CN105314872A - Rare earth ion doped CeI3 glass ceramics and preparation method thereof - Google Patents

Abstract

The invention discloses rare earth ion doped CeI3 glass ceramics. The CeI3 glass ceramics comprise 80-94mol% of SiO2, 5.5-15mol% of CeI3 and 0.5-5mol% of LnI3, wherein LnI3 is at least one of YbI3, ErI3, TmI3 and HoI3. The rare earth ion doped CeI3 glass ceramics and the preparation method have the advantages that the prepared rare earth ion doped CeI3 glass ceramics are transparent, are resistant to deliquescence, have good mechanical properties and higher blue and violet light transmittance, have the properties, such as low phonon energy and high upconversion efficiency, and have the effect of greatly improving the efficiency of upconversion lasers; a preparation method of the glass ceramics is simple and is low in production cost.

Description

A kind of rare earth ion doped CeI 3devitrified 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 CeI being used as up-conversion luminescent material ₃devitrified 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.CeI ₃the lattice phonon energy Ratios fluorochemical of crystal is lower, is more suitable for as rear-earth-doped up-conversion luminescence matrix, rare earth ion doped CeI ₃crystal has the upper efficiency of conversion higher than rare earth ion doped crystal of fluoride, but CeI ₃crystal easily absorbs water, need special processing and storage and be difficult to its practical application of the disadvantages affect such as preparation, chemical stability and physical strength be 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, if publication number is CN103951209, and name is called " rare earth ion doped LaI ₃devitrified glass and preparation method thereof " application for a patent for invention disclose a kind of crystallite mutually for LaI ₃, glassy phase is GeO ₂be main devitrified glass, the rare earth ion of doping is Ce ³⁺, Eu ³⁺, Tb ³⁺, Pr ³⁺and Nd ³⁺, adopt melt supercooled method and subsequent heat treatment preparation, there is good scintillation properties.But at present also not about trivalent rare earth ions Yb ³⁺, Er ³⁺, Tm ³⁺and Ho ³⁺the CeI of doping ₃devitrified glass is used for the open report of up-conversion luminescent material.

Summary of the invention

The rare earth ion doped CeI 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 ₃devitrified 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 CeI ₃devitrified glass, its molar percentage consists of: SiO ₂80 ~ 94mol%, CeI ₃5.5 ~ 15mol%, LnI ₃0.5 ~ 5mol%, wherein LnI ₃for YbI ₃, ErI ₃, TmI ₃and HoI ₃in at least one.

This molar percentage is composed as follows: SiO ₂80.5mol%, CeI ₃15mol%, TmI ₃0.5mol%, YbI ₃4mol%.

This molar percentage is composed as follows: SiO ₂80mol%, CeI ₃15mol%, ErI ₃0.5mol%, YbI ₃4.5mol%.

This molar percentage is composed as follows: SiO ₂85mol%, CeI ₃12mol%, ErI ₃0.1mol%, TmI ₃0.1mol%, YbI ₃2.8mol%.

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

(1) by mole% composition SiO ₂80 ~ 94mol%, CeI ₃5.5 ~ 15mol%, LnI ₃0.5 ~ 5mol%, wherein LnI ₃for YbI ₃, ErI ₃, TmI ₃and HoI ₃in at least one; Take at least one in cerous acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of cerous acetate is by mole% CeI in composition ₃molar 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 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 2 weeks, is warming up to 150 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 610 ~ 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 CeI ₃devitrified glass.

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

Fig. 2 is the Tm that embodiment 1 obtains ³⁺, Yb ³⁺the CeI of doping ₃the 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 CeF of doping ₃the 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⁺doped Ce I ₃the molar percentage of devitrified glass consists of: SiO ₂80.5mol%, CeI ₃15mol%, TmI ₃0.5mol%, YbI ₃4mol%, the technique preparing devitrified glass of above composition is as follows:

(1) take cerous acetate, acetic acid thulium, acetic acid ytterbium, and deal is respectively by the CeI in above-mentioned molar percentage composition ₃, ErI ₃, YbI 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 2 weeks, is warming up to 150 DEG C of dryings 8 days, obtains transparent xerogel;

(4) xerogel that step (3) obtains is placed in nitrogen fine annealing stove, 610 ~ 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 CeI of doping ₃devitrified glass.

To the CeI of preparation ₃devitrified 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 CeI ₃the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and the material therefore obtained is CeI ₃the 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 7.27 × 10 of blue light (476nm) ⁵, blue up-conversion luminous very strong.

Embodiment 2

Er ³⁺, Yb ³⁺doped Ce I ₃the molar percentage of devitrified glass consists of: SiO ₂80mol%, CeI ₃15mol%, ErI ₃0.5mol%, YbI ₃4.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Yb ³⁺the CeI of doping ₃devitrified 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⁺doped Ce I ₃the molar percentage of devitrified glass consists of: SiO ₂85mol%, CeI ₃12mol%, ErI ₃0.1mol%, TmI ₃0.1mol%, YbI 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 CeI of doping ₃devitrified 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⁺doped Ce I ₃the molar percentage of devitrified glass consists of: SiO ₂: 94mol%, CeI ₃: 5.5mol%, HoI ₃: 0.5mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Ho ³⁺the CeI of doping ₃devitrified glass.This devitrified glass TRIAX550 fluorescence spectrophotometer is measured, under 970nm laser apparatus shooting conditions, observes strong green and red up-conversion luminescence.

Comparative example 1

Tm ³⁺, Yb ³⁺doped Ce F ₃the molar percentage of devitrified glass consists of: SiO ₂80.5mol%, CeF ₃15mol%, TmF ₃0.5mol%, YbF ₃4mol%, after the preparation identical with embodiment 1 and heat treatment process, obtains transparent rare earth ion Er ³⁺, Yb ³⁺doped Ce F ₃devitrified 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 6.34 × 10 of blue light (476nm) ⁴, compare with embodiment 1, blue up-conversion luminous intensity is low, and the Tm that embodiment 1 obtains is described ³⁺, Yb ³⁺the CeI of doping ₃the Tm that the up-conversion luminescence performance test ratio 1 of devitrified glass obtains ³⁺, Yb ³⁺the CeF of doping ₃devitrified glass is better.

Claims (5)

1. a rare earth ion doped CeI ₃devitrified glass, its molar percentage consists of: SiO ₂80 ~ 94mol%, CeI ₃5.5 ~ 15mol%, LnI ₃0.5 ~ 5mol%, wherein LnI ₃for YbI ₃, ErI ₃, TmI ₃and HoI ₃in at least one.

2. CeI rare earth ion doped as claimed in claim 1 ₃devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂80.5mol%, CeI ₃15mol%, TmI ₃0.5mol%, YbI ₃4mol%.

3. CeI rare earth ion doped as claimed in claim 1 ₃devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂80mol%, CeI ₃15mol%, ErI ₃0.5mol%, YbI ₃4.5mol%.

4. CeI rare earth ion doped as claimed in claim 1 ₃devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂85mol%, CeI ₃12mol%, ErI ₃0.1mol%, TmI ₃0.1mol%, YbI ₃2.8mol%.

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

(1) by mole% composition SiO ₂80 ~ 94mol%, CeI ₃5.5 ~ 15mol%, LnI ₃0.5 ~ 5mol%, wherein LnI ₃for YbI ₃, ErI ₃, TmI ₃and HoI ₃in at least one; Take at least one in cerous acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of cerous acetate is by mole% CeI in composition ₃molar 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 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 2 weeks, is warming up to 150 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 610 ~ 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 CeI ₃devitrified glass.