CN105271770A - Rare-earth-ion-doped NaBaLaBr6 microcrystalline glass and preparation method thereof - Google Patents

Abstract

The invention discloses rare-earth-ion-doped NaBaLaBr6 microcrystalline glass. The rare-earth-ion-doped NaBaLaBr6 microcrystalline glass comprises the following components in mole percentage: 87-94mol% of SiO2, 5.5-10mol% of NaBaLaBr6 and 0.5-3mol% of LnBr3, wherein LnBr3 is at least one of YbBr3, ErBr3 and TmBr3. The obtained rare-earth-ion-doped NaBaLaBr6 microcrystalline glass has the advantages of transparency, deliquescence resistance, good mechanical properties and high blue and violet light transmittance and has performances of low phonon energy and high upconversion efficiency, efficiency of an upconversion laser can be greatly improved, and the preparation method of the rare-earth-ion-doped NaBaLaBr6 microcrystalline glass is simple and low in production cost.

Description

A kind of rare earth ion doped NaBaLaBr 6devitrified 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 NaBaLaBr being used as up-conversion luminescent material ₆devitrified 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.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.NaBaLaBr ₆crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped NaBaLaBr ₆crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but NaBaLaBr ₆the easy moisture absorption of crystal, be difficult to preparation, need special processing and the disadvantages affect such as storage, chemical stability and physical strength the be poor practical application of its up-conversion luminescence.

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 CN103951241, name is called " rare earth ion doped Cs ₂liLaBr ₆devitrified glass and preparation method thereof " application for a patent for invention disclose a kind of crystallite mutually for Cs ₂liLaBr ₆, glassy phase is P 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⁺and Tm ³⁺the NaBaLaBr of doping ₆devitrified glass is used for the open report of up-conversion luminescent material.

Summary of the invention

The rare earth ion doped NaBaLaBr 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 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 NaBaLaBr ₆devitrified glass, its molar percentage is composed as follows: SiO ₂87 ~ 94mol%, NaBaLaBr ₆5.5 ~ 10mol%, LnBr ₃0.5 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂89mol%, NaBaLaBr ₆9mol%, TmBr ₃0.5mol%, YbBr ₃1.5mol%.

This devitrified glass molar percentage consists of: SiO ₂94mol%, NaBaLaBr ₆5.5mol%, ErBr ₃0.5mol%.

This devitrified glass molar percentage consists of: SiO ₂87mol%, NaBaLaBr ₆10mol%, ErBr ₃0.1mol%, TmBr ₃0.1mol%, YbBr ₃2.8mol%.

Described rare earth ion doped NaBaLaBr ₆the preparation method of devitrified glass, comprises the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, NaBaLaBr ₆5.5 ~ 10mol%, LnBr ₃0.5 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃in at least one; Take at least one in lanthanum acetate, sodium-acetate, barium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium, wherein the deal of lanthanum acetate, sodium-acetate, barium acetate is respectively by mole% NaBaLaBr in composition ₆molar 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 141 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 630 ~ 660 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 NaBaLaBr ₆devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has NaBaLaBr 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 NaBaLaBr obtained by preparation method of the present invention 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 the transmission electron microscope figure (TEM) of the devitrified glass that embodiment 1 obtains;

Fig. 2 is the Tm that embodiment 1 obtains ³⁺, Yb ³⁺the NaBaLaBr of doping ₆the up-conversion luminescence spectrum that the 970nm laser apparatus of devitrified glass excites;

Fig. 3 is the Tm that comparative example 1 obtains ³⁺, Yb ³⁺the NaBaLaF of doping 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

Tm ³⁺, Yb ³⁺doping NaBaLaBr ₆the molar percentage of devitrified glass consists of: SiO ₂89mol%, NaBaLaBr ₆9mol%, TmBr ₃0.5mol%, YbBr ₃1.5mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take lanthanum acetate, sodium-acetate, barium acetate, acetic acid ytterbium and acetic acid thulium, wherein the deal of lanthanum acetate, sodium-acetate and barium acetate is respectively by mole% NaBaLaBr in composition ₆molar content take, the deal of acetic acid ytterbium, acetic acid thulium is respectively by YbBr in above-mentioned identical molar percentage composition 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 141 DEG C of dryings 9 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 630 ~ 660 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 NaBaLaBr devitrified glass of doping.

To obtained NaBaLaBr ₆devitrified 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 NaBaLaBr ₆phase, the material therefore obtained is NaBaLaBr 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 blue light (476nm) and ruddiness (679nm) respectively about 4.99 × 10 ⁵, 8.26 × 10 ⁵, blue and red up-conversion luminescence is very strong.

Embodiment 2

Er ³⁺doping NaBaLaBr ₆the molar percentage of devitrified glass consists of: SiO ₂94mol%, NaBaLaBr ₆5.5mol%, ErBr ₃0.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺the NaBaLaBr of doping ₆devitrified glass.Spectrum test is carried out to this devitrified glass, when exciting with 543nm and 548.8nm wavelength light source, observes strong ultraviolet and purple up-conversion luminescence.

Embodiment 3

Er ³⁺, Tm ³⁺, Yb ³⁺doping NaBaLaBr ₆the molar percentage of devitrified glass consists of: SiO ₂87mol%, NaBaLaBr ₆10mol%, ErBr ₃0.1mol%, TmBr ₃0.1mol%, YbBr ₃2.8mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Tm ³⁺, Yb ³⁺the NaBaLaBr of doping 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.

Comparative example 1

Tm ³⁺, Yb ³⁺doping NaBaLaF ₆the molar percentage of devitrified glass consists of: SiO ₂89mol%, NaBaLaF ₆9mol%, TmF ₃0.5mol%, YbF ₃1.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the NaBaLaF of doping ₆devitrified glass.Measure by TRIAX550 fluorescence spectrophotometer, under 970nm laser apparatus excites, record the up-conversion luminescence spectrum of this devitrified glass as shown in Figure 3, the integration luminous intensity of blue light (476nm) and ruddiness (679nm) respectively about 3.56 × 10 ⁴, 5.90 × 10 ⁴, compare with embodiment 1, blue and red Up-conversion Intensity is low, and the Tm that embodiment 1 obtains is described ³⁺, Yb ³⁺the NaBaLaBr of doping ₆the Tm that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the NaBaLaF of doping ₆devitrified glass is better.

Claims (5)

1. a rare earth ion doped NaBaLaBr ₆devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, NaBaLaBr ₆5.5 ~ 10mol%, LnBr ₃0.5 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃in at least one.

2. NaBaLaBr rare earth ion doped as claimed in claim 1 ₆devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂89mol%, NaBaLaBr ₆9mol%, TmBr ₃0.5mol%, YbBr ₃1.5mol%.

3. NaBaLaBr rare earth ion doped as claimed in claim 1 ₆devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂94mol%, NaBaLaBr ₆5.5mol%, ErBr ₃0.5mol%.

4. NaBaLaBr rare earth ion doped as claimed in claim 1 ₆devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂87mol%, NaBaLaBr ₆10mol%, ErBr ₃0.1mol%, TmBr ₃0.1mol%, YbBr ₃2.8mol%.

5. NaBaLaBr rare earth ion doped as claimed in claim 1 ₆the preparation method of devitrified glass, is characterized in that comprising the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, NaBaLaBr ₆5.5 ~ 10mol%, LnBr ₃0.5 ~ 3mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃in at least one; Take at least one in lanthanum acetate, sodium-acetate, barium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium, wherein the deal of lanthanum acetate, sodium-acetate, barium acetate takes by mole% the molar content of NaBaLaBr6 in composition respectively, LnBr during acetic acid ytterbium, acetic acid erbium form by above-mentioned identical molar percentage respectively with the deal of at least one in acetic acid thulium 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 141 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 630 ~ 660 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 NaBaLaBr ₆devitrified glass.