CN105314866A - Rare earth ion doped CaBr2 glass ceramic and preparation method thereof - Google Patents

Abstract

The invention discloses a rare earth ion doped CaBr2 glass ceramic comprising the following components in percentage by mole: 80-95mol% of SiO2, 4.7-16mol% of CaBr2 and 0.3-5mol% of LnBr3, wherein LnBr3 is at least one selected from YbBr3, ErBr3, TmBr3 and HoBr3. The rare earth ion doped CaBr2 glass ceramic has the advantages of good transparency, deliquescence resistance and mechanical property and relatively high hyacinthine transmittance, has the performances of low phonon energy, high up-conversion efficiency and the like and is capable of greatly increasing the efficiency of an up-conversion laser; and the glass ceramic is simple in preparation method of and relatively low in production cost.

Description

A kind of rare earth ion doped CaBr 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 CaBr 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.CaBr ₂crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped CaBr ₂crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but CaBr ₂the 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 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 CaBr of doping ₂devitrified glass is used for the open report of up-conversion luminescent material.

Summary of the invention

The rare earth ion doped CaBr 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 CaBr ₂devitrified glass, its molar percentage consists of: SiO ₂80 ~ 95mol%, CaBr ₂4.7 ~ 16mol%, LnBr ₃0.3 ~ 5mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂80mol%, CaBr ₂16mol%, TmBr ₃0.5mol%, YbBr ₃3.5mol%.

This devitrified glass molar percentage consists of: SiO ₂80mol%, CaBr ₂15mol%, ErBr ₃0.5mol%, YbBr ₃4.5mol%.

This devitrified glass molar percentage consists of: SiO ₂82mol%, CaBr ₂14mol%, ErBr ₃0.3mol%, TmBr ₃0.3mol%, YbBr ₃3.4mol%.

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

(1) by mole% composition SiO ₂80 ~ 95mol%, CaBr ₂4.7 ~ 16mol%, LnBr ₃0.3 ~ 5mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one; Take at least one in calcium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of calcium acetate is by mole% CaBr 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 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 640 ~ 670 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 CaBr ₂devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has CaBr 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 CaBr 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 CaBr 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 CaF 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 CaBr ₂the molar percentage of devitrified glass consists of: SiO ₂80mol%, CaBr ₂16mol%, TmBr ₃0.5mol%, YbBr ₃3.5mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take calcium acetate, acetic acid ytterbium, acetic acid thulium, and deal is respectively by the CaBr 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 140 DEG C of dryings 9 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 640 ~ 670 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 CaBr of doping ₂devitrified glass.

To the CaBr of preparation ₂devitrified 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 CaBr ₂the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is CaBr 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 5.63 × 10 of blue light (476nm) ⁵, blue up-conversion luminous very strong.

Embodiment 2

Er ³⁺, Yb ³⁺doping CaBr ₂the molar percentage of devitrified glass consists of: SiO ₂80mol%, CaBr 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 CaBr 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 CaBr ₂the molar percentage of devitrified glass consists of: SiO ₂82mol%, CaBr ₂14mol%, ErBr ₃0.3mol%, TmBr ₃0.3mol%, YbBr ₃3.4mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Tm ³⁺, Yb ³⁺the CaBr 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 CaBr ₂the molar percentage of devitrified glass consists of: SiO ₂95mol%, CaBr ₂4.7mol%, HoBr ₃: 0.3mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho ³⁺the CaBr 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 CaF ₂the molar percentage of devitrified glass consists of: SiO ₂80mol%, CaF ₂16mol%, TmF ₃0.5mol%, YbF ₃3.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the CaF 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 3.81 × 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 CaBr of doping ₂the Tm that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the CaF of doping ₂devitrified glass is better.

Claims (5)

1. a rare earth ion doped CaBr ₂devitrified glass, its molar percentage consists of: SiO ₂80 ~ 95mol%, CaBr ₂4.7 ~ 16mol%, LnBr ₃0.3 ~ 5mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one.

2. CaBr rare earth ion doped as claimed in claim 1 ₂devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂80mol%, CaBr ₂16mol%, TmBr ₃0.5mol%, YbBr ₃3.5mol%.

3. CaBr rare earth ion doped as claimed in claim 1 ₂devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂80mol%, CaBr ₂5mol%, ErBr ₃0.5mol%, YbBr ₃4.5mol%.

4. CaBr rare earth ion doped as claimed in claim 1 ₂devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂82mol%, CaBr ₂14mol%, ErBr ₃0.3mol%, TmBr ₃0.3mol%, YbBr ₃3.4mol%.

5. CaBr 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 ~ 95mol%, CaBr ₂4.7 ~ 16mol%, LnBr ₃0.3 ~ 5mol%, wherein LnBr ₃for YbBr ₃, ErBr ₃, TmBr ₃and HoBr ₃in at least one; Take at least one in calcium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of calcium acetate is by mole% CaBr 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 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 640 ~ 670 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 CaBr ₂devitrified glass.