CN105314864A - Rare-earth ion doping SrBr2 glass ceramics and preparation method thereof - Google Patents
Rare-earth ion doping SrBr2 glass ceramics and preparation method thereof Download PDFInfo
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- CN105314864A CN105314864A CN201510853352.6A CN201510853352A CN105314864A CN 105314864 A CN105314864 A CN 105314864A CN 201510853352 A CN201510853352 A CN 201510853352A CN 105314864 A CN105314864 A CN 105314864A
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- srbr
- devitrified glass
- earth ion
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Abstract
The invention discloses rare-earth ion doping SrBr2 glass ceramics. The rare-earth ion doping SrBr2 glass ceramics consists of the following components by molar percent: 80 to 89.9 percent of SiO2, 10 to 15 percent of SrBr2 and 0.1 to 5 percent of LnBr, wherein LnBr3 is at least one of YbBr3, ErBr3 and TmBr3. The rare-earth ion doping SrBr2 glass ceramics have advantages of transparency, deliquesce resistance, good mechanical performance and high blue-ultraviolet transmittance, have performances such as low phono energy, high upconversion efficiency and the like and can greatly improve the efficiency of an upconversion laser; moreover, the preparation method of the glass ceramics is simple, and the production cost is relatively low.
Description
Technical field
The present invention relates to a kind of rare earth ion doped devitrified glass, especially relate to a kind of rare earth ion doped SrBr being used as up-conversion luminescent material
2devitrified glass and preparation method thereof.
Background technology
When the up-conversion luminescence of rare earth ion refers to the sample when the excitation light irradiation doping with rare-earth ions adopting wavelength longer, launch the phenomenon that wavelength is less than the light of excitation wavelength.The upconversion laser of the green wave band of purplish blue is in HIGH-DENSITY OPTICAL STORAGE, and color laser shows, and all many-sides such as ocean color and extra large resource detection have good application prospect.The efficiency improving up-conversion luminescence need reduce the phonon energy of substrate material, this is mainly because lower phonon energy can reduce the generation of non-radiative relaxation probability, improve the fluorescence lifetime of metastable level in the middle of rare earth ion, effectively can improve the efficiency of up-conversion luminescence.SrBr
2crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped SrBr
2crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but SrBr
2the easy moisture absorption of crystal, need special processing and storage, be difficult to preparation, chemical stability and its practical application of the disadvantages affect such as physical strength is poor.
Transparent glass-ceramics is a kind of photoelectron material having crystal and glass advantage concurrently.Current bromide transparent glass-ceramics is mainly used as flash luminous material, and its doping activator is Ce
3+, Eu
3+, Tb
3+, Pr
3+and Nd
3+plasma, if publication number is CN103951222, name is called " rare earth ion doped SrBr
2devitrified glass and preparation method thereof " application for a patent for invention disclose a kind of crystallite mutually for SrBr
2, glassy phase is P
2o
5with B
2o
3be main devitrified glass, adopt melt supercooled method and subsequent heat treatment preparation, there is good scintillation properties.But also there is no trivalent rare earth ions Yb at present
3+, Er
3+and Tm
3+the SrBr of doping
2devitrified glass is used for the open report of up-conversion luminescent material.
Summary of the invention
The rare earth ion doped SrBr that technical problem to be solved by this invention is to provide that a kind of phonon energy is low, little, the upper conversion quantum yield of radiationless transition probability is high, Deliquescence-resistant, good mechanical property, up-conversion luminescence are very strong
2devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of rare earth ion doped SrBr
2devitrified glass, its molar percentage consists of: SiO
280 ~ 89.9mol%, SrBr
210 ~ 15mol%, LnBr
30.1 ~ 5mol%, wherein LnBr
3for YbBr
3, ErBr
3and TmBr
3in at least one.
This devitrified glass molar percentage consists of: SiO
280mol%, SrBr
215mol%, ErBr
30.1mol%, TmBr
30.1mol%, YbBr
34.8mol%.
This devitrified glass molar percentage consists of: SiO
280.5mol%, SrBr
215mol%, TmBr
30.5mol%, YbBr
34mol%.
This devitrified glass molar percentage consists of: SiO
289.9mol%, SrBr
210mol%, ErBr
30.1mol%.
Described rare earth ion doped SrBr
2the preparation method of devitrified glass, comprises the following steps:
(1) by mole% composition SiO
280 ~ 89.9mol%, SrBr
210 ~ 15mol%, LnBr
30.1 ~ 5mol%, wherein LnBr
3for YbBr
3, ErBr
3and TmBr
3in at least one; Take at least one in strontium acetate and acetic acid ytterbium, acetic acid erbium and acetic acid thulium, wherein the deal of strontium acetate is by mole% SrBr in composition
2molar content take, the deal of acetic acid ytterbium, acetic acid erbium and at least one in acetic acid thulium is respectively by LnBr in above-mentioned identical molar percentage composition
3molar content take, and above-mentioned acetate is dissolved in deionized water forms Acetate Solution, in Acetate Solution, add tribromoacetic acid obtain transparent mixing solutions, wherein in tribromoacetic acid and Acetate Solution, the mol ratio of metal ion summation is 3: 1;
(2) SiO in forming by the molar percentage identical with step (1)
2molar content take tetraethoxy and be dissolved in ethanol, obtain teos solution, then stir 1 hour after being mixed with teos solution by mixing solutions obtained for step (1), then regulate its pH value to 5 with dust technology, obtain precursor liquid;
(3) the precursor liquid room temperature ageing that step (2) obtains is placed on baking oven in 3 weeks, is warming up to 150 DEG C of dryings 7 days, obtains transparent xerogel;
(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, thermal treatment 10 hours at the temperature of 500 ~ 530 DEG C, and then be cooled to 50 DEG C with the speed of 10 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped SrBr
2devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass has SrBr
2the feature that in the excellence of crystalline host material, the physical strength of conversion performance and silica glass, stability and being easy to is processed; The experiment proved that: by the rare earth ion doped SrBr obtained by preparation method of the present invention
2devitrified glass is transparent, Deliquescence-resistant, good mechanical property, royal purple light transmission rate are higher, has the performances such as low, the upper efficiency of conversion of phonon energy is high, upconversion laser efficiency can be made greatly to improve; By changing rear-earth-doped concentration, RGB light luminous intensity ratio can be controlled; In addition, the preparation method of this devitrified glass is simple and have good repeatability, and production cost is lower.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the devitrified glass that embodiment 1 obtains;
Fig. 2 is the Er that embodiment 1 obtains
3+, Tm
3+, Yb
3+the SrBr of doping
2the 970nm laser apparatus of devitrified glass excites up-conversion luminescence spectrum;
Fig. 3 is the Er that comparative example 1 obtains
3+, Tm
3+, Yb
3+the SrF of doping
2the 970nm laser apparatus of devitrified glass excites up-conversion luminescence spectrum.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
Er
3+, Tm
3+, Yb
3+doping SrBr
2the molar percentage of devitrified glass consists of: SiO
280mol%, SrBr
215mol%, ErBr
30.1mol%, TmBr
30.1mol%, YbBr
34.8mol%, the technique preparing devitrified glass of above composition is as follows:
(1) take strontium acetate, acetic acid ytterbium, acetic acid erbium, acetic acid thulium, and deal is respectively by the SrBr in above-mentioned molar percentage composition
2, YbBr
3, ErBr
3, TmBr
3molar content take, be dissolved in deionized water by above-mentioned acetate and form Acetate Solution, add tribromoacetic acid and obtain transparent mixing solutions in Acetate Solution, wherein in tribromoacetic acid and Acetate Solution, the mol ratio of metal ion summation is 3: 1;
(2) SiO in forming by the molar percentage identical with step (1)
2molar content take tetraethoxy and be dissolved in ethanol, obtain teos solution, then stir 1 hour after being mixed with teos solution by mixing solutions obtained for step (1), then regulate its pH value to 5 with dust technology, obtain precursor liquid;
(3) the precursor liquid room temperature ageing that step (2) obtains is placed on baking oven in 3 weeks, is warming up to 150 DEG C of dryings 7 days, obtains transparent xerogel;
(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 500 ~ 530 DEG C of thermal treatments 10 hours, and then be cooled to 50 DEG C with the speed of 10 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion Er
3+, Tm
3+, Yb
3+the SrBr of doping
2devitrified glass.
To obtained SrBr
2devitrified glass carries out X-ray diffraction test, obtains the XRD figure of this devitrified glass as shown in Figure 1, and its result is as follows: the XRD diffraction peak of the sample obtained through Overheating Treatment and SrBr
2the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is SrBr
2the devitrified glass of crystallization phase.Measure by TRIAX550 fluorescence spectrophotometer, under 970nm laser apparatus shooting conditions, the up-conversion luminescence spectrum of this devitrified glass as shown in Figure 2, the integration luminous intensity of blue light (476nm), green glow (533nm), green glow (546nm) and ruddiness (653nm) respectively about 3.87 × 10
5, 6.62 × 10
5, 3.29 × 10
5, 3.44 × 10
5, blueness, green and red up-conversion luminescence are very strong.By changing rear-earth-doped concentration, RGB light luminous intensity ratio can be controlled.
Embodiment 2
Tm
3+, Yb
3+doping SrBr
2the molar percentage of devitrified glass consists of: SiO
280.5mol%, SrBr
215mol%, TmBr
30.5mol%, YbBr
34mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm
3+, Yb
3+the SrBr of doping
2devitrified glass.This devitrified glass TRIAX550 fluorescence spectrophotometer is measured, under 970nm laser apparatus shooting conditions, observes strong blue up-conversion luminous.
Embodiment 3
Er
3+doping SrBr
2the molar percentage of devitrified glass consists of: SiO
289.9mol%, SrBr
210mol%, ErBr
30.1mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er
3+the SrBr of doping
2devitrified glass.Spectral quality test is carried out to this devitrified glass, when pumping wavelength is respectively 543nm and 548.8nm, observes strong ultraviolet and purple up-conversion fluorescence.
Comparative example 1
Er
3+, Tm
3+, Yb
3+doping SrF
2the molar percentage of devitrified glass consists of: SiO
280mol%, SrF
215mol%, ErF
30.1mol%, TmF
30.1mol%, YbF
34.8mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er
3+, Tm
3+, Yb
3+the SrF of doping
2devitrified glass.Measure by TRIAX550 fluorescence spectrophotometer, under 970nm laser apparatus shooting conditions, the up-conversion luminescence spectrum of this devitrified glass as shown in Figure 3, the integration luminous intensity of blue light (476nm), green glow (523nm), green glow (546nm) and ruddiness (653nm) respectively about 3.17 × 10
4, 5.42 × 10
4, 2.69 × 10
4, 2.81 × 10
4, compare with embodiment 1, blueness, green and red Up-conversion Intensity are low, and the Er that embodiment 1 obtains is described
3+, Tm
3+, Yb
3+the SrBr of doping
2the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains
3+, Tm
3+, Yb
3+the SrF of doping
2devitrified glass is better.
Claims (5)
1. a rare earth ion doped SrBr
2devitrified glass, its molar percentage consists of: SiO
280 ~ 89.9mol%, SrBr
210 ~ 15mol%, LnBr
30.1 ~ 5mol%, wherein LnBr
3for YbBr
3, ErBr
3and TmBr
3in at least one.
2. rare earth ion doped SrBr according to claim 1
2devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
280mol%, SrBr
215mol%, ErBr
30.1mol%, TmBr
30.1mol%, YbBr
34.8mol%.
3. rare earth ion doped SrBr according to claim 1
2devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
280.5mol%, SrBr
215mol%, TmBr
30.5mol%, YbBr
34mol%.
4. rare earth ion doped SrBr according to claim 1
2devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
289.9mol%, SrBr
210mol%, ErBr
30.1mol%.
5. rare earth ion doped SrBr according to claim 1
2the preparation method of devitrified glass, is characterized in that comprising the following steps:
(1) by mole% composition SiO
280 ~ 89.9mol%, SrBr
210 ~ 15mol%, LnBr
30.1 ~ 5mol%, wherein LnBr
3for YbBr
3, ErBr
3and TmBr
3in at least one; Take at least one in strontium acetate and acetic acid ytterbium, acetic acid erbium and acetic acid thulium, wherein the deal of strontium acetate is by mole% SrBr in composition
2molar content take, the deal of acetic acid ytterbium, acetic acid erbium and at least one in acetic acid thulium is respectively by LnBr in above-mentioned identical molar percentage composition
3molar content take, and above-mentioned acetate is dissolved in deionized water forms Acetate Solution, in Acetate Solution, add tribromoacetic acid obtain transparent mixing solutions, wherein in tribromoacetic acid and Acetate Solution, the mol ratio of metal ion summation is 3: 1;
(2) SiO in forming by the molar percentage identical with step (1)
2molar content take tetraethoxy and be dissolved in ethanol, obtain teos solution, then stir 1 hour after being mixed with teos solution by mixing solutions obtained for step (1), then regulate its pH value to 5 with dust technology, obtain precursor liquid;
(3) the precursor liquid room temperature ageing that step (2) obtains is placed on baking oven in 3 weeks, is warming up to 150 DEG C of dryings 7 days, obtains transparent xerogel;
(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, thermal treatment 10 hours at the temperature of 500 ~ 530 DEG C, and then be cooled to 50 DEG C with the speed of 10 DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped SrBr
2devitrified glass.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103951258A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped SrI2 microcrystalline glass and preparation method thereof |
-
2015
- 2015-11-27 CN CN201510853352.6A patent/CN105314864A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103951258A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped SrI2 microcrystalline glass and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
MOSLEMIZADEH S等: "UV-Blue Up-Conversion Phenomena in Nd3+ Doped CaCl2 Nano-Crystals", 《CHINESE JOURNAL OF PHYSICS》 * |
花景田等: "稀土掺杂材料的上转换发光", 《中国光学与应用光学》 * |
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