CN105254183A - K2CeI5 glass ceramics doped with rare earth ions and preparation method of K2CeI5 glass ceramics - Google Patents

Abstract

The invention discloses K2CeI5 glass ceramics doped with rare earth ions. The K2CeI5 glass ceramics is prepared from 87-92 mol% of SiO2, 7.5-10 mol% of K2CeI5 and 0.5-3 mol% of LnI3, wherein LnI3 is at least one of YbI3, ErI3 and TmI3. The K2CeI5 glass ceramics has the advantages of being transparent, resistant to air slake, good in mechanical performance, high in blue and purple light transmittance, low in phonon energy, high in up-conversion efficiency, capable of greatly improving efficiency of an up-conversion laser device, simple in preparation method and low in production cost.

Description

A kind of rare earth ion doped K 2ceI 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 ₂ceI 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 ₂ceI 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 ₂ceI ₅crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but K ₂ceI ₅the easy moisture absorption of crystal, need special processing and storage, be difficult to preparation, the practical application of its up-conversion luminescence of chemical stability and 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 iodide 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 CN103951219, name is called " rare earth ion doped K ₂laI ₅devitrified glass and preparation method thereof " application for a patent for invention disclose a kind of crystallite mutually for K ₂laI ₅, glassy phase is TeO ₂with Nb ₂o ₅be 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⁺the K of doping ₂ceI 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 ₂ceI 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 ₂ceI ₅devitrified glass, its molar percentage is composed as follows: SiO ₂87 ~ 92mol%, K ₂ceI ₅7.5 ~ 10mol%, LnI ₃0.5 ~ 3mol%, wherein LnI ₃for YbI ₃, ErI ₃and TmI ₃in at least one.

This devitrified glass molar percentage consists of: SiO ₂87mol, K ₂ceI ₅10mol%, ErI ₃0.1mol%, TmI ₃0.1mol%, YbI ₃2.8mol%.

This devitrified glass molar percentage consists of: SiO ₂88.5mol%, K ₂ceI ₅9mol%, TmI ₃0.5mol%, YbI ₃2mol%.

This devitrified glass molar percentage consists of: SiO ₂92mol%, K ₂ceI ₅7.5mol%, ErI ₃0.5mol%.

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

(1) by mole% composition SiO ₂87 ~ 92mol%, K ₂ceI ₅7.5 ~ 10mol%, LnI ₃0.5 ~ 3mol%, wherein LnI ₃for YbI ₃, ErI ₃and TmI ₃in at least one; Take at least one in cerous acetate, Potassium ethanoate and acetic acid ytterbium, acetic acid erbium and acetic acid thulium, wherein the deal of cerous acetate and Potassium ethanoate is respectively by mole% K in composition ₂ceI ₅molar content take, the deal of acetic acid ytterbium, acetic acid erbium and at least one in acetic acid thulium is respectively by LnI 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 triiodoacetic acid obtain transparent mixing solutions, wherein in triiodoacetic 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 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 K ₂ceI ₅devitrified glass.

Compared with prior art, the invention has the advantages that: this devitrified glass has K ₂ceI 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 ₂ceI 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; 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 the transmission electron microscope figure (TEM) of the devitrified glass that embodiment 1 obtains;

Fig. 2 is the Er that embodiment 1 obtains ³⁺, Tm ³⁺, Yb ³⁺the K of doping ₂ceI ₅the 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 K of doping ₂ceF ₅the 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 K ₂ceI ₅the molar percentage of devitrified glass consists of: SiO ₂87mol, K ₂ceI ₅10mol%, ErI ₃0.1mol%, TmI ₃0.1mol%, YbI ₃2.8mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take cerous acetate, Potassium ethanoate, acetic acid ytterbium, acetic acid erbium and acetic acid thulium, wherein the deal of cerous acetate and Potassium ethanoate is respectively by mole% K in composition ₂ceI ₅molar content take, the deal of acetic acid ytterbium, acetic acid erbium and acetic acid thulium is respectively by YbI in above-mentioned identical molar percentage composition ₃, ErI ₃, TmI ₃molar content take, be dissolved in deionized water by above-mentioned acetate and form Acetate Solution, add triiodoacetic acid and obtain transparent mixing solutions in Acetate Solution, wherein in triiodoacetic 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, 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 Er ³⁺, Tm ³⁺, Yb ³⁺the K of doping ₂ceI ₅devitrified glass.

To obtained K ₂ceI 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 ₂ceI ₅phase, the material therefore obtained is K ₂ceI 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), green glow (533nm), green glow (546nm) and ruddiness (653nm) respectively about 4.82 × 10 ⁵, 8.23 × 10 ⁵, 4.12 × 10 ⁵, 4.28 × 10 ⁵, blueness, green and red up-conversion luminescence are very strong.

Embodiment 2

Tm ³⁺, Yb ³⁺doping K ₂ceI ₅the molar percentage of devitrified glass consists of: SiO ₂88.5mol%, K ₂ceI ₅9mol%, TmI ₃0.5mol%, YbI ₃2mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Tm ³⁺, Yb ³⁺the K of doping ₂ceI ₅devitrified 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⁺doping K ₂ceI ₅the molar percentage of devitrified glass consists of: SiO ₂92mol%, K ₂ceI ₅7.5mol%, ErI ₃0.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺the K of doping ₂ceI 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.

Comparative example 1

Er ³⁺, Tm ³⁺, Yb ³⁺doping K ₂ceF ₅the molar percentage of devitrified glass consists of: SiO ₂87mol%, K ₂ceF ₅10mol%, ErF ₃0.1mol%, TmF ₃0.1mol%, YbF 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 ₂ceF 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), green glow (533nm), green glow (546nm) and ruddiness (653nm) respectively about 4.18 × 10 ⁴, 7.15 × 10 ⁴, 3.56 × 10 ⁴, 3.72 × 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 K of doping ₂ceI ₅the Er that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Tm ³⁺, Yb ³⁺the K of doping ₂ceF ₅devitrified glass is better.

Claims (5)

1. a rare earth ion doped K ₂ceI ₅devitrified glass, its molar percentage consists of: SiO ₂87 ~ 92mol%, K ₂ceI ₅7.5 ~ 10mol%, LnI ₃0.5 ~ 3mol%, wherein LnI ₃for YbI ₃, ErI ₃and TmI ₃in at least one.

2. K rare earth ion doped as claimed in claim 1 ₂ceI ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂87mol, K ₂ceI ₅10mol%, ErI ₃0.1mol%, TmI ₃0.1mol%, YbI ₃2.8mol%.

3. K rare earth ion doped as claimed in claim 1 ₂ceI ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂88.5mol%, K ₂ceI ₅9mol%, TmI ₃0.5mol%, YbI ₃2mol%.

4. K rare earth ion doped as claimed in claim 1 ₂ceI ₅devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂92mol%, K ₂ceI ₅7.5mol%, ErI ₃0.5mol%.

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

(1) by mole% composition SiO ₂87 ~ 92mol%, K ₂ceI ₅7.5 ~ 10mol%, LnI ₃0.5 ~ 3mol%, wherein LnI ₃for YbI ₃, ErI ₃and TmI ₃in at least one; Take at least one in cerous acetate, Potassium ethanoate and acetic acid ytterbium, acetic acid erbium and acetic acid thulium, wherein the deal of cerous acetate and Potassium ethanoate is respectively by mole% K in composition ₂ceI ₅molar content take, the deal of acetic acid ytterbium, acetic acid erbium and at least one in acetic acid thulium is respectively by LnI 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 triiodoacetic acid obtain transparent mixing solutions, wherein in triiodoacetic 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 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 K ₂ceI ₅devitrified glass.