CN105314860A - Rare earth ion doped LaCl3 glass ceramics and preparation method thereof - Google Patents
Rare earth ion doped LaCl3 glass ceramics and preparation method thereof Download PDFInfo
- Publication number
- CN105314860A CN105314860A CN201510853318.9A CN201510853318A CN105314860A CN 105314860 A CN105314860 A CN 105314860A CN 201510853318 A CN201510853318 A CN 201510853318A CN 105314860 A CN105314860 A CN 105314860A
- Authority
- CN
- China
- Prior art keywords
- lacl
- rare earth
- devitrified glass
- earth ion
- ion doped
- 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.)
- Withdrawn
Links
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses rare earth ion doped LaCl3 glass ceramics. The rare earth ion doped LaCl3 glass ceramics are prepared from SiO2 75-90.5 mol%, LaCl3 9-20 mol% and LnCl3 0.5-5 mol%, wherein the LnCl3 is at least one of YbCl3, ErCl3, TmCl3 and HoCl3. The rare earth ion doped LaCl3 glass ceramics have the advantages that the prepared rare earth ion doped LaCl3 glass ceramics are transparent, are resistant to deliquescence, are good in mechanical performance and higher in blue and violet light transmittance, have the performances of low phonon energy, high upconversion efficiency and the like, enable the efficiency of an upconversion laser to be improved greatly, a preparation method of the glass ceramics is simple, and the production cost is lower.
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 LaCl being used as up-conversion luminescent material
3devitrified glass and preparation method thereof.
Background technology
Up-conversion luminescence is a kind of process utilizing the absorption of multi-photon to produce radiative transition, and the photon energy of radiation is usually high than the energy of pump photon.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.LaCl
3crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped LaCl
3crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but LaCl
3the 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.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 CN103951211, name is called " rare earth ion doped LaCl
3devitrified glass and preparation method thereof " application for a patent for invention also disclose a kind of crystallite mutually for LaCl
3, glassy phase is P
2o
5be main devitrified glass, the rare earth ion of doping is La
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 LaCl of doping
3devitrified glass is used for the open report of up-conversion luminescent material.
Summary of the invention
The rare earth ion doped LaCl 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
3devitrified 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 LaCl
3devitrified glass, its molar percentage consists of: SiO
275 ~ 90.5mol%, LaCl
39 ~ 20mol%, LnCl
30.5 ~ 5mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one.
This devitrified glass molar percentage consists of: SiO
275mol%, LaCl
320mol%, ErCl
30.5mol%, YbCl
3, 4.5mol%.
This devitrified glass molar percentage consists of: SiO
280.5mol%, LaCl
315mol%, TmCl
30.5mol%, YbCl
34mol%.
This devitrified glass molar percentage consists of: SiO
281mol%, LaCl
314mol%, ErCl
30.5mol%, TmCl
30.5mol%, YbCl
34mol%.
Described rare earth ion doped LaCl
3the preparation method of devitrified glass, comprises the following steps:
(1) by mole% composition SiO
275 ~ 90.5mol%, LaCl
39 ~ 20mol%, LnCl
30.5 ~ 5mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one; Take at least one in lanthanum acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of lanthanum acetate is by mole% LaCl in composition
3molar 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 140 DEG C of dryings 9 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 660 ~ 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 LaCl
3devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass has LaCl
3the 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 LaCl obtained by preparation method of the present invention
3devitrified 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 LaCl of doping
3the 970nm laser apparatus of devitrified glass excites up-conversion luminescence spectrum;
Fig. 3 is the Er that comparative example 1 obtains
3+, Yb
3+the LaF of doping
3the 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+, Yb
3+doping LaCl
3the molar percentage of devitrified glass consists of: SiO
275mol%, LaCl
320mol%, ErCl
30.5mol%, YbCl
3, 4.5mol%, the technique preparing devitrified glass of above composition is as follows:
(1) take lanthanum acetate, acetic acid ytterbium, acetic acid erbium, and deal is respectively by the LaCl in above-mentioned molar percentage composition
3, YbCl
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 140 DEG C of dryings 9 days, obtains transparent xerogel;
(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 660 ~ 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 LaCl of doping
3devitrified glass.
To obtained LaCl
3devitrified 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 LaCl
3the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is LaCl
3the 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 (523nm, 546nm) and ruddiness (653nm) respectively about 1.43 × 10
6, 1.51 × 10
6, green and red up-conversion luminescence is very strong.
Embodiment 2
Tm
3+, Yb
3+doping LaCl
3the molar percentage of devitrified glass consists of: SiO
280.5mol%, LaCl
315mol%, TmCl
30.5mol%, YbCl
34mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm
3+, Yb
3+the LaCl of doping
3devitrified 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 LaCl
3the molar percentage of devitrified glass consists of: SiO
281mol%, LaCl
314mol%, ErCl
30.5mol%, TmCl
30.5mol%, YbCl
34mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er
3+, Tm
3+, Yb
3+the LaCl of doping
3devitrified 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 LaCl
3the molar percentage of devitrified glass consists of: SiO
290.5mol%, LaCl
39mol%, HoCl
30.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho
3+the LaCl of doping
3devitrified 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 LaF
3the molar percentage of devitrified glass consists of: SiO
275mol%, LaF
320mol%, ErF
30.5mol%, YbF
34.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er
3+, Yb
3+the LaF of doping
3devitrified 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 (523nm, 546nm) and ruddiness (653nm) respectively about 1.42 × 10
4, 1.49 × 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 LaCl of doping
3the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains
3+, Yb
3+the LaF of doping
3devitrified glass is better.
Claims (5)
1. a rare earth ion doped LaCl
3devitrified glass, its molar percentage consists of: SiO
275 ~ 90.5mol%, LaCl
39 ~ 20mol%, LnCl
30.5 ~ 5mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one.
2. LaCl rare earth ion doped as claimed in claim 1
3devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
275mol%, LaCl
320mol%, ErCl
30.5mol%, YbCl
3, 4.5mol%.
3. LaCl rare earth ion doped as claimed in claim 1
3devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
280.5mol%, LaCl
315mol%, TmCl
30.5mol%, YbCl
34mol%.
4. LaCl rare earth ion doped as claimed in claim 1
3devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO
281mol%, LaCl
314mol%, ErCl
30.5mol%, TmCl
30.5mol%, YbCl
34mol%.
5. LaCl rare earth ion doped as claimed in claim 1
3the preparation method of devitrified glass, is characterized in that comprising the following steps:
(1) by mole% composition SiO
275 ~ 90.5mol%, LaCl
39 ~ 20mol%, LnCl
30.5 ~ 5mol%, wherein LnCl
3for YbCl
3, ErCl
3, TmCl
3and HoCl
3in at least one; Take at least one in lanthanum acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of lanthanum acetate is by mole% LaCl in composition
3molar 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 140 DEG C of dryings 9 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 660 ~ 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 LaCl
3devitrified glass.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510853318.9A CN105314860A (en) | 2015-11-27 | 2015-11-27 | Rare earth ion doped LaCl3 glass ceramics and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510853318.9A CN105314860A (en) | 2015-11-27 | 2015-11-27 | Rare earth ion doped LaCl3 glass ceramics and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105314860A true CN105314860A (en) | 2016-02-10 |
Family
ID=55243279
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510853318.9A Withdrawn CN105314860A (en) | 2015-11-27 | 2015-11-27 | Rare earth ion doped LaCl3 glass ceramics and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105314860A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110040967A (en) * | 2019-05-14 | 2019-07-23 | 哈尔滨工程大学 | Transparent glass-ceramics and preparation method with monochromatic Upconversion luminescence |
CN114276023A (en) * | 2021-11-17 | 2022-04-05 | 宁波大学 | Infrared chalcogenide glass ceramic optical fiber and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101209899A (en) * | 2006-12-27 | 2008-07-02 | 中国科学院福建物质结构研究所 | Erbium-doped calcium-fluoride-nanocrystalline-containing transparent glass ceramic and its sol-gel preparation |
-
2015
- 2015-11-27 CN CN201510853318.9A patent/CN105314860A/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101209899A (en) * | 2006-12-27 | 2008-07-02 | 中国科学院福建物质结构研究所 | Erbium-doped calcium-fluoride-nanocrystalline-containing transparent glass ceramic and its sol-gel preparation |
Non-Patent Citations (3)
Title |
---|
KARL W. KRAMER等: "Infrared-to-visible upconversion in LaCl3_1%Er3+_Energy-level and line-strength calculations", 《PHYSICAL REVIEW B》 * |
田永君 等主编: "《先进材料导论》", 31 January 2005, 哈尔滨工业大学出版社 * |
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》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110040967A (en) * | 2019-05-14 | 2019-07-23 | 哈尔滨工程大学 | Transparent glass-ceramics and preparation method with monochromatic Upconversion luminescence |
CN110040967B (en) * | 2019-05-14 | 2021-10-01 | 哈尔滨工程大学 | Transparent microcrystalline glass with monochromatic up-conversion luminescence characteristic and preparation method thereof |
CN114276023A (en) * | 2021-11-17 | 2022-04-05 | 宁波大学 | Infrared chalcogenide glass ceramic optical fiber and preparation method thereof |
CN114276023B (en) * | 2021-11-17 | 2024-05-10 | 宁波大学 | Infrared chalcogenide glass ceramic optical fiber and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105254184A (en) | Li3YCl6 glass ceramics doped with rare earth ions and preparation method of Li3YCl6 glass ceramics | |
CN105314860A (en) | Rare earth ion doped LaCl3 glass ceramics and preparation method thereof | |
CN105314863A (en) | Rare earth ion doped BaCl2 glass ceramics and preparation method thereof | |
CN105293921A (en) | Rare earth ion doped K3LuCl6 glass ceramic and preparation method thereof | |
CN105314871A (en) | Rare earth ion doped YCl3 microcrystalline glass and preparation method thereof | |
CN105330164A (en) | Rare earth ion doped PbCl2 microcrystalline glass and preparation method thereof | |
CN105314876A (en) | Rare-earth ion doping Cs2YCl5 glass ceramics and preparation method thereof | |
CN105314873A (en) | Rare earth ion-doped CeBr3 microcrystalline glass and preparation method thereof | |
CN105330163A (en) | Rare earth ion doped SrI2 microcrystalline glass and preparation method thereof | |
CN105293926A (en) | Rear earth ion-doped K2GdBr5 microcrystalline glass and preparation method thereof | |
CN105314867A (en) | Rare earth ion doped CaCl2 glass-ceramic and preparation method thereof | |
CN105314874A (en) | Rare earth ion doped CeCl3 glass ceramic and preparation method thereof | |
CN105314875A (en) | Rare-earth-ion-doped Cs2LaCl5 microcrystalline glass and preparation method thereof | |
CN105330162A (en) | Rare earth ion doped GdCl3 microcrystalline glass and preparation method thereof | |
CN105314869A (en) | Rare earth ion doped CdCl2 glass ceramic and preparation method thereof | |
CN105314877A (en) | Rare earth ion doped KY2Cl7 glass-ceramic and preparation method thereof | |
CN105293923A (en) | Rare earth ion doped K3GdCl6 glass ceramic and preparation method thereof | |
CN105314865A (en) | Rare earth ion doped SrCl2 microcrystalline glass and preparation method thereof | |
CN105271774A (en) | Rare-earth ion doped NaLuCl4 microcrystalline glass and preparation method thereof | |
CN105271775A (en) | Rare earth ion doped KGd2Cl7 microcrystal glass and preparation method thereof | |
CN105314857A (en) | Rare earth ion doped LuCl3 glass ceramics and preparation method thereof | |
CN101125734A (en) | Tm3+/Yb3+ codoping phosphate glass and its preparing method | |
CN105271771A (en) | Rare earth ion doped Rb3LaC16 microcrystal glass and preparation method thereof | |
CN105271773A (en) | Rare earth ion doped Cs3CeC16 glass ceramic and preparation method thereof | |
CN105271776A (en) | Rare-earth-ion-doped Cs2LuCl5 microcrystalline glass and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20160210 |