CN105254184A - A kind of rare earth ion doped Li3YCl6 glass-ceramics and its preparation method - Google Patents

Abstract

The invention discloses a Li ₃ YCl ₆ glass-ceramic doped with rare earth ions, the mole percentage composition of which is: SiO ₂ : 87.8-94 mol%, Li ₃ YCl ₆ : 5.5-10 mol%, LnCl ₃ : 0.5-3 mol% , wherein LnCl ₃ is at least one of YbCl _{3 , ErCl 3 ,} TmCl ₃ and HoCl ₃ ; the advantage is that the rare earth ion-doped Li ₃ YCl ₆ glass-ceramic prepared by the present invention is transparent, deliquescence resistance, good mechanical properties, The blue-violet light has high transmittance, low phonon energy and high up-conversion efficiency, which can greatly improve the efficiency of up-conversion lasers. Moreover, the preparation method of the glass-ceramic is simple and the production cost is low.

Description

A kind of rare earth ion doped Li3YCl6 glass-ceramics and its preparation method

technical field

The invention relates to a rare earth ion-doped glass-ceramic, in particular to a rare-earth ion-doped _Li3YCl6 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. 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. Li ₃ YCl ₆ crystal has lower phonon energy than fluoride, which is more suitable as a rare earth-doped up-conversion luminescent host. Rare-earth ion-doped Li ₃ YCl ₆ crystal has a higher However, Li ₃ YCl ₆ 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 their practical applications.

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 , affecting the up-conversion luminescence output; for example, the invention patent application with the publication number CN103951243 and the name "Cs ₂ LiYCl ₆ glass-ceramics doped with rare earth ions and its preparation method" also discloses that a crystallite phase is Cs ₂ LiYCl _6. Glass-ceramics whose glass phase is mainly GeO ₂ , doped rare earth ions are one of Ce ³⁺ , Eu ³⁺ , Tb ³⁺ , Pr ³⁺ and Nd ³⁺ . Prepared by subsequent heat treatment, it has good scintillation performance and is mainly used as scintillation material. However, there is no public report on Li ₃ YCl ₆ glass-ceramics doped with rare earth ions Yb ³⁺ , Er ³⁺ , Tm ³⁺ and Ho ³⁺ for 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 Li ₃ YCl ₆ microparticle 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. Crystal glass and its preparation method.

The technical solution adopted by the present invention to solve the above-mentioned technical problems is: a rare earth ion-doped Li ₃ YCl ₆ glass-ceramics, the molar percentage composition of which is as follows: SiO ₂ 87.8-94 mol%, Li ₃ YCl ₆ 5.5-10 mol%, LnCl ₃ 0.5-3mol%, 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 87.8 mol%, Li ₃ YCl ₆ 10 mol%, TmCl ₃ 0.2 mol%, YbCl ₃ 2 mol%.

The molar percentage composition of the glass-ceramic is: SiO ₂ 89 mol%, Li ₃ YCl ₆ 8 mol%, ErCl ₃ 0.5 mol%, YbCl ₃ 2.5 mol%.

The molar percentage composition of the glass-ceramic is: SiO ₂ 88 mol%, Li ₃ YCl ₆ 9 mol%, ErCl ₃ 0.1 mol%, TmCl ₃ 0.1 mol%, YbCl ₃ 2.8 mol%.

The preparation method of the _{Li3YCl6 glass} ceramics doped with rare earth ions comprises the following steps:

(1) SiO ₂ 87.8-94 mol%, Li ₃ YCl ₆ 5.5-10 mol%, LnCl ₃ 0.5-3 mol% 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 yttrium acetate, lithium acetate and ytterbium acetate, erbium acetate, thulium acetate and holmium acetate, wherein the parts of yttrium acetate and lithium acetate are respectively _weighed by the mole percentage of _Li3YCl6 in the mole percentage composition Get, the part of at least one in ytterbium acetate, erbium acetate, thulium acetate and holmium acetate is weighed according to the mole percentage content of _LnCl3 in the above-mentioned same mole percentage composition respectively, and above-mentioned acetate is dissolved in deionized water Form acetate solution, add trichloroacetic acid to obtain transparent mixed solution in acetate solution, wherein the mol ratio of trichloroacetic acid and metal ion summation 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 142°C and drying it for 9 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 560-590°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 Li ₃ YCl ₆ glass ceramics.

Compared with the prior art, the present invention has the advantages that: the glass-ceramics has the excellent up-conversion performance of Li ₃ YCl ₆ crystal matrix material and the characteristics of mechanical strength, stability and easy processing of silica glass; it is proved by experiments : The rare earth ion doped Li ₃ YCl ₆ glass-ceramics prepared by the preparation method of the present invention is transparent, deliquescence resistance, good mechanical properties, high blue-violet light transmittance, low phonon energy, high up-conversion efficiency and other properties , can greatly improve the efficiency of the up-conversion laser; 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 upconversion luminescent spectrum of Tm ³⁺ , Yb ³⁺ doped Li ₃ YCl ₆ glass ceramics obtained in Example 1;

3 is the 970nm laser excitation upconversion luminescence spectrum of Tm ³⁺ , Yb ³⁺ doped Li ₃ YF ₆ 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 Tm ³⁺ and Yb ³⁺ doped Li ₃ YCl ₆ glass ceramics is: SiO ₂ 87.8mol%, Li ₃ YCl ₆ 10mol%, TmCl ₃ 0.2mol%, YbCl ₃ 2mol%, the preparation of the above composition The glass-ceramic process is as follows:

( ₁ ) Weigh yttrium acetate, lithium acetate, ytterbium acetate, and thulium acetate, wherein the parts of yttrium acetate and lithium acetate are weighed according to the molar percentage of _Li3YCl6 in the molar percentage composition, and the parts of ytterbium acetate and thulium acetate Weigh the molar percentages of YbCl ₃ and TmCl ₃ in the same molar percentage composition as above, dissolve the above-mentioned acetate in deionized water to form an acetate solution, add trichloroacetic acid to the acetate solution to obtain a transparent A mixed 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 142°C and drying it for 9 days to obtain a transparent xerogel;

(4) Place the xerogel obtained in step (3) in a nitrogen precision annealing furnace, heat-treat at 560-590°C for 10 hours, then cool down to 50°C at a rate of 10°C/hour, and turn off the power of the precision annealing furnace, The temperature is automatically lowered to room temperature, and transparent rare earth ion Tm ³⁺ , Yb ³⁺ doped Li ₃ YCl ₆ glass-ceramic is obtained.

X-ray diffraction test was carried out _on the prepared Li _{3 YCl 6} glass-ceramics, and the XRD pattern of the glass-ceramics obtained is shown in Figure 1, and the results are as follows: The main diffraction peaks of the standard XRD patterns of the phases are consistent, so the obtained material is a glass-ceramic of Li ₃ YCl ₆ devitrification 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, and the integrated luminescence intensities of blue light (476nm) and red light (679nm) are respectively about 4.43×10 ^5. 7.34×10 ⁵ , the blue and red up-conversion luminescence is very strong.

Example 2

Er ³⁺ , Yb ³⁺ doped Li ₃ YCl ₆ glass-ceramic mole percent composition: SiO ₂ 89mol%, Li ₃ YCl ₆ 8mol%, ErCl ₃ 0.5mol%, YbCl ₃ 2.5mol%, after and the embodiment 1 After the same preparation and heat treatment process, a transparent rare earth ion Er ³⁺ , Yb ³⁺ doped Li ₃ YCl ₆ glass-ceramic was obtained. The glass-ceramic was measured with a TRIAX550 fluorescence spectrometer, under the excitation condition of a 970nm laser, strong green and red upconversion luminescence were observed.

Example 3

The mole percentage composition of Er ³⁺ , Tm ³⁺ , Yb ³⁺ doped Li ₃ YCl ₆ glass ceramics is: SiO ₂ 88mol%, Li ₃ YCl ₆ 9mol%, ErCl ₃ 0.1mol%, TmCl ₃ 0.1mol%, YbCl ₃ 2.8mol%, after the same preparation and heat treatment process as in Example 1, a transparent Li ₃ YCl ₆ 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 Li ₃ YCl ₆ glass ceramics is: SiO ₂ 94mol%, Li ₃ YCl ₆ 5.5mol%, HoCl ₃ 0.5mol%, after the same preparation and heat treatment process as in Example 1, A transparent rare earth ion Ho ³⁺ doped Li ₃ YCl ₆ glass-ceramic was obtained. 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 Tm ³⁺ and Yb ³⁺ doped Li ₃ YF ₆ glass-ceramic is: SiO ₂ 87.8 mol%, Li ₃ YF ₆ 10 mol%, TmF ₃ 0.2 mol%, YbF ₃ 2 mol%, through and embodiment 1 After the same preparation and heat treatment process, a transparent rare earth ion Tm ³⁺ , Yb ³⁺ doped Li ₃ YF ₆ 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, and the integrated luminescence intensities of blue light (476nm) and red light (679nm) are respectively about 3.96×10 ^4. 6.56×10 ⁴ , compared with Example 1, the blue and red up-conversion luminescence intensity is lower, indicating the up-conversion luminescence of Tm ³⁺ , Yb ³⁺ doped Li ₃ YCl ₆ glass ceramics obtained in Example 1 The performance is better than the Tm ³⁺ , Yb ³⁺ doped Li ₃ YF ₆ glass ceramics obtained in Comparative Example 1.

Claims (5)

1. A rare-earth ion-doped _Li3YCl6 glass _- ceramic, its molar percentage composition is: _SiO2 87.8～ _94mol %, _Li3YCl6 5.5～10mol%, _LnCl3 0.5～3mol%, wherein _LnCl3 is At least one of YbCl _{3 , ErCl 3 ,} TmCl ₃ and HoCl ₃ . 2. The rare earth ion-doped Li ₃ YCl ₆ glass-ceramic according to claim 1, characterized in that the glass-ceramic has a molar percentage composition of: SiO ₂ 87.8 mol%, Li ₃ YCl ₆ 10 mol%, TmCl ₃ 0.2 mol%, YbCl ₃ 2mol%. 3. The rare earth ion-doped Li ₃ YCl ₆ glass-ceramic according to claim 1, characterized in that the glass-ceramic is composed of: SiO ₂ 89 mol%, Li ₃ YCl ₆ 8 mol%, ErCl ₃ 0.5 mol %, YbCl ₃ 2.5 mol%. 4. The rare earth ion-doped Li ₃ YCl ₆ glass-ceramic as claimed in claim 1, characterized in that the glass-ceramic has a molar percentage composition of: SiO ₂ 88 mol%, Li ₃ YCl ₆ 9 mol%, ErCl ₃ 0.1 mol %, TmCl ₃ 0.1 mol%, YbCl ₃ 2.8 mol%. _5. The preparation method of _Li3YCl6 glass ceramics doped with rare earth ions as claimed in claim 1, characterized in that it comprises the following steps: (1) SiO ₂ 87.8-94 mol%, Li ₃ YCl ₆ 5.5-10 mol%, LnCl ₃ 0.5-3 mol% 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 yttrium acetate, lithium acetate and ytterbium acetate, erbium acetate, thulium acetate and holmium acetate, wherein the parts of yttrium acetate and lithium acetate are respectively _weighed by the mole percentage of _Li3YCl6 in the mole percentage composition Get, the part of at least one in ytterbium acetate, erbium acetate, thulium acetate and holmium acetate is weighed according to the mole percentage content of _LnCl3 in the above-mentioned same mole percentage composition respectively, and above-mentioned acetate is dissolved in deionized water Form acetate solution, add trichloroacetic acid to obtain transparent mixed solution in acetate solution, wherein the mol ratio of trichloroacetic acid and metal ion summation 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 142°C and drying it for 9 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 560-590°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 Li ₃ YCl ₆ glass ceramics.