CN105271776A - Rare-earth-ion-doped Cs2LuCl5 microcrystalline glass and preparation method thereof - Google Patents

Abstract

The invention discloses rare-earth-ion-doped Cs2LuCl5 microcrystalline glass. The rare-earth-ion-doped Cs2LuCl5 microcrystalline glass comprises the following components in mole percentage: 87-94mol% of SiO2, 5.4-10mol% of Cs2LuCl5 and 0.6-3mol% of LnCl3, wherein LnCl3 is at least one of YbCl3, ErCl3, TmCl3 and HoCl3. The obtained rare-earth-ion-doped Cs2LuCl5 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 Cs2LuCl5 microcrystalline glass is simple and low in production cost.

Description

A kind of rare earth ion doped Cs 2luCl 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 Cs being used as up-conversion luminescent material ₂luCl 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.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.Cs ₂luCl ₅crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped Cs ₂luCl ₅crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but Cs ₂luCl 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.Chloride current transparent glass-ceramics is mainly used as flashing and up-conversion luminescent material, and if publication number is CN103382089, name is called " containing Cs ₃laCl ₆nanocrystalline transparent sulfur-halogen glass pottery and preparation thereof " application for a patent for invention disclose doping Nd ³⁺or Er ³⁺ion, with Cs ₃laCl ₆for crystallite phase, glassy phase are the devitrified glass of sulfide, but the physical and chemical performance of sulfide is poorer than oxide compound, and not saturating in visible ray shortwave strong point, have impact on up-conversion luminescence efficiency; As publication number be CN103951229, name is called " rare earth ion doped Sr ₂luCl ₇devitrified glass and preparation method thereof " application for a patent for invention also disclose a kind of crystallite mutually for Sr ₂luCl ₇, glassy phase is P ₂o ₅with SiO ₂be main devitrified glass, the rare earth ion of doping is Ce ³⁺, Eu ³⁺, Tb ³⁺, Pr ³⁺and Nd ³⁺in one, adopt melt supercooled method and subsequent heat treatment preparation, there is good scintillation properties, as flash luminous material.But also there is no trivalent rare earth ions Yb at present ³⁺, Er ³⁺, Tm ³⁺and Ho ³⁺the Cs of doping ₂luCl ₅devitrified glass is used for the open report of up-conversion luminescent material.

Summary of the invention

The rare earth ion doped Cs 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 ₂luCl 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 Cs ₂luCl ₅devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, Cs ₂luCl ₅5.4 ~ 10mol%, LnCl ₃0.6 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂90mol%, Cs ₂luCl ₅8mol%, TmCl ₃0.5mol%, YbCl ₃1.5mol%.

This devitrified glass molar percentage consists of: SiO ₂88.5mol%, Cs ₂luCl ₅9mol%, ErCl ₃0.5mol%, YbCl ₃2mol%.

This devitrified glass molar percentage consists of: SiO ₂87mol%, Cs ₂luCl ₅10mol%, ErCl ₃0.1mol%, TmCl ₃0.1mol%, YbCl ₃2.8mol%.

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

(1) by mole% composition SiO ₂87 ~ 94mol%, Cs ₂luCl ₅5.4 ~ 10mol%, LnCl ₃0.6 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one; Take at least one in acetic acid lutetium, cesium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of vinegar acetic acid lutetium, cesium acetate is respectively by mole% Cs in composition ₂luCl 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 LnCl 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 trichoroacetic acid(TCA) obtain transparent mixing solutions, wherein in trichoroacetic acid(TCA) 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 2 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 600 ~ 630 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 Cs ₂luCl ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has Cs ₂luCl 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 Cs obtained by preparation method of the present invention ₂luCl 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 Tm that embodiment 1 obtains ³⁺, Yb ³⁺the Cs of doping ₂luCl ₅the 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 Cs of doping ₂luF ₅the 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 Cs ₂luCl ₅the molar percentage of devitrified glass consists of: SiO ₂90mol%, Cs ₂luCl ₅8mol%, TmCl ₃0.5mol%, YbCl ₃1.5mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take acetic acid lutetium, cesium acetate, acetic acid ytterbium and acetic acid thulium, wherein the deal of acetic acid lutetium, cesium acetate is respectively by mole% Cs in composition ₂luCl ₅molar content take, the deal of acetic acid ytterbium, acetic acid thulium is respectively by YbCl in above-mentioned identical molar percentage composition ₃, TmCl ₃molar content take, be dissolved in deionized water by above-mentioned acetate and form Acetate Solution, add trichoroacetic acid(TCA) and obtain transparent mixing solutions in Acetate Solution, wherein in trichoroacetic acid(TCA) 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 2 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, 600 ~ 630 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 Cs of doping ₂luCl ₅devitrified glass.

To obtained Cs ₂luCl 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 Cs ₂luCl ₅phase, the material therefore obtained is Cs ₂luCl 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 blue light (476nm) and ruddiness (679nm) respectively about 5.72 × 10 ⁵, 9.43 × 10 ⁵, blue and red up-conversion luminescence is very strong.

Embodiment 2

Er ³⁺, Yb ³⁺doping Cs ₂luCl ₅the molar percentage of devitrified glass consists of: SiO ₂88.5mol%, Cs ₂luCl ₅9mol%, ErCl ₃0.5mol%, YbCl ₃2mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Yb ³⁺the Cs of doping ₂luCl ₅devitrified 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 Cs ₂luCl ₅the molar percentage of devitrified glass consists of: SiO ₂87mol%, Cs ₂luCl ₅10mol%, ErCl ₃0.1mol%, TmCl ₃0.1mol%, YbCl 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 Cs of doping ₂luCl 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 Cs ₂luCl ₅the molar percentage of devitrified glass consists of: SiO ₂94mol%, Cs ₂luCl ₅5.4mol%, HoCl ₃0.6mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho ³⁺the Cs of doping ₂luCl 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

Tm ³⁺, Yb ³⁺doping Cs ₂luF ₅the molar percentage of devitrified glass consists of: SiO ₂90mol%, Cs ₂luF ₅8mol%, 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 Cs of doping ₂luF 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 blue light (476nm) and ruddiness (679nm) respectively about 4.53 × 10 ⁴, 7.56 × 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 Cs of doping ₂luCl ₅the Tm that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the Cs of doping ₂luF ₅devitrified glass is better.

Claims (5)

1. a rare earth ion doped Cs ₂luCl ₅devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, Cs ₂luCl ₅5.4 ~ 10mol%, LnCl ₃0.6 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one.

2. rare earth ion doped Cs according to claim 1 ₂luCl ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂90mol%, Cs ₂luCl ₅8mol%, TmCl ₃0.5mol%, YbCl ₃1.5mol%.

3. rare earth ion doped Cs according to claim 1 ₂luCl ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂88.5mol%, Cs ₂luCl ₅9mol%, ErCl ₃0.5mol%, YbCl ₃2mol%.

4. rare earth ion doped Cs according to claim 1 ₂luCl ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂87mol%, Cs ₂luCl ₅10mol%, ErCl ₃0.1mol%, TmCl ₃0.1mol%, YbCl ₃2.8mol%.

5. rare earth ion doped Cs according to claim 1 ₂luCl ₅the preparation method of devitrified glass, is characterized in that comprising the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, Cs ₂luCl ₅5.4 ~ 10mol%, LnCl ₃0.6 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one; Take at least one in acetic acid lutetium, cesium acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of vinegar acetic acid lutetium, cesium acetate is respectively by mole% Cs in composition ₂luCl 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 LnCl 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 trichoroacetic acid(TCA) obtain transparent mixing solutions, wherein in trichoroacetic acid(TCA) 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 2 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 600 ~ 630 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 Cs ₂luCl ₅devitrified glass.