CN105293928A - Rear earth ion-doped K2GdCl5 microcrystalline glass and preparation method thereof - Google Patents

Abstract

The invention discloses rear earth ion-doped K2GdCl5 microcrystalline glass, which is prepared from the following components in mole percent: 87 to 94 mole percent of SiO2, 5.5 to 10 mole percent of K2GdCl5 and 0.5 to 3 mole percent of LnCl3, wherein the LnCl3 is at least one of YbCl3, ErCl3 and TmCl3. The prepared rear earth ion-doped K2GdCl5 microcrystalline glass has the advantages of transparence, anti-deliquescence, good mechanical property and relatively high hyacinthine light transmittance, and has the properties of low photon energy, high up-conversion efficiency and the like, so that the efficiency of an up-conversion laser can be greatly improved, and a preparation method of the microcrystalline glass is simple, and the production cost is relatively low.

Description

A kind of rare earth ion doped K 2gdCl 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 K being used as up-conversion luminescent material ₂gdCl ₅devitrified 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.K ₂gdCl ₅crystal has the phonon energy lower than fluorochemical, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped K ₂gdCl ₅crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but K ₂gdCl ₅the 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.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 CN103951205, name is called " rare earth ion doped SrGdCl ₅devitrified glass and preparation method thereof " application for a patent for invention also disclose a kind of crystallite mutually for SrGdCl ₅, glassy phase is P ₂o ₅be main devitrified glass, the rare earth ion of doping is Ce ³⁺, Eu ³⁺and Tb 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⁺the K of doping ₂gdCl ₅devitrified glass is used for the open report 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 ₂gdCl 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 K ₂gdCl ₅devitrified glass, its molar percentage is composed as follows: SiO ₂87 ~ 94mol%, K ₂gdCl ₅5.5 ~ 10mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂89mol%, K ₂gdCl ₅9mol%, TmCl ₃0.5mol%, YbCl ₃1.5mol%.

This devitrified glass molar percentage consists of: SiO ₂94mol%, K ₂gdCl ₅5.5mol%, ErCl ₃0.5mol%.

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

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

(1) by mole% composition SiO ₂87 ~ 94mol%, K ₂gdCl ₅5.5 ~ 10mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃in at least one; Take at least one in gadolinium acetate, Potassium ethanoate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium, wherein the deal of gadolinium acetate, Potassium ethanoate is respectively by mole% K in composition ₂gdCl ₅molar content take, the deal of acetic acid ytterbium, acetic acid erbium and at least one in acetic acid thulium 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 137 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 560 ~ 590 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 ₂gdCl ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has K ₂gdCl 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 K obtained by preparation method of the present invention ₂gdCl 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 K of doping ₂gdCl 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 K of doping ₂gdF 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 K ₂gdCl ₅the molar percentage of devitrified glass consists of: SiO ₂89mol%, K ₂gdCl ₅9mol%, TmCl ₃0.5mol%, YbCl ₃1.5mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take gadolinium acetate, Potassium ethanoate, acetic acid ytterbium and acetic acid thulium, wherein the deal of gadolinium acetate, Potassium ethanoate is respectively by mole% K in composition ₂gdCl 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 3 weeks, is warming up to 137 DEG C of dryings 9 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 560 ~ 590 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 K of doping ₂gdCl ₅devitrified glass.

To obtained K ₂gdCl 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 K ₂gdCl ₅phase, the material therefore obtained is K ₂gdCl 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 5.23 × 10 ⁵, 8.61 × 10 ⁵, blue and red up-conversion luminescence is very strong.

Embodiment 2

Er ³⁺doping K ₂gdCl ₅the molar percentage of devitrified glass consists of: SiO ₂94mol%, K ₂gdCl ₅5.5mol%, ErCl ₃0.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺the K of doping ₂gdCl ₅devitrified 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 K ₂gdCl ₅the molar percentage of devitrified glass consists of: SiO ₂87mol%, K ₂gdCl 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 K of doping ₂gdCl 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.

Comparative example 1

Tm ³⁺, Yb ³⁺doping K ₂gdF ₅the molar percentage of devitrified glass consists of: SiO ₂: 89mol%, K ₂gdF ₅: 9mol%, TmF ₃: 0.5mol%, YbF ₃: 1.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the K of doping ₂gdF ₅devitrified 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 3.74 × 10 ⁴, 6.02 × 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 K of doping ₂gdCl ₅the Tm that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the K of doping ₂gdF ₅devitrified glass is better.

Claims (5)

1. a rare earth ion doped devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, K ₂gdCl ₅5.5 ~ 10mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃in at least one.

2. K rare earth ion doped as claimed in claim 1 ₂gdCl ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂89mol%, K ₂gdCl ₅9mol%, TmCl ₃0.5mol%, YbCl ₃1.5mol%.

3. K rare earth ion doped as claimed in claim 1 ₂gdCl ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂94mol%, K ₂gdCl ₅5.5mol%, ErCl ₃0.5mol%.

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

5. K rare earth ion doped as claimed in claim 1 ₂gdCl ₅the preparation method of devitrified glass, is characterized in that comprising the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, K ₂gdCl ₅5.5 ~ 10mol%, LnCl ₃0.5 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃in at least one; Take at least one in gadolinium acetate, Potassium ethanoate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium, wherein the deal of gadolinium acetate, Potassium ethanoate is respectively by mole% K in composition ₂gdCl ₅molar content take, the deal of acetic acid ytterbium, acetic acid erbium and at least one in acetic acid thulium 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 137 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 560 ~ 590 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 ₂gdCl ₅devitrified glass.