CN105314859A - Rare earth ion doped LaBr3 glass ceramics and preparation method thereof - Google Patents

Abstract

The invention discloses rare earth ion doped LaBr3 glass ceramics. The rare earth ion doped LaBr3 glass ceramics are prepared from SiO2 80-95 mol%, LaBr3 4.6-16 mol% and LnBr3 0.4-6 mol%, wherein the LnBr3 is at least one of YbBr3, ErBr3, TmBr3 and HoBr3. The rare earth ion doped LaBr3 glass ceramics have the advantages that the prepared rare earth ion doped LaBr3 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

A kind of rare earth ion doped LaBr 3devitrified 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 LaBr 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.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.LaBr ₃crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped LaBr ₃crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but LaBr 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.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 CN103951212, name is called " rare earth ion doped LaBr ₃devitrified glass and preparation method thereof " application for a patent for invention disclose a kind of crystallite mutually for LaBr ₃, glassy phase is 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 LaBr of doping ₃devitrified glass is used for the open report of up-conversion luminescent material.

Summary of the invention

The rare earth ion doped LaBr 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 LaBr ₃devitrified glass, its molar percentage consists of: SiO ₂80 ~ 95mol%, LaBr ₃4.6 ~ 16mol%, LnBr ₃0.4 ~ 6mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂81mol%, LaBr ₃15mol%, ErBr ₃0.2mol%, TmBr ₃0.1mol%, YbBr ₃3.7mol%.

This devitrified glass molar percentage consists of: SiO ₂80mol%, LaBr ₃16mol%, TmBr ₃0.3mol%, YbBr ₃3.7mol%.

This devitrified glass molar percentage consists of: SiO ₂82mol%, LaBr ₃12mol%, ErBr ₃0.5mol%, YbBr ₃5.5mol%.

Described rare earth ion doped LaBr ₃the preparation method of devitrified glass, comprises the following steps:

(1) by mole% composition SiO ₂80 ~ 95mol%, LaBr ₃4.6 ~ 16mol%, LnBr ₃0.4 ~ 6mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr 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% LaBr 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 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 8 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 ~ 650 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 LaBr ₃devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has LaBr 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 LaBr 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; By changing rear-earth-doped concentration, RGB light luminous intensity ratio can be controlled; 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 Er that embodiment 1 obtains ³⁺, Tm ³⁺, Yb ³⁺the LaBr 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⁺, Tm 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⁺, Tm ³⁺, Yb ³⁺doping LaBr ₃the molar percentage of devitrified glass consists of: SiO ₂81mol%, LaBr ₃15mol%, ErBr ₃0.2mol%, TmBr ₃0.1mol%, YbBr ₃3.7mol%, the technique of the devitrified glass of above composition is as follows:

(1) take lanthanum acetate, acetic acid ytterbium, acetic acid erbium and acetic acid thulium, and deal is respectively by the LaBr in above-mentioned molar percentage composition ₃, YbBr ₃, ErBr ₃and 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 8 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 630 ~ 650 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⁺, Tm ³⁺, Yb ³⁺doping LaBr ₃devitrified glass.

To obtained LaBr 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 LaBr ₃the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is LaBr 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 blue light (476nm), green glow (533nm), green glow (546nm) and ruddiness (653nm) respectively about 4.43 × 10 ⁵, 7.58 × 10 ⁵, 3.78 × 10 ⁵, 3.95 × 10 ⁵, blueness, green and red up-conversion luminescence are very strong.

Embodiment 2

Tm ³⁺, Yb ³⁺doping LaBr ₃the molar percentage of devitrified glass consists of: SiO ₂80mol%, LaBr ₃16mol%, TmBr ₃0.3mol%, YbBr ₃3.7mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the LaBr 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⁺, Yb ³⁺doping LaBr ₃the molar percentage of devitrified glass consists of: SiO ₂82mol%, LaBr ₃12mol%, ErBr ₃0.5mol%, YbBr ₃5.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Yb ³⁺the LaBr of doping ₃devitrified glass.This devitrified glass TRIAX550 fluorescence spectrophotometer is measured, under 970nm laser apparatus shooting conditions, observes strong green and red up-conversion luminescence.

Embodiment 4

Ho ³⁺doping LaBr ₃the molar percentage of devitrified glass consists of: SiO ₂95mol%, LaBr ₃4.6mol%, HoBr ₃0.4mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho ³⁺the LaBr 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⁺, Tm ³⁺, Yb ³⁺doping LaF ₃the molar percentage of devitrified glass consists of: SiO ₂81mol%, LaF ₃15mol%, ErF ₃0.2mol%, TmF ₃0.1mol%, YbF ₃3.7mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Tm 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 blue light (476nm), green glow (533nm), green glow (546nm) and ruddiness (653nm) respectively about 3.81 × 10 ⁴, 6.51 × 10 ⁴, 3.23 × 10 ⁴, 3.38 × 10 ⁴, compare with embodiment 1, blueness, green and red Up-conversion Intensity are low, and the Er that embodiment 1 obtains is described ³⁺, Tm ³⁺, Yb ³⁺the LaBr of doping ₃the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Tm ³⁺, Yb ³⁺the LaF of doping ₃devitrified glass is better.

Claims (5)

1. a rare earth ion doped LaBr ₃devitrified glass, its molar percentage consists of: SiO ₂80 ~ 95mol%, LaBr ₃4.6 ~ 16mol%, LnBr ₃0.4 ~ 6mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one.

2. LaBr rare earth ion doped as claimed in claim 1 ₃devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂81mol%, LaBr ₃15mol%, ErBr ₃0.2mol%, TmBr ₃0.1mol%, YbBr ₃3.7mol%.

3. LaBr rare earth ion doped as claimed in claim 1 ₃devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂20mol%, LaBr ₃16mol%, TmBr ₃0.3mol%, YbBr ₃3.7mol%.

4. LaBr rare earth ion doped as claimed in claim 1 ₃devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂82mol%, LaBr ₃12mol%, ErBr ₃0.5mol%, YbBr ₃5.5mol%.

5. LaBr 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 ₂80 ~ 95mol%, LaBr ₃4.6 ~ 16mol%, LnBr ₃0.4 ~ 6mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr 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% LaBr 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 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 8 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 ~ 650 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 LaBr ₃devitrified glass.