CN105271767A - Rare earth ion-doped Rb2CeBr5 glass ceramic and preparation method thereof - Google Patents

Abstract

The invention discloses rare earth ion-doped Rb2CeBr5 glass ceramic, which comprises the following components by mole percentage: 87-94mol% of SiO2, 5.6-10mol% of Rb2CeBr5 and 0.4-3mol% of LnBr3, wherein the LnBr3 is at least one of YbBr3, ErBr3, TmBr3 and HoBr3. The prepared rare earth ion-doped Rb2CeBr5 glass ceramic has the advantages of being transparent, deliquescence proof, good in mechanical property and relatively high in blue-violet light transmittance, and has the properties of low phonon energy, high upconversion efficiency and the like; the efficiency of an upconversion laser device can be greatly improved; and the glass ceramic is simple in preparation method and relatively low in production cost.

Description

A kind of rare earth ion doped Rb 2ceBr 5devitrified 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 Rb being used as up-conversion luminescent material ₂ceBr ₅devitrified 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 ₂ceBr ₅the lattice phonon energy Ratios fluorochemical of crystal is lower, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped Rb ₂ceBr ₅crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but Rb ₂ceBr ₅the 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 CN103951218, name is called " rare earth ion doped K ₂laBr ₅devitrified glass and preparation method thereof " application for a patent for invention disclose a kind of crystallite mutually for K ₂laBr ₅, glassy phase is B ₂o ₃with Nb ₂o ₅be 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 Rb of doping ₂ceBr ₅devitrified 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 ₂ceBr ₅devitrified 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 ₂ceBr ₅devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, Rb ₂ceBr ₅5.6 ~ 10mol%, LnBr ₃0.4 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂88mol%, Rb ₂ceBr ₅10mol%, ErBr ₃0.5mol%, YbBr ₃1.5mol%.

This devitrified glass molar percentage consists of: SiO ₂88.8mol%, Rb ₂ceBr ₅9mol%, TmBr ₃0.2mol%, YbBr ₃2mol%.

This devitrified glass molar percentage consists of: SiO ₂87mol%, Rb ₂ceBr ₅10mol%, ErBr ₃0.1mol%, TmBr ₃0.1mol%, YbBr ₃: 2.8mol%.

Described rare earth ion doped Rb ₂ceBr ₅the preparation method of devitrified glass, comprises the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, Rb ₂ceBr ₅5.6 ~ 10mol%, LnBr ₃0.4 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one; Take at least one in cerous acetate, acetic acid rubidium and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of cerous acetate, acetic acid rubidium is respectively by mole% Rb in composition ₂ceBr ₅molar 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 135 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 570 ~ 590 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 ₂ceBr ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has Rb ₂ceBr ₅the 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 ₂ceBr ₅devitrified 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 the transmission electron microscope figure (TEM) of the devitrified glass that embodiment 1 obtains;

Fig. 2 is the Er that embodiment 1 obtains ³⁺, Yb ³⁺the Rb of doping ₂ceBr ₅the 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 Rb of doping ₂ceF ₅the 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 Rb ₂ceBr ₅the molar percentage of devitrified glass consists of: SiO ₂88mol%, Rb ₂ceBr ₅10mol%, ErBr ₃0.5mol%, YbBr ₃1.5mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take cerous acetate, acetic acid rubidium, acetic acid ytterbium and acetic acid erbium, wherein the deal of cerous acetate, acetic acid rubidium is respectively by mole% Rb in composition ₂ceBr ₅molar content take, the deal of acetic acid ytterbium, acetic acid erbium is respectively by YbBr in above-mentioned identical molar percentage composition ₃, ErBr 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 135 DEG C of dryings 9 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 570 ~ 590 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 ₂ceBr ₅devitrified glass.

To obtained Rb ₂ceBr ₅devitrified glass carries out transmission electron microscope test, obtains the transmission electron microscope picture of this devitrified glass as shown in Figure 1, and its result is as follows: in photo, the nano microcrystalline of glass basis and precipitation seems more clearly, and the stain distributed in glass basis is microcrystal grain.X-ray diffraction test shows that crystalline phase is Rb ₂ceBr ₅phase, the material therefore obtained is Rb ₂ceBr ₅the 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), green glow (546nm) and ruddiness (653nm) respectively about 5.72 × 10 ⁵, 7.93 × 10 ⁵, 5.29 × 10 ⁵, green and red up-conversion luminescence is very strong.

Embodiment 2

Tm ³⁺, Yb ³⁺doping Rb ₂ceBr ₅the molar percentage of devitrified glass consists of: SiO ₂88.8mol%, Rb ₂ceBr ₅9mol%, TmBr ₃0.2mol%, YbBr ₃2mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the Rb of doping ₂ceBr ₅devitrified 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 ₂ceBr ₅the molar percentage of devitrified glass consists of: SiO ₂87mol%, Rb ₂ceBr ₅10mol%, ErBr ₃0.1mol%, TmBr ₃0.1mol%, YbBr ₃: 2.8mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Tm ³⁺, Yb ³⁺the Rb of doping ₂ceBr ₅devitrified 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 ₂ceBr ₅the molar percentage of devitrified glass consists of: SiO ₂94mol%, Rb ₂ceBr ₅5.6mol%, HoBr ₃0.4mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho ³⁺the Rb of doping ₂ceBr ₅devitrified 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 ₂ceF ₅the molar percentage of devitrified glass consists of: SiO ₂88mol%, Rb ₂ceF ₅10mol%, ErF ₃0.5mol%, YbF ₃1.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Yb ³⁺the Rb of doping ₂ceF ₅devitrified 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), green glow (546nm) and ruddiness (653nm) respectively about 4.57 × 10 ⁴, 6.41 × 10 ⁴, 4.37 × 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 ₂ceBr ₅the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the Rb of doping ₂ceF ₅devitrified glass is better.

Claims (5)

1. a rare earth ion doped Rb ₂ceBr ₅devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, Rb ₂ceBr ₅5.6 ~ 10mol%, LnBr ₃0.4 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one.

2. Rb rare earth ion doped as claimed in claim 1 ₂ceBr ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂88mol%, Rb ₂ceBr ₅10mol%, ErBr ₃0.5mol%, YbBr ₃1.5mol%.

3. Rb rare earth ion doped as claimed in claim 1 ₂ceBr ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂88.8mol%, Rb ₂ceBr ₅9mol%, TmBr ₃0.2mol%, YbBr ₃2mol%.

4. Rb rare earth ion doped as claimed in claim 1 ₂ceBr ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂87mol%, Rb ₂ceBr ₅10mol%, ErBr ₃0.1mol%, TmBr ₃0.1mol%, YbBr ₃: 2.8mol%.

5. Rb rare earth ion doped as claimed in claim 1 ₂ceBr ₅the preparation method of devitrified glass, is characterized in that comprising the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, Rb ₂ceBr ₅5.6 ~ 10mol%, LnBr ₃0.4 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one; Take at least one in cerous acetate, acetic acid rubidium and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of cerous acetate, acetic acid rubidium is respectively by mole% Rb in composition ₂ceBr ₅molar 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 135 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 570 ~ 590 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 ₂ceBr ₅devitrified glass.