Enhancement of luminescence in Er3+ doped Ge20Ga10S70 glass-ceramics

doi:10.1016/j.optmat.2020.109677

Optical Materials

Volume 100, February 2020, 109677

https://doi.org/10.1016/j.optmat.2020.109677 Get rights and content

Highlights

•
The luminescence intensity at 1.54 μm in glass-ceramics with 20 h annealing time is twice than that in the base glass.
•
The luminescence enhancement is related to the Ga₂S₃ crystals in glass-ceramics.
•
The Er ions could only be found near the Ga₂S₃ crystalline grains of elemental mapping.

Abstract

We have fabricated Ge₂₀Ga₁₀S₇₀ glasses doped with 1.0 at% Er and annealed them to create chalcogenide glass-ceramics. We further characterized their optical transmission, luminescence, and microstructure for investigating the mechanism of the fluorescence enhancement. The results showed that, Ga₂S₃ and GeS₂ crystals are precipitated successively, the transmittance of the glass-ceramics decreases, and the transmission edge shifts towards longer wavelengths with prolonged annealing time. Photoluminescence (PL) intensity at 1.54 μm in glass-ceramics with 20 h annealing time is twice than that in the base glass. From the similar evolution of PL and XRD intensity, we concluded that the luminescence enhancement is related to the Ga₂S₃ crystals in glass-ceramics. The Er ions are registered near tht Ga₂S₃ crystalline grains with a size of 50 nm as evident by elemental mapping. The results are helpful to optimize the chalcogenide glass components doped with REI and improve the solubility of REI.

Introduction

Chalcogenide glasses (ChGs) have wide transmission range, low maximum phonon energy (MPE, <450 cm⁻¹), high third-order optical nonlinearity (~10³ higher than SiO₂ glass) [1,2], and thus are finding their various applications in the field of nonlinear optics, infrared fibers and windows, optical amplifiers and laser media [[3], [4], [5], [6], [7], [8], [9]], and so on. For example, the radiative emission quantum efficiency of rare-earth ions (REI) dissolved in the glass matrix [10] can be promoted by lower phonon energy, and thus the emission in the infrared region becomes possible in chalcogenide glasses doped by REIs. For this reasons, REI-doped chalcogenide glasses have been extensively investigated as a solution available to develop new lasers working at the mid-infrared regions [[11], [12], [13]].

However, chalcogenide glasses are notorious for their weak mechanical properties, this usually leads to heavy damage of the glasses when exposed to strong laser/ion irradiation. One of the solutions is to anneal the glass at a temperature which is slightly higher than its glass transition temperature, and this creates a large amount of micro- or nano-crystals inside. While the mechanical properties of chalcogenide glasses can be improved, it has been found that, emission from the REIs in the chalcogenide glass can also be enhanced. For instance, while the glass-ceramics is fabricated in chemically stoichiometric (GeS₂)_x (Ga₂S₃)_1-x system, GeS₂ crystals usually are precipitated on the surface of the glass while Ga₂S₃ crystals are located in the interior of the glass [[14], [15], [16], [17], [18], [19]], and an enhancement of the luminescence has been discovered in sulfur-based glass-ceramics [[19], [20], [21]]. The change in crystalline-field during nucleation has been considered as a reason to account for longer radiative lifetimes in the glass-ceramics. However, the mechanism of fluorescence enhancement in glass ceramics and the relationship between luminescence intensity and crystal field changes have been rarely reported.

In this paper, we prepared Ge₂₀Ga₁₀S₇₀ glasses doped with 1.0 at% Er. On the one hand, although, the addition of Ga could avoid the formation of the REI clusters, it has been reported that the optimal ratio between Ga and REI was ~10:1 can promote homogeneous doping of REIs in ChGs[22,23]. On the other hand, excessive sulfur can ensure less formation of Ge–Ge or Ga–Ga clusters in the glass-ceramics, and then chemically stoichiometric GeS₂ and Ga₂S₃ crystals can be precipitated in glass-ceramics. This would be helpful to analyze the effect of individual Ga₂S₃ or GeS₂ crystals on the luminescence. We therefore investigate how the crystallization process affects photoluminescence intensity in Er-doped Ge₂₀Ga₁₀S₇₀ glass-ceramics.

Section snippets

Experimental procedures

The melt-quenching method was employed to prepare Ge₂₀Ga₁₀S₇₀ glasses (20 g) doped with 1.0 at% Er (GGS-1.0Er). High pure Ge, Ga, S elements (5 N) and Er elements (3 N) were weighted and introduced into cleaned quartz glass ampule before the ampule was evacuated to ~ 10⁻³ Pa and sealed. Then the ampule was put into in a rocking furnace and the mixture was melted at 920 °C for 12 h before it was quenched in cold water. The glass rod was then annealed at 300 °C for 5 h and cut into glass disks (Φ

Results and discussion

Fig. 1 is XRD patterns of the base glass and the glasses annealed for different durations. The XRD pattern of the base glass exhibits a broad band and no any sharp peaks can be detected. Weak crystallization peaks begin to appear in the glasses annealed for 15 h, and the crystallization peaks becomes strong in the glasses annealed for 20 h. The position of these peaks (2θ = 29.12° and 49.83°) are in excellent agreement with those in JCPDF card of no.49–1361 that are attributed to the Ga₂S₃.

Conclusions

Ge₂₀Ga₁₀S₇₀ glasses and glass-ceramics doped with 1.0 at% Er were prepared for investigating the relationship between fluorescence intensity, crystallization process and local chemical environment of REI. The XRD analysis showed that, the Ga₂S₃ crystals were precipitated in the glasses with an gradually prolonged annealing duration less than 20 h, and then GeS₂ crystal phase appeared gradually with further prolonged annealing duration. Emission at 1.54 μm was found to be about double enhanced

Author agreement

I would like to declare on behalf of my co-authors that the work described is original research that has not been published previously, and not under consideration for publication elsewhere, in whole or in part. All the authors listed have approved the manuscript that is enclosed.

CRediT authorship contribution statement

Zhen Yang: Writing - original draft. Rongping Wang: Writing - review & editing. Xiang Shen: Funding acquisition. Tiefeng Xu: Funding acquisition.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work is financially supported by the Natural Science Foundation of China (Grant Nos. 61775109, 61775111, 61627815, and 61675105); 3315 Innovation Team in Ningbo City, Zhejiang Province, China; and sponsored by the K. C. Wong Magna Fund in Ningbo University, China.

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Enhancement of luminescence in Er3+ doped Ge20Ga10S70 glass-ceramics

Highlights

Abstract

Introduction

Section snippets

Experimental procedures

Results and discussion

Conclusions

Author agreement

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgments

J. Non-Cryst. Solids

J. Non-Cryst. Solids

J. Non-Cryst. Solids

J. Non-Cryst. Solids

J. Am. Ceram. Soc.

J. Solid State Chem.

Mater. Res. Bull.

Opt. Mater.

Opt. Mater.

Prog. Mater. Sci.

Opt. Mater.

Semiconduct. Semimet.

J. Non-Cryst. Solids

Amorphous Chalcogenides: Advances and Applications

Amorphous Chalcogenide Semiconductors and Related Materials

Enhancement of luminescence in Er³⁺ doped Ge₂₀Ga₁₀S₇₀ glass-ceramics