CN105271771A - Rare earth ion doped Rb3LaC16 microcrystal glass and preparation method thereof - Google Patents
Rare earth ion doped Rb3LaC16 microcrystal glass and preparation method thereof Download PDFInfo
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- CN105271771A CN105271771A CN201510852652.2A CN201510852652A CN105271771A CN 105271771 A CN105271771 A CN 105271771A CN 201510852652 A CN201510852652 A CN 201510852652A CN 105271771 A CN105271771 A CN 105271771A
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- lacl
- devitrified glass
- acetic acid
- rare earth
- earth ion
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Abstract
The invention discloses rare earth ion doped Rb3LaC16 microcrystal glass which comprises the following components in percentage by mole: 87-93mol% of SiO2, 6.5-10mol% of Rb3LaC16 and 0.5-3mol% of LnC13, wherein LnC13 is at least one of YbC13, ErC13, TmC13 and HoC13. The rare earth ion doped Rb3LaC16 microcrystal glass has the advantages of transparency, good air-slake resistance, good mechanical property and high blue-violet emission transmittance and has properties such as low phonon energy and high upconversion efficiency, the efficiency of an upconversion laser can be greatly improved, and moreover the microcrystal glass is simple in preparation method and relatively low in production cost.
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 Rb being used as up-conversion luminescent material
3laCl
6devitrified 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.Utilize the upper conversion characteristic of rare earth ion, can obtain cheap, that can at room temperature work and export purplish blue green-light fiber laser continuously.The green up-conversion lasing of purplish blue can be applicable to the every field such as color monitor, data storing, information technology, laser printing and medical treatment.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.Rb
3laCl
6crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped Rb
3laCl
6crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but Rb
3laCl
6the easy moisture absorption of crystal, need special processing and storage, be difficult to preparation, chemical stability and the disadvantages affect such as physical strength the is poor practical application of its up-conversion luminescence.
Transparent glass-ceramics is a kind of photoelectron material having crystal and glass advantage concurrently.Chloride current transparent glass-ceramics is mainly used as flashing and up-conversion luminescent material, and if publication number is CN103382089, name is called " containing Cs
3laCl
6nanocrystalline transparent sulfur-halogen glass pottery and preparation thereof " application for a patent for invention disclose doping Nd
3+or Er
3+ion, with Cs
3laCl
6for crystallite phase, glassy phase are the devitrified glass of sulfide, but the physical and chemical performance of sulfide is poorer than oxide compound, and not saturating in visible ray shortwave strong point, have impact on up-conversion luminescence and exports; If publication number is CN103951240, name is called " rare earth ion doped Cs
2liLaCl
6devitrified glass and preparation method thereof " application for a patent for invention also disclose a kind of crystallite mutually for Cs
2liLaCl
6, glassy phase is SiO
2be main devitrified glass, the rare earth ion of doping is Ce
3+, Eu
3+, Tb
3+, Pr
3+and Nd
3+in one, adopt melt supercooled method and subsequent heat treatment preparation, there is good scintillation properties, as flash luminous material.But also there is no trivalent rare earth ions Yb at present
3+, Er
3+, Tm
3+and Ho
3+the Rb of doping
3laCl
6devitrified glass is used for the open report of up-conversion luminescent material.
Summary of the invention
The rare earth ion doped Rb 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
3laCl
6devitrified 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 Rb
3laCl
6devitrified glass, its molar percentage consists of: SiO
287 ~ 93mol%, Rb
3laCl
66.5 ~ 10mol%, LnCl
30.5 ~ 3mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one.
This devitrified glass molar percentage consists of: SiO
287mol%, Rb
3laCl
610mol%, ErCl
30.5mol%, YbCl
32.5mol%.
This devitrified glass molar percentage consists of: SiO
290mol%, Rb
3laCl
68mol%, TmCl
30.2mol%, YbCl
31.8mol%.
This devitrified glass molar percentage consists of: SiO
288mol%, Rb
3laCl
69mol%, ErCl
30.1mol%, TmCl
30.1mol%, YbCl
32.8mol%.
Described rare earth ion doped Rb
3laCl
6the preparation method of devitrified glass, comprises the following steps:
(1) by mole% composition SiO
287 ~ 93mol%, Rb
3laCl
66.5 ~ 10mol%, LnCl
30.5 ~ 3mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one; Take at least one in lanthanum acetate, acetic acid rubidium and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of lanthanum acetate, acetic acid rubidium is respectively by mole% Rb in composition
3laCl
6molar content take, the deal of acetic acid ytterbium, acetic acid erbium, acetic acid thulium and at least one in acetic acid holmium is respectively by LnCl 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 trichoroacetic acid(TCA) obtain transparent mixing solutions, wherein in trichoroacetic acid(TCA) 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 650 ~ 680 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 Rb
3laCl
6devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass has Rb
3laCl
6the 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 Rb obtained by preparation method of the present invention
3laCl
6devitrified 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; 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+, Yb
3+the Rb of doping
3laCl
6the up-conversion luminescence spectrum that the 970nm laser apparatus of devitrified glass excites;
Fig. 3 is the Er that comparative example 1 obtains
3+, Yb
3+the Rb of doping
3laF
6the up-conversion luminescence spectrum that the 970nm laser apparatus of devitrified glass excites.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
Er
3+, Yb
3+doping Rb
3laCl
6the molar percentage of devitrified glass consists of: SiO
287mol%, Rb
3laCl
610mol%, ErCl
30.5mol%, YbCl
32.5mol%, the technique preparing devitrified glass of above composition is as follows:
(1) take lanthanum acetate, acetic acid rubidium, acetic acid ytterbium and acetic acid erbium, wherein the deal of lanthanum acetate and acetic acid rubidium is respectively by mole% Rb in composition
3laCl
6molar content take, the deal of acetic acid ytterbium, acetic acid erbium is respectively by YbCl in above-mentioned identical molar percentage composition
3, ErCl
3molar content take, be dissolved in deionized water by above-mentioned acetate and form Acetate Solution, add trichoroacetic acid(TCA) and obtain transparent mixing solutions in Acetate Solution, wherein in trichoroacetic acid(TCA) 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, 650 ~ 680 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+, Yb
3+the Rb of doping
3laCl
6devitrified glass.
To obtained Rb
3laCl
6devitrified 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 Rb
3laCl
6the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is Rb
3laCl
6the 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 recorded as shown in Figure 2, the integration luminous intensity of green glow (553nm) and ruddiness (667nm) respectively about 1.13 × 10
6, 6.87 × 10
5, green and red up-conversion luminescence is very strong.
Embodiment 2
Tm
3+, Yb
3+doping Rb
3laCl
6the molar percentage of devitrified glass consists of: SiO
290mol%, Rb
3laCl
68mol%, TmCl
30.2mol%, YbCl
31.8mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm
3+, Yb
3+the Rb of doping
3laCl
6devitrified 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+, Tm
3+, Yb
3+doping Rb
3laCl
6the molar percentage of devitrified glass consists of: SiO
288mol%, Rb
3laCl
69mol%, ErCl
30.1mol%, TmCl
30.1mol%, YbCl
32.8mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent Er
3+, Tm
3+, Yb
3+the Rb of doping
3laCl
6devitrified glass.This devitrified glass TRIAX550 fluorescence spectrophotometer is measured, under 970nm laser apparatus shooting conditions, observes strong blueness, green and red up-conversion luminescence.
Embodiment 4
Ho
3+doping Rb
3laCl
6the molar percentage of devitrified glass consists of: SiO
293mol%, Rb
3laCl
66.5mol%, HoCl
30.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho
3+the Rb of doping
3laCl
6devitrified glass.This devitrified glass TRIAX550 fluorescence spectrophotometer is measured, and under 970nm laser apparatus shooting conditions, observes strong green and red up-conversion luminescence.
Comparative example 1
Er
3+, Yb
3+doping Rb
3laF
6the molar percentage of devitrified glass consists of: SiO
287mol%, Rb
3laF
610mol%, ErF
30.5mol%, YbF
32.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er
3+, Yb
3+the Rb of doping
3laF
6devitrified glass.Measure by TRIAX550 fluorescence spectrophotometer, under 970nm laser apparatus shooting conditions, the up-conversion luminescence spectrum of this devitrified glass recorded as shown in Figure 3, the integration luminous intensity of green glow (553nm) and ruddiness (667nm) respectively about 9.07 × 10
4, 5.87 × 10
4, compare with embodiment 1, green and red Up-conversion Intensity is low, and the Er that embodiment 1 obtains is described
3+, Yb
3+the Rb of doping
3laCl
6the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains
3+, Yb
3+the Rb of doping
3laF
6devitrified glass is better.
Claims (5)
1. a rare earth ion doped Rb
3laCl
6devitrified glass, its molar percentage consists of: SiO
287 ~ 93mol%, Rb
3laCl
66.5 ~ 10mol%, LnCl
30.5 ~ 3mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one.
2. Rb rare earth ion doped as claimed in claim 1
3laCl
6devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
287mol%, Rb
3laCl
610mol%, ErCl
30.5mol%, YbCl
32.5mol%.
3. Rb rare earth ion doped as claimed in claim 1
3laCl
6devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
290mol%, Rb
3laCl
68mol%, TmCl
30.2mol%, YbCl
31.8mol%.
4. Rb rare earth ion doped as claimed in claim 1
3laCl
6devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
288mol%, Rb
3laCl
69mol%, ErCl
30.1mol%, TmCl
30.1mol%, YbCl
32.8mol%.
5. Rb rare earth ion doped as claimed in claim 1
3laCl
6the preparation method of devitrified glass, is characterized in that comprising the following steps:
(1) by mole% composition SiO
287 ~ 93mol%, Rb
3laCl
66.5 ~ 10mol%, LnCl
30.5 ~ 3mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one; Take at least one in lanthanum acetate, acetic acid rubidium and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of lanthanum acetate, acetic acid rubidium is respectively by mole% Rb in composition
3laCl
6molar content take, the deal of acetic acid ytterbium, acetic acid erbium, acetic acid thulium and at least one in acetic acid holmium is respectively by LnCl 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 trichoroacetic acid(TCA) obtain transparent mixing solutions, wherein in trichoroacetic acid(TCA) 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 650 ~ 680 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 Rb
3laCl
6devitrified glass.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003018592A1 (en) * | 2001-08-24 | 2003-03-06 | Photon-X, Inc. | Optical gain media |
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 |
CN103382089A (en) * | 2013-07-11 | 2013-11-06 | 中国科学院福建物质结构研究所 | Cs3LaCl6 nanocrystalline-containing transparent chalcohalide glass ceramic and its preparation |
-
2015
- 2015-11-27 CN CN201510852652.2A patent/CN105271771A/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003018592A1 (en) * | 2001-08-24 | 2003-03-06 | Photon-X, Inc. | Optical gain media |
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 |
CN103382089A (en) * | 2013-07-11 | 2013-11-06 | 中国科学院福建物质结构研究所 | Cs3LaCl6 nanocrystalline-containing transparent chalcohalide glass ceramic and its preparation |
Non-Patent Citations (2)
Title |
---|
徐军: "《激光材料科学与技术前沿》", 30 April 2007 * |
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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