CN105271774A - A kind of NaLuCl4 glass ceramics doped with rare earth ions and preparation method thereof - Google Patents

Abstract

The invention discloses rare-earth ion doped NaLuCl4 microcrystalline glass comprising the following components in mole percentage: 87-94mol% of SiO2, 5.3-10mol% of NaLuCl4 and 0.7-3mol% of LnCl3, wherein the LnCl3 is at least one of YbCl3, ErCl3, TmCl3 and HoCl3. The rare-earth ion doped NaLuCl4 microcrystalline glass disclosed by the invention has the advantages of being transparent and deliquescence-resistant, good in mechanical property and relatively high in blue-violet light transmission, having the performances of low phonon energy, high up-conversion efficiency and the like, and being capable of greatly improving the efficiency of an up-conversion laser; moreover, the preparation method of the microcrystalline glass is simple, and is relatively low in production cost.

Description

A kind of NaLuCl4 glass ceramics doped with rare earth ions and preparation method thereof

technical field

The invention relates to a rare earth ion-doped glass-ceramic, in particular to a rare-earth ion-doped _NaLuCl4 glass-ceramic used as an up-conversion luminescent material and a preparation method thereof.

Background technique

The up-conversion luminescence of rare earth ions refers to the phenomenon that when a sample doped with rare earth ions is irradiated with excitation light with a longer wavelength, light with a wavelength shorter than that of the excitation light is emitted. Utilizing the up-conversion properties of rare earth ions, an inexpensive fiber laser that can work at room temperature and continuously output violet-blue-green light can be obtained. Violet-blue-green up-conversion lasers can be used in various fields such as color displays, data storage, information technology, laser printing, and medical treatment. To improve the efficiency of upconversion luminescence, it is necessary to reduce the phonon energy of the host material, mainly because the lower phonon energy can reduce the probability of non-radiative relaxation, improve the fluorescence lifetime of the metastable state energy level in the middle of rare earth ions, and can Effectively improve the efficiency of up-conversion luminescence. NaLuCl ₄ crystal has lower phonon energy than fluoride, which is more suitable as a rare earth doped up-conversion luminescent host, and rare earth ion-doped NaLuCl ₄ crystal has higher up-conversion efficiency than rare earth ion-doped fluoride crystal , but NaLuCl ₄ crystals are easy to absorb moisture, require special handling and storage, are difficult to prepare, and have poor chemical stability and mechanical strength, which affect the practical application of up-conversion luminescent materials.

Transparent glass-ceramics is a new type of optoelectronic material that combines the advantages of both crystal and glass. At present, chloride transparent glass-ceramic is mainly used as scintillation and up-conversion luminescent material. For example, the publication number is CN103382089, and the invention patent application titled "transparent sulfur halide glass ceramics containing Cs ₃ LaCl ₆ nanocrystals and its preparation" has been published Glass-ceramics doped with Nd ³⁺ or Er ³⁺ ions, with Cs ₃ LaCl ₆ as the microcrystalline phase and the glass phase as sulfide, but the physical and chemical properties of sulfide are worse than those of oxides, and they are opaque at short wavelengths of visible light , which affects the up-conversion luminescence output; for example, the invention patent application with the publication number CN103951256 and the name "LiLuCl ₄ glass ceramics doped with rare earth ions and its preparation method" also discloses a microcrystalline phase LiLuCl ₄ , the glass phase is SiO ₂ and B ₂ O ₃ based glass-ceramics, doped rare earth ions are one of Ce ³⁺ , Eu ³⁺ , Tb ³⁺ , Pr ³⁺ , Nd ³⁺ and Dy ³⁺ . It is prepared by body quenching method and subsequent heat treatment. It has good scintillation performance and is used as a scintillation luminescent material. However, there is no public report on NaLuCl ₄ glass-ceramics doped with trivalent rare earth ions Yb ³⁺ , Er ³⁺ , Tm ³⁺ and Ho ³⁺ as up-conversion luminescent materials.

Contents of the invention

The technical problem to be solved by the present invention is to provide a rare earth ion-doped _NaLuCl4 glass-ceramic with low phonon energy, low probability of non-radiative transition, high up-conversion quantum efficiency, deliquescence resistance, good mechanical properties, and strong up-conversion luminescence and its preparation method.

The technical scheme adopted by the present invention to solve the above-mentioned technical problems is: a rare earth ion-doped NaLuCl ₄ glass-ceramics, the molar percentage composition of which is as follows: SiO ₂ 87-94 mol%, NaLuCl ₄ 5.3-10 mol%, LnCl ₃ 0.7- 3mol%, wherein LnCl ₃ is at least one of YbCl _{3 , ErCl 3 ,} TmCl ₃ and HoCl ₃ .

The molar percentage composition of the glass-ceramic is: SiO ₂ 91 mol%, NaLuCl ₄ 7 mol%, ErCl ₃ 0.5 mol%, YbCl ₃ 1.5 mol%.

The molar percentage composition of the glass-ceramic is: SiO ₂ 89.5 mol%, NaLuCl ₄ 8 mol%, TmCl ₃ 0.5 mol%, YbCl ₃ 2 mol%.

The molar percentage composition of the glass-ceramic is: SiO ₂ 87 mol%, NaLuCl ₄ 10 mol%, ErCl ₃ 0.2 mol%, TmCl ₃ 0.1 mol%, YbCl ₃ 2.7 mol%.

The preparation method of described rare earth ion-doped _NaLuCl4 glass-ceramic, comprises the following steps:

(1) SiO ₂ 87-94mol%, NaLuCl ₄ 5.3-10mol%, LnCl ₃ 0.7-3mol% by mole percentage, wherein LnCl ₃ is at least one of YbCl _{3 , ErCl 3 ,} TmCl ₃ and HoCl ₃ ; Take at least one of lutetium acetate, sodium acetate and ytterbium acetate, erbium acetate, thulium acetate and holmium acetate, wherein the parts of lutetium acetate and sodium acetate are weighed according to the molar percentage of _NaLuCl in the molar percentage composition, and ytterbium acetate , erbium acetate, thulium acetate and holmium acetate are weighed according to the molar percentage of _LnCl3 in the above-mentioned same molar percentage composition, and the above-mentioned acetate is dissolved in deionized water to form acetate solution, adding trichloroacetic acid in the acetate solution to obtain a transparent mixed solution, wherein the molar ratio of trichloroacetic acid to the sum of the metal ions in the acetate solution is 3:1;

( ₂ ) by weighing SiO in the same molar percentage composition as step (1) The molar percentage content is taken tetraethyl orthosilicate and is dissolved in ethanol, obtains tetraethyl orthosilicate solution, then step (1) is prepared The mixed solution was mixed with tetraethyl orthosilicate solution and stirred for 1 hour, and then adjusted to pH 5 with dilute nitric acid to obtain a precursor solution;

(3) Aging the precursor solution obtained in step (2) at room temperature for 2 weeks, then placing it in an oven, raising the temperature to 150°C and drying it for 7 days to obtain a transparent xerogel;

(4) Place the xerogel obtained in step (3) in a nitrogen precision annealing furnace, heat-treat at a temperature of 590-620°C for 10 hours, then cool down to 50°C at a rate of 10°C/hour, and turn off the precision annealing furnace. Furnace power supply, automatic cooling to room temperature, to obtain transparent rare earth ion doped NaLuCl ₄ glass-ceramics.

Compared with the prior art, the present invention has the advantages that: the glass-ceramic has the excellent up-conversion performance of _NaLuCl crystal matrix material and the characteristics of mechanical strength, stability and easy processing of silica glass; it is proved by experiments that: The rare earth ion-doped NaLuCl ₄ glass-ceramic prepared by the preparation method of the present invention is transparent, deliquescence-resistant, good in mechanical properties, high in blue-violet light transmittance, low in phonon energy, high in upconversion efficiency, etc. The conversion laser efficiency is greatly improved; in addition, the preparation method of the glass-ceramics is simple and has good repeatability, and the production cost is low.

Description of drawings

Fig. 1 is the X-ray diffraction (XRD) figure of the crystallized glass that embodiment 1 obtains;

Fig. 2 is the 970nm laser excitation up-conversion luminescent spectrum of the _NaLuCl4 glass-ceramic of Er3 ⁺ , Yb3 ⁺ doping that embodiment 1 obtains;

3 is the 970nm laser excitation upconversion luminescence spectrum of the Er ³⁺ , Yb ³⁺ doped NaLuF ₄ glass ceramics obtained in Comparative Example 1.

detailed description

The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

Example 1

The mole percentage composition of Er ³⁺ and Yb ³⁺ doped NaLuCl ₄ glass-ceramic is: SiO ₂ 91mol%, NaLuCl ₄ 7mol%, ErCl ₃ 0.5mol%, YbCl ₃ 1.5mol%. The process of crystal glass material is as follows:

(1) Take by weighing lutetium acetate, sodium acetate, ytterbium acetate and erbium acetate, wherein the parts of lutetium acetate and sodium acetate are weighed according to the molar percentage of _NaLuCl4 in the molar percentage composition respectively, and the parts of ytterbium acetate and erbium acetate are respectively weighed by Weigh the molar percentages of YbCl ₃ and ErCl ₃ in the same molar percentage composition above, dissolve the above acetate in deionized water to form an acetate solution, add trichloroacetic acid to the acetate solution to obtain a transparent mixture solution, wherein the molar ratio of trichloroacetic acid to the sum of metal ions in the acetate solution is 3:1;

( ₂ ) by weighing SiO in the same molar percentage composition as step (1) The molar percentage content is taken tetraethyl orthosilicate and is dissolved in ethanol, obtains tetraethyl orthosilicate solution, then step (1) is prepared The mixed solution was mixed with tetraethyl orthosilicate solution and stirred for 1 hour, and then adjusted to pH 5 with dilute nitric acid to obtain a precursor solution;

(3) Aging the precursor solution obtained in step (2) at room temperature for 2 weeks, then placing it in an oven, raising the temperature to 150°C and drying it for 7 days to obtain a transparent xerogel;

(4) Place the xerogel obtained in step (3) in a nitrogen precision annealing furnace, heat-treat at 590-620°C for 10 hours, then cool down to 50°C at a rate of 10°C/hour, turn off the power of the precision annealing furnace, The temperature is automatically lowered to room temperature, and transparent rare earth ion Er ³⁺ , Yb ³⁺ doped NaLuCl ₄ glass-ceramic is obtained.

Carry out X-ray diffraction test to the _NaLuCl4 crystallized glass that makes, obtain the XRD figure of this glass-ceramic as shown in Figure 1, its result is as follows: the XRD diffraction peak of the sample that obtains through heat treatment and the standard XRD of _NaLuCl4 crystalline phase The main diffraction peaks of the figures are consistent, so the obtained material is glass-ceramic of _NaLuCl crystallization phase. Measured with a TRIAX550 fluorescence spectrometer, under the excitation condition of a 970nm laser, the measured up-conversion luminescence spectrum of the glass-ceramics is shown in Figure 2, the integral of green light (532nm), green light (546nm) and red light (660nm) The luminous intensities are about 3.87×10 ⁵ , 7.54×10 ⁵ , and 1.93×10 ⁶ , respectively, and the green and red up-conversion luminescence are very strong.

Example 2

The mole percentage composition of Tm ³⁺ and Yb ³⁺ doped NaLuCl ₄ glass-ceramic is: SiO ₂ 89.5 mol%, NaLuCl ₄ 8 mol%, TmCl ₃ 0.5 mol%, YbCl ₃ 2 mol%, after the same preparation as in Example 1 And after the heat treatment process, the transparent rare earth ion Tm ³⁺ , Yb ³⁺ doped NaLuCl ₄ glass ceramics is obtained. The glass-ceramic was measured with a TRIAX550 fluorescence spectrometer, under the excitation condition of a 970nm laser, a strong blue up-conversion luminescence was observed.

Example 3

The mole percentage composition of Er ³⁺ , Tm ³⁺ , Yb ³⁺ doped NaLuCl ₄ glass ceramics is: SiO ₂ : 87mol%, NaLuCl ₄ : 10mol%, ErCl ₃ : 0.2mol%, TmCl ₃ : 0.1mol%, YbCl ₃ : 2.7mol%. After the same preparation and heat treatment process as in Example 1, a transparent NaLuCl ₄ glass-ceramics doped with rare earth ions Er ³⁺ , Tm ³⁺ , and Yb ³⁺ was obtained. The glass-ceramic was measured with a TRIAX550 fluorescence spectrometer, under the excitation condition of a 970nm laser, strong blue, green and red upconversion luminescence were observed.

Example 4

The mole percentage composition of Ho ³⁺ doped NaLuCl ₄ glass ceramics is: SiO ₂ 94mol%, NaLuCl ₄ 5.3mol%, HoCl ₃ 0.7mol%, after the same preparation and heat treatment process as in Example 1, a transparent rare earth Ionic Ho ³⁺ doped NaLuCl ₄ glass-ceramics. The glass-ceramic is measured by a TRIAX550 fluorescence spectrometer, under the excitation condition of a 970nm laser, strong green and red up-conversion luminescence are observed.

Comparative example 1

The mole percentage composition of Er ³⁺ and Yb ³⁺ doped NaLuF ₄ glass-ceramic is: SiO ₂ 90mol%, NaLuF ₄ 8mol%, ErF ₃ 0.5mol%, YbF ₃ 1.5mol%, after the same preparation as in Example 1 And after the heat treatment process, the transparent rare earth ion Er ³⁺ , Yb ³⁺ doped NaLuF ₄ glass-ceramic is obtained. Measured with a TRIAX550 fluorescence spectrometer, under the excitation condition of a 970nm laser, the measured up-conversion luminescence spectrum of the glass-ceramics is shown in Figure 3, the integral of green light (533nm), green light (548nm) and red light (658nm) The luminous intensities are about 3.02×10 ⁴ , 5.94×10 ⁴ , and 1.45×10 ⁵ , respectively. Compared with Example 1, the green and red upconversion luminous intensities are lower, indicating that the Er ³⁺ and Yb ³⁺ doped The up-conversion luminescence performance of the NaLuCl ₄ glass-ceramics is better than that of the Er ³⁺ , Yb ³⁺ -doped NaLuF ₄ glass-ceramics obtained in Comparative Example 1.

Claims (5)

1. a rare earth ion doped NaLuCl ₄devitrified glass, its molar percentage consists of: SiO ₂87 ~ 94mol%, NaLuCl ₄5.3 ~ 10mol%, LnCl ₃0.7 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one.

2. NaLuCl rare earth ion doped as claimed in claim 1 ₄devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂91mol%, NaLuCl ₄7mol%, ErCl ₃0.5mol%, YbCl ₃1.5mol%.

3. NaLuCl rare earth ion doped as claimed in claim 1 ₄devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂89.5mol%, NaLuCl ₄8mol%, TmCl ₃0.5mol%, YbCl ₃2mol%.

4. NaLuCl rare earth ion doped as claimed in claim 1 ₄devitrified glass, is characterized in that this devitrified glass molar percentage consists of: SiO ₂87mol%, NaLuCl ₄10mol%, ErCl ₃0.2mol%, TmCl ₃0.1mol%, YbCl ₃2.7mol%.

5. NaLuCl rare earth ion doped as claimed in claim 1 ₄the preparation method of devitrified glass, is characterized in that comprising the following steps:

(1) by mole% composition SiO ₂87 ~ 94mol%, NaLuCl ₄5.3 ~ 10mol%, LnCl ₃0.7 ~ 3mol%, wherein LnCl ₃for YbCl ₃, ErCl ₃, TmCl ₃and HoCl ₃in at least one; Take at least one in acetic acid lutetium, sodium-acetate and acetic acid ytterbium, acetic acid erbium, acetic acid thulium and acetic acid holmium, wherein the deal of acetic acid lutetium, sodium-acetate is respectively by mole% NaLuCl in composition ₄molar 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 150 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 590 ~ 620 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 NaLuCl ₄devitrified glass.