CN105314868A - Rare-earth ion doped CdBr2 micro-crystal glass and preparation method thereof - Google Patents

Rare-earth ion doped CdBr2 micro-crystal glass and preparation method thereof Download PDF

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Publication number
CN105314868A
CN105314868A CN201510853396.9A CN201510853396A CN105314868A CN 105314868 A CN105314868 A CN 105314868A CN 201510853396 A CN201510853396 A CN 201510853396A CN 105314868 A CN105314868 A CN 105314868A
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cdbr
devitrified glass
earth ion
acetic acid
ion doped
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张志雄
张约品
欧阳绍业
张为欢
王倩
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Ningbo University
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Ningbo University
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Abstract

The invention discloses rare-earth ion doped CdBr2 micro-crystal glass which consists of the following components in percentage by mole: 80-94.5% of SiO2, 5-15% of CdBr2 and 0.5-5% of LnBr3, wherein LnBr3 is at least one of YbBr3, ErBr3, TmBr3 and HoBr3. The rare-earth ion doped CdBr2 micro-crystal glass has the advantages of transparency, air-slake resistance, good mechanical property, relatively high blue-purple light transmissivity, low phonon energy, upper conversion efficiency, and the like, the efficiency of an upper conversion laser can be greatly improved, and moreover the micro-crystal glass is simple in preparation method and relatively low in production cost.

Description

A kind of rare earth ion doped CdBr 2devitrified glass and preparation method thereof
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 CdBr 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.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.Up-conversion lasing 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.CdBr 2crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped CdBr 2crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, rare earth ion doped CdBr 2crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but CdBr 2the easy moisture absorption of crystal, easily moisture absorption, need special processing and storage, be difficult to its practical application of the disadvantages affect such as preparation, chemical stability and physical strength be 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+, Tm 3+and Ho 3+the CdBr of doping 2devitrified glass is used for the open report of up-conversion luminescent material.
Summary of the invention
The rare earth ion doped CdBr 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 CdBr 2devitrified glass, its molar percentage consists of: SiO 280 ~ 94.5mol%, CdBr 25 ~ 15mol%, LnBr 30.5 ~ 5mol%, wherein LnBr 3for YbBr 3, ErBr 3, TmBr 3and HoBr 3in at least one.
This devitrified glass molar percentage consists of: SiO 280.5mol%, CdBr 215mol%, TmBr 30.5mol%, YbBr 34mol%.
This devitrified glass molar percentage consists of: SiO 280mol%, CdBr 215mol%, ErBr 30.5mol%, YbBr 34.5mol%.
This devitrified glass molar percentage consists of: SiO 285mol%, CdBr 211mol%, ErBr 30.1mol%, TmBr 30.1mol%, YbBr 33.8mol%.
Described rare earth ion doped CdBr 2the preparation method of devitrified glass, comprises the following steps:
(1) by mole% composition SiO 280 ~ 94.5mol%, CdBr 25 ~ 15mol%, LnBr 30.5 ~ 5mol%, wherein LnBr 3for YbBr 3, ErBr 3, TmBr 3and HoBr 3in at least one; Take at least one in cadmium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of cadmium acetate is by mole% CdBr in composition 2molar 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 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 145 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 460 ~ 480 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 CdBr 2devitrified glass
Compared with prior art, the invention has the advantages that: this devitrified glass has CdBr 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 CdBr 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; 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 devitrified glass X-ray diffraction (XRD) figure that embodiment 1 obtains;
Fig. 2 is the Tm that embodiment 1 obtains 3+, Yb 3+the CdBr of doping 2the 970nm laser apparatus of devitrified glass excites up-conversion luminescence spectrum;
Fig. 3 is the Tm that comparative example 1 obtains 3+, Yb 3+the CdF 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
Tm 3+, Yb 3+doping CdBr 2the molar percentage of devitrified glass consists of: SiO 280.5mol%, CdBr 215mol%, TmBr 30.5mol%, YbBr 34mol%, the technique of the preparation up-conversion luminescence microcrystal glass material of above composition is as follows:
(1) amount of taking cadmium acetate, acetic acid ytterbium, acetic acid thulium, and deal is respectively by the CdBr in above-mentioned molar percentage composition 2, YbBr 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 145 DEG C of dryings 7 days, obtains transparent xerogel;
(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 460 ~ 480 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 Tm 3+, Yb 3+the CdBr of doping 2devitrified glass.
Carry out X-ray diffraction test to this devitrified glass, obtain the XRD figure of glass after micritization process as shown in Figure 1, its result is as follows: the XRD diffraction peak of the sample obtained through Overheating Treatment and CdBr 2the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is CdBr 2the devitrified glass of crystallization phase.With TRIAX550 fluorescence spectrophotometer measure, under 970nm laser apparatus shooting conditions, the up-conversion luminescence spectrum of this devitrified glass as shown in Figure 2, the integration luminous intensity about 6.55 × 10 of blue light (476nm) 5, blue up-conversion luminous very strong.
Embodiment 2
Er 3+, Yb 3+doping CdBr 2the molar percentage of devitrified glass consists of: SiO 280mol%, CdBr 215mol%, ErBr 30.5mol%, YbBr 34.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er 3+, Yb 3+the CdBr of doping 2devitrified glass.This devitrified glass TRIAX550 fluorescence spectrophotometer is measured, under 970nm laser apparatus shooting conditions, observes strong green and red up-conversion luminescence.
Embodiment 3
Er 3+, Tm 3+, Yb 3+doping CdBr 2the molar percentage of devitrified glass consists of: SiO 285mol%, CdBr 211mol%, ErBr 30.1mol%, TmBr 30.1mol%, YbBr 33.8mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er 3+, Tm 3+, Yb 3+the CdBr of doping 2devitrified 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 CdBr 2the molar percentage of devitrified glass consists of: SiO 294.5mol%, CdBr 25mol%, HoBr 30.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho 3+the CdBr of doping 2devitrified 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
Tm 3+, Yb 3+doping CdF 2the molar percentage of devitrified glass consists of: SiO 280.5mol%, CdF 215mol%, TmF 30.5mol%, YbF 34mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm 3+, Yb 3+the CdF of doping 2devitrified glass.With TRIAX550 fluorescence spectrophotometer measure, under 970nm laser apparatus shooting conditions, the up-conversion luminescence spectrum of this devitrified glass as shown in Figure 3, the integration luminous intensity about 4.22 × 10 of blue light (476nm) 4, compare with embodiment 1, blue up-conversion luminous low, the Tm that embodiment 1 obtains is described 3+, Yb 3+the CdBr of doping 2the Tm that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains 3+, Yb 3+the CdF of doping 2devitrified glass is better.

Claims (5)

1. a rare earth ion doped CdBr 2devitrified glass, its molar percentage consists of: SiO 280 ~ 94.5mol%, CdBr 25 ~ 15mol%, LnBr 30.5 ~ 5mol%, wherein LnBr 3for YbBr 3, ErBr 3, TmBr 3and HoBr 3in at least one.
2. CdBr rare earth ion doped as claimed in claim 1 2devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO 280.5mol%, CdBr 215mol%, TmBr 30.5mol%, YbBr 34mol%.
3. CdBr rare earth ion doped as claimed in claim 1 2devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO 280mol%, CdBr 215mol%, ErBr 30.5mol%, YbBr 34.5mol%.
4. CdBr rare earth ion doped as claimed in claim 1 2devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO 285mol%, CdBr 211mol%, ErBr 30.1mol%, TmBr 30.1mol%, YbBr 33.8mol%.
5. CdBr rare earth ion doped as claimed in claim 1 2the preparation method of devitrified glass, is characterized in that comprising the following steps:
(1) by mole% composition SiO 280 ~ 94.5mol%, CdBr 25 ~ 15mol%, LnBr 30.5 ~ 5mol%, wherein LnBr 3for YbBr 3, ErBr 3, TmBr 3and HoBr 3in at least one; Take at least one in cadmium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of cadmium acetate is by mole% CdBr in composition 2molar 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 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 145 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 460 ~ 480 DEG C, and then be cooled to 50 DEG C with the speed of 10 DEG C DEG C/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped CdBr 2devitrified glass.
CN201510853396.9A 2015-11-27 2015-11-27 Rare-earth ion doped CdBr2 micro-crystal glass and preparation method thereof Withdrawn CN105314868A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987005287A1 (en) * 1986-02-28 1987-09-11 Japan Oxygen Co., Ltd. Process for manufacturing glass
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987005287A1 (en) * 1986-02-28 1987-09-11 Japan Oxygen Co., Ltd. Process for manufacturing glass
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MASANORI SHOJIYA等: ""Upconversion luminescence of Er3+ in CdX 2 system glasses (X=Cl, Br, I)"", 《APPL. PHYS. LETT》 *
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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Application publication date: 20160210