有限公司 | Luminous enhanced terbium-doped nano microcrystalline glass and preparation method thereof |
| CN101940933A (en) * | 2010-07-30 | 2011-01-12 | 武汉理工大学 | Preparation method for visible light photocatalyst prepared by CdS quantum dot sensitization Zn1-xCdxs and photodecomposition of water into hydrogen |
| CN101940933B (en) * | 2010-07-30 | 2011-11-02 | 武汉理工大学 | Preparation method for visible light photocatalyst prepared by CdS quantum dot sensitization Zn1-xCdxs and photodecomposition of water into hydrogen |
| CN102515549A (en) * | 2011-12-06 | 2012-06-27 | 中国科学院福建物质结构研究所 | Rare earth doping cerium oxide contained nano-crystal glass ceramic and preparation method thereof |
| CN102992618A (en) * | 2012-12-25 | 2013-03-27 | 河北联合大学 | Rare earth europium-doped nitrogen oxide luminescent glass and preparation method thereof |
| CN103601368A (en) * | 2013-11-13 | 2014-02-26 | 东华大学 | Method of preparing NaYF4-based up-conversion luminescent glass by quick solid phase sintering technology |
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