CN105293923A - Rare earth ion doped K3GdCl6 glass ceramic and preparation method thereof - Google Patents

Abstract

The invention discloses rare earth ion doped K3GdCl6 glass ceramic which comprises the following elements by mole percent: 88-93mol% of SiO2, 6.5-9mol% of K3GdCl6 and 0.5-3mol% of LnCl3, wherein LnCl3 is at least one of YbCl3, ErCl3, TmCl3 and HoCl3. The rare earth ion doped K3GdCl6 glass ceramic has the advantages as follows: the prepared rare earth ion doped K3GdCl6 glass ceramic is transparent, deliquescence-proof, good in mechanical property and relatively high in blue-violet light transmittance, has the properties of low phonon energy, high up-conversion efficiency, and the like, and enables the efficiency of an up-conversion laser to be improved greatly, in addition, a preparation method for the glass ceramic is simple and the production cost is relatively low.

Description

A kind of rare earth ion doped K 3gdCl 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 K being used as up-conversion luminescent material ₃gdCl ₆devitrified 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.K ₃gdCl ₆crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped K ₃gdCl ₆crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but K ₃gdCl ₆the easy moisture absorption of crystal, need special processing and storage, be difficult to preparation, chemical stability and the disadvantages affect such as physical strength the is poor practical application of its up-conversion luminescence.

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 and exports; If publication number is CN103951239, name is called " rare earth ion doped Cs ₂liGdCl ₆devitrified glass and preparation method thereof " application for a patent for invention also disclose a kind of crystallite mutually for Cs ₂liGdCl ₆, glassy phase is P ₂o ₅with Nb ₂o ₅be 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 K of doping ₃gdCl ₆devitrified glass is used for openly reporting mutually of up-conversion luminescent material.

Summary of the invention

The rare earth ion doped K 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 ₃gdCl 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 K ₃gdCl ₆devitrified glass, its molar percentage consists of: SiO ₂88 ~ 93mol%, K ₃gdCl ₆6.5 ~ 9mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂89mol%, K ₃gdCl ₆8mol%, ErCl ₃0.5mol%, YbCl ₃2.5mol%.

This devitrified glass molar percentage consists of: SiO ₂89mol%, K ₃gdCl ₆9mol%, TmCl ₃0.3mol%, YbCl ₃1.7mol%.

This devitrified glass molar percentage consists of: SiO ₂88mol%, K ₃gdCl ₆9mol%, ErCl ₃0.1mol%, TmCl ₃0.1mol%, YbCl ₃2.8mol%.

Described rare earth ion doped K ₃gdCl ₆the preparation method of devitrified glass, comprises the following steps:

(1) by mole% composition SiO ₂88 ~ 93mol%, K ₃gdCl ₆6.5 ~ 9mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one; Take at least one in gadolinium acetate, Potassium ethanoate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of gadolinium acetate, Potassium ethanoate is respectively by mole% K in composition ₃gdCl ₆molar 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 3 weeks, is warming up to 149 DEG C of dryings 7 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 550 ~ 580 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 K ₃gdCl ₆devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has K ₃gdCl 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 K obtained by preparation method of the present invention ₃gdCl 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 X-ray diffraction (XRD) figure of the devitrified glass that embodiment 1 obtains;

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

Fig. 3 is the Er that comparative example 1 obtains ³⁺, Yb ³⁺the K of doping ₃gdF 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

Er ³⁺, Yb ³⁺doping K ₃gdCl ₆the molar percentage of devitrified glass consists of: SiO ₂89mol%, K ₃gdCl ₆8mol%, ErCl ₃0.5mol%, YbCl ₃2.5mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take gadolinium acetate, Potassium ethanoate, acetic acid ytterbium and acetic acid erbium, wherein the deal of gadolinium acetate, Potassium ethanoate is respectively by mole% K in composition ₃gdCl ₆molar content take, the deal of acetic acid ytterbium, acetic acid erbium is respectively by YbCl in above-mentioned identical molar percentage composition ₃, ErCl 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 3 weeks, is warming up to 149 DEG C of dryings 7 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 550 ~ 580 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 K of doping ₃gdCl ₆devitrified glass.

To obtained K ₃gdCl ₆devitrified 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 K ₃gdCl ₆the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is K ₃gdCl 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 green glow (551nm), green glow (548nm) and ruddiness (660nm) respectively about 2.17 × 10 ⁵, 8.97 × 10 ⁵, 1.71 × 10 ⁵, green and red up-conversion luminescence is very strong.

Embodiment 2

Tm ³⁺, Yb ³⁺doping K ₃gdCl ₆the molar percentage of devitrified glass consists of: SiO ₂89mol%, K ₃gdCl ₆9mol%, TmCl ₃0.3mol%, YbCl ₃1.7mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the K of doping ₃gdCl ₆devitrified 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 K ₃gdCl ₆the molar percentage of devitrified glass consists of: SiO ₂88mol%, K ₃gdCl ₆9mol%, 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 K of doping ₃gdCl 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.

Embodiment 4

Ho ³⁺doping K ₃gdCl ₆the molar percentage of devitrified glass consists of: SiO ₂93mol%, K ₃gdCl ₆6.5mol%, HoCl ₃0.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho ³⁺the K of doping ₃gdCl ₆devitrified 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 K ₃gdF ₆the molar percentage of devitrified glass consists of: SiO ₂89mol%, K ₃gdF ₆8mol%, ErF ₃0.5mol%, YbF ₃2.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Yb ³⁺the K of doping ₃gdF ₆devitrified 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 (524nm), green glow (546nm) and ruddiness (660nm) respectively about 2.87 × 10 ⁴, 5.97 × 10 ⁴, 1.23 × 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 K of doping ₃gdCl ₆the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the K of doping ₃gdF ₆devitrified glass is better.

Claims (5)

1. a rare earth ion doped K ₃gdCl ₆devitrified glass, its molar percentage consists of: SiO ₂88 ~ 93mol%, K ₃gdCl ₆6.5 ~ 9mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one.

2. K rare earth ion doped as claimed in claim 1 ₃gdCl ₆devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂89mol%, K ₃gdCl ₆8mol%, ErCl ₃0.5mol%, YbCl ₃2.5mol%.

3. K rare earth ion doped as claimed in claim 1 ₃gdCl ₆devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂89mol%, K ₃gdCl ₆9mol%, TmCl ₃0.3mol%, YbCl ₃1.7mol%.

4. K rare earth ion doped as claimed in claim 1 ₃gdCl ₆devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂88mol%, K ₃gdCl ₆9mol%, ErCl ₃0.1mol%, TmCl ₃0.1mol%, YbCl ₃2.8mol%.

5. K rare earth ion doped as claimed in claim 1 ₃gdCl ₆the preparation method of devitrified glass, is characterized in that comprising the following steps:

(1) by mole% composition SiO ₂88 ~ 93mol%, K ₃gdCl ₆6.5 ~ 9mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one; Take at least one in gadolinium acetate, Potassium ethanoate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of gadolinium acetate, Potassium ethanoate is respectively by mole% K in composition ₃gdCl ₆molar 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 3 weeks, is warming up to 149 DEG C of dryings 7 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 550 ~ 580 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 K ₃gdCl ₆devitrified glass.