CN102515549A - Rare earth doping cerium oxide contained nano-crystal glass ceramic and preparation method thereof - Google Patents
Rare earth doping cerium oxide contained nano-crystal glass ceramic and preparation method thereof Download PDFInfo
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- CN102515549A CN102515549A CN2011104008757A CN201110400875A CN102515549A CN 102515549 A CN102515549 A CN 102515549A CN 2011104008757 A CN2011104008757 A CN 2011104008757A CN 201110400875 A CN201110400875 A CN 201110400875A CN 102515549 A CN102515549 A CN 102515549A
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Abstract
The invention provides a rare earth doping cerium oxide contained nano-crystal glass ceramic and a preparation method thereof. The nano-crystal glass ceramic comprises the component of xSiO2-yCeO2-zREF3, wherein x is 75-99 mol%, y is 1-25 mol%, z is 0-10 mol%, and RE is rare earth Eu or Sm. A sample is prepared by using a sol-gel method. A cerium oxide nano-crystal is a good matrix material of rare earth ions and has very good sensitizing and protecting effects on rare earth ion luminescence.
Description
Technical field
The present invention relates to field of light emitting materials, especially relate to the rare earth glass ceramic luminescent material and the process for preparing sol-gel thereof of cerium dioxide sensitization.
Background technology
Oxidiferous rare earth glass pottery is one type oxidate nano crystal grain evenly is embedded in the Illuminant nanometer composite material in the rear-earth-doped oxidation silex glass matrix, has wide application prospect at fiber amplifier and three-dimensional light demonstration field.Discover, in the oxycompound glass-ceramic,, just can improve the luminescent properties of rare earth ion significantly if oxide nanocrystalline has sensibilized to rare earth ion.In the world this type material has been carried out a series of research; But in the oxycompound of having reported (like semiconductor oxide zinc, tindioxide, indium trioxide) glass-ceramic; Rare earth ion all is difficult to get into oxide nanocrystalline, and this has limited the further lifting of glass-ceramic luminescent properties.Therefore, the novel glass pottery of research and development rare earth ion entering oxide nanocrystalline is significant.Cerium ion in the cerium dioxide crystal has the ionic radius close with rare earth ion; Thereby rare earth ion be easy to the displacement solid solution mode get in the lattice, make cerium dioxide become a kind of good rare earth ion substrate material [J.Phys.Chem.C, 2009; 113,610-617].In recent years, both at home and abroad to the existing a small amount of report of the research of rear-earth-doped ceria nano-crystalline powder, but Shang Weijian contains the report of ceria nano-crystalline rare earth glass ceramic luminescent material.The present invention adopts sol-gel method, in conjunction with subsequent heat treatment, prepares doped with rare earth ceria nano-crystalline glass-ceramic first.Get in the ceria nano-crystalline as the rare earth ion of luminescence center in this material, on the one hand, the cerium dioxide crystal shields to the luminous of rare earth ion, reduces the water that remains in the silica glass matrix and organic molecule to luminous quenching effect; On the other hand, ceria nano-crystalline ability sensitization rare earth ion, thus strengthen rare earth luminescence.
Summary of the invention
The present invention proposes a kind of doped with rare earth ceria nano-crystalline glass-ceramic component and process for preparing sol-gel thereof, and purpose is to prepare the novel glass stupalith that rare earth ion gets into ceria nano-crystalline and has good luminous performance.
The chemical composition of the glass-ceramic of the present invention's preparation is: xSiO
2-yCeO
2-zREF
3, x=75-99mol%, y=1-25mol%, z=0-10mol%, RE are rare earth Eu or Sm.
The present invention adopts the method that is prepared as follows: an amount of solubility cerium salt and soluble rare-earth salt is soluble in water by a certain percentage, obtain solution A; With tetraethoxysilance and ethanol uniform mixing, obtain solution B; Solution A is mixed with solution B, and added the acid of hydrolyzation catalysis effect, obtain xerogel, then be heated to 300-1000 ℃ and be incubated certain hour, obtain glass ceramic material through ageing, drying.High-resolution-ration transmission electric-lens is observed and is shown have a large amount of ceria nano-crystallines evenly to be embedded in the silica glass matrix in the glass-ceramic.
With the FLS920 XRF sample is excited and the emission spectroscopy measurements analysis; The result shows; The above glass-ceramic that obtains of design component and preparation method in the rare earth ion entering ceria nano-crystalline, and nanocrystallinely has good luminous sensibilized to rare earth ion.
Glass-ceramic of the present invention has the advantage of chemical purity height, good uniformity, controllable components, and the preparation method is simple, with low cost, has good luminous property, is a kind of luminescent material with important application prospect.
Description of drawings
Fig. 1 is the X-ray diffractogram of glass-ceramic sample in the instance 1;
Fig. 2 is the transmission electron microscope bright field image of glass-ceramic in the instance 1;
Fig. 3 is the excitation spectrum (left side) and emmission spectrum (the right) of glass and glass-ceramic in the instance 1.
Embodiment
Instance 1: 0.005mol cerous nitrate, 0.6mol deionized water and 0.001mol europium nitrate are mixed, and stirring and dissolving obtains clear solution A; 0.094mol tetraethoxy and 0.36mol absolute ethyl alcohol are mixed, stirred 0.5 hour, obtain settled solution B.Solution A is added dropwise to solution B, and, covers preservative film and stirred 4 hours, obtain the colloidal sol of homogeneous transparent with nitre acid for adjusting pH value to 3; 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 800 ℃ with 2 ℃/min speed in retort furnace, and is incubated 40 hours, obtaining component is 94SiO
2-5CeO
2-1EuF
3(mol%) glass-ceramic.Powder X-ray diffraction analysis (Fig. 1) and transmission electron microscope observation (Fig. 2) result show that the ceria nano-crystalline that a large amount of yardsticks are about 5 nanometers is evenly separated out from the silica glass matrix.Excite and emmission spectrum (Fig. 3) analysis revealed, as the Eu of luminescence center
3+Ion has got in the ceria nano-crystalline, and nanocrystalline to Eu
3+Ionoluminescence has strong sensibilized.
Instance 2: 0.02mol cerous nitrate, 0.6mol deionized water and 0.001mol europium nitrate are mixed, and stirring and dissolving obtains clear solution A; 0.079mol tetraethoxy and 0.36mol absolute ethyl alcohol are mixed, stirred 0.5 hour, obtain settled solution B.Solution A is added dropwise to solution B, and, covers preservative film and stirred 4 hours, obtain the colloidal sol of homogeneous transparent with nitre acid for adjusting pH value to 3; 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 800 ℃ with 2 ℃/min speed in retort furnace, and is incubated 40 hours, obtaining component is 79SiO
2-20CeO
2-1EuF
3(mol%) glass-ceramic.Powder X-ray diffraction analysis and transmission electron microscope observation result show that the ceria nano-crystalline that a large amount of yardsticks are about 5 nanometers is evenly separated out from the silica glass matrix.Excite with emmission spectrometric analysis to show, as the Eu of luminescence center
3+Ion has got in the ceria nano-crystalline, and nanocrystalline to Eu
3+Ionoluminescence has strong sensibilized.With Eu in the instance 1
3+Luminous comparing, Eu in the instance 2
3+Luminous remarkable enhancing.
Instance 3: 0.01mol cerous nitrate, 0.6mol deionized water and 0.001mol samaric nitrate are mixed, and stirring and dissolving obtains clear solution A; 0.089mol tetraethoxy and 0.36mol absolute ethyl alcohol are mixed, stirred 0.5 hour, obtain settled solution B.Solution A is added dropwise to solution B, and, covers preservative film and stirred 4 hours, obtain the colloidal sol of homogeneous transparent with nitre acid for adjusting pH value to 3; 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 1000 ℃ with 2 ℃/min speed in retort furnace, and is incubated 40 hours, obtaining component is 89SiO
2-10CeO
2-1SmF
3(mol%) glass-ceramic.Powder X-ray diffraction analysis and transmission electron microscope observation result show that the ceria nano-crystalline that a large amount of yardsticks are about 5 nanometers is evenly separated out from the silica glass matrix.Excite with emmission spectrometric analysis to show, as the Sm of luminescence center
3+Ion has got in the ceria nano-crystalline, and nanocrystalline to Sm
3+Ionoluminescence has strong sensibilized.
Claims (2)
1. doped with rare earth ceria nano-crystalline glass-ceramic, it is characterized in that: its chemical composition is xSiO
2-yCeO
2-zREF
3, x=75-99mol%, y=1-25mol%, z=0-10mol%, RE are rare earth Eu or Sm.
2. the method for glass-ceramic of preparation claim 1 adopts the sol-gel preparation method, comprises the steps: solubility cerium salt and soluble rare-earth salt soluble in waterly, passes through and arrives solution A; With tetraethoxysilance and ethanol uniform mixing, obtain solution B; A solution is mixed with B solution, obtain xerogel, then be heated to 300-1000 ℃ and insulation, obtain glass ceramic material through ageing, drying.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271801A (en) * | 2015-11-16 | 2016-01-27 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystalline |
| CN105293941A (en) * | 2015-11-16 | 2016-02-03 | 宁波大学 | Preparation method for glass film containing divalent-europium-ion-doped strontium iodide microcrystalline |
| CN106927683A (en) * | 2017-03-22 | 2017-07-07 | 温州大学 | Wet chemistry method builds the preparation method of controllable nano crystal glass ceramics |
| CN110128018A (en) * | 2019-05-07 | 2019-08-16 | 福建江夏学院 | Erbium ion-doped ceramics of up-conversion luminescent glass containing ceria nano-crystalline and its preparation method and application |
| CN111740308A (en) * | 2020-06-04 | 2020-10-02 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of on-chip micro-ring white light laser based on rare earth doped nanocrystalline |
| CN111847886A (en) * | 2020-07-01 | 2020-10-30 | 暨南大学 | Tin dioxide-containing nano microcrystalline glass and preparation method thereof |
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| CN101024553A (en) * | 2006-02-24 | 2007-08-29 | 中国科学院福建物质结构研究所 | Alkaline-earth contained fluoride nano crystal transparent glass ceramic and its sol-gel preparing method |
| CN101376566A (en) * | 2007-08-30 | 2009-03-04 | 中国科学院福建物质结构研究所 | Zinc oxide quantum dots sensitized rare earth doping glass ceramics and sol-gel preparation thereof |
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| CN101024553A (en) * | 2006-02-24 | 2007-08-29 | 中国科学院福建物质结构研究所 | Alkaline-earth contained fluoride nano crystal transparent glass ceramic and its sol-gel preparing method |
| CN101376566A (en) * | 2007-08-30 | 2009-03-04 | 中国科学院福建物质结构研究所 | Zinc oxide quantum dots sensitized rare earth doping glass ceramics and sol-gel preparation thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271801A (en) * | 2015-11-16 | 2016-01-27 | 宁波大学 | Preparation method of glass film containing cerium ion doped lanthanum bromide microcrystalline |
| CN105293941A (en) * | 2015-11-16 | 2016-02-03 | 宁波大学 | Preparation method for glass film containing divalent-europium-ion-doped strontium iodide microcrystalline |
| CN106927683A (en) * | 2017-03-22 | 2017-07-07 | 温州大学 | Wet chemistry method builds the preparation method of controllable nano crystal glass ceramics |
| CN110128018A (en) * | 2019-05-07 | 2019-08-16 | 福建江夏学院 | Erbium ion-doped ceramics of up-conversion luminescent glass containing ceria nano-crystalline and its preparation method and application |
| CN111740308A (en) * | 2020-06-04 | 2020-10-02 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of on-chip micro-ring white light laser based on rare earth doped nanocrystalline |
| CN111847886A (en) * | 2020-07-01 | 2020-10-30 | 暨南大学 | Tin dioxide-containing nano microcrystalline glass and preparation method thereof |
| CN111847886B (en) * | 2020-07-01 | 2022-03-22 | 暨南大学 | Tin dioxide-containing nano microcrystalline glass and preparation method thereof |
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Application publication date: 20120627 |