Physicochemical, optical properties and stability against crystallization of GaxGey-xS100-y (x=0–8; y = 40–42) glasses

https://doi.org/10.1016/j.jnoncrysol.2020.120615Get rights and content

Highlights

  • The physicochemical, optical and crystallization properties of GaxGey-xS100-y (x=0–8; y = 40–42) glasses are studied.

  • The Ga-Ge-S glass annealing results in the formation of the phases of germanium monosulfide, germanium disulfide, and gallium sesquisulfide.

  • The transparency of glasses in the 8–15 µm region rises with an increase in Ga content.

  • GaxGe40-xS60 (x = 0–8) and Ga3Ge38S59 glasses have highest stability against crystallization.

Abstract

In this work, the physicochemical, optical properties and stability against crystallization of GaxGey-xS100-y (x=0–8; y = 40–42) glasses are studied. A method for determining the chemical macrocomposition of glasses with an accuracy of 0.02–0.1 at. % based on inductively coupled plasma atomic emission spectroscopy has been developed. It has been established that the glass annealing results in the formation of the phases of germanium monosulfide, germanium disulfide, and gallium sesquisulfide. Crystallization of glasses with a gallium content of 8 at.% occurs with the formation of an additional phase of unknown composition. When the glass-forming GaxGe40-xS60 (x=0–3) glass melts are air-quenched, GeS2 crystals are formed. The transparency of glasses in the 8–15 µm region rises with an increase in the gallium content. Among the studied compositions, GaxGe40-xS60 (x = 0–8) and Ga3Ge38S59 glasses have highest stability against crystallization.

Introduction

Glasses of the Ga - Ge - S system are promising materials for infrared (IR) fiber optics. They are transparent in the spectral range 0.8–12 µm, have high glass transition temperature (up to 470°C), and low toxicity compared to arsenic sulfide glasses [1]. The significant ability to dissolve rare-earth elements (REE), which increases with the addition of alkali metal halides, makes these glasses suitable for active IR optics [2,3]. Controlled crystallization of glasses based on germanium and gallium sulfides makes it possible to manufacture glass-ceramic materials with improved mechanical characteristics [4,5].

At present, according to literature data, in the Ga-Ge-S system, the properties of glasses in the GeS2-Ga2S3 section with a sulfur content of more than 60 at.% are mainly studied [6], [7], [8]. It is known that a decrease in the atomic fraction of sulfur in Ge-S-based glasses leads to an increase in the solubility of REEs, an improvement of luminescence parameters, and a shift of the long-wavelength transmission edge to the far-IR region [9], [10], [11]. From this point of view, Ga - Ge - S glasses containing no more than 60 at.% sulfur may be preferable for some practical applications. The transparency in the near and middle (mid) IR ranges and the stability against crystallization of these glasses, as key parameters for fiber optics, are not studied in detail. For individual compositions (GaxGe45-xS55, GaxGe40-xS60; x = 5, 10, 15 at.%), the difference between the temperature of the onset crystallization and glass transition temperature, which is a characteristic of the glass-forming ability [12], was determined. For some compositions, glass transition temperature and molar volume were measured [13], which do not provide direct information on their stability against crystallization.

Gallium increases the solubility of REEs in chalcogenide glasses and improves their luminescence characteristics [14], [15], [16], [17], [18]. Gallium, forming stable oxides, pulls oxygen from germanium atoms, which reduces absorption in chalcogenide glasses in the wavelength ranges of near 7.9 and 12.5 μm [19,20]. On the other hand, a high gallium concentration reduces stability against crystallization of chalcogenide glasses [12,[21], [22], [23]]; therefore, optimization of its composition is an urgent problem for practical applications of these materials in IR optics.

The aim of this work was to study the effect of the composition of GaxGey-xS100-y (x = 0–8; y = 40–42 at.%) glasses on the physicochemical, optical properties and their stability against crystallization. On the basis of the results obtained, glass compositions that are most suitable for a use in fiber IR optics were chosen.

Section snippets

Glass synthesis

For the synthesis of Ga-Ge-S glasses, germanium of 6N purity grade (JSC "Germanium", Russia), gallium of 7N purity (JSC "Girmet", Russia) and sulfur of OSCh 17-5 grade (Norilsk, Russia) were used. Sulfur was additionally purified from organic impurities and heterogeneous particles by passing its vapor through catalysts with subsequent vacuum distillation [24]. Germanium was preliminarily calcined in vacuum at 700°C to remove the impurity of germanium monoxide from the surface of granules. The

Chemical glass composition

The macrocompositions of the obtained glasses are given in Table 1. The calculated values ​​of the expanded uncertainty for the determination of Ga, Ge, and S are in the range 0.02–0.1 at. %. The deviations of the glass compositions from the specified ones did not exceed 0.5 at.% for sulfur, 0.4 at.% for germanium, and 0.11 at.% for gallium. The observed deviations may be due to the partial volatilization of sulfur during its melting for degassing before the ampoules are sealed off from the

Discussion

The results obtained in this work indicate a significant effect of the chemical composition of GaxGey-xS100-y (x = 0–8; y = 40–42) glasses on their properties. For most of the studied samples, a change in the sulfur content by 1 at.% makes the glass, which is initially resistant to crystallization, unsuitable for fiber drawing (∆T <120°C). Such deviations can occur during the production of especially pure glasses at the stages of vacuum loading of the charge components into the reactor and

Conclusions

The properties of GaxGey-xS100-y glasses with a sulfur content of 58–60 at.% substantially depend on the chemical composition. When glasses are annealed, crystalline phases of germanium monosulfide, germanium disulfide, and germanium sesquisulfide are formed. Crystallization of glasses with a gallium content of 8 at.% is accompanied by the formation of an additional phase of unknown composition. When the melt is quenched in air, germanium disulfide crystallizes in GaxGe40-xS60 glasses with

CRediT authorship contribution statement

A.P. Velmuzhov: Conceptualization, Methodology, Investigation, Writing - original draft, Visualization, Writing - review & editing. M.V. Sukhanov: Conceptualization, Investigation. E.A. Tyurina: Investigation. A.D. Plekhovich: Investigation. D.A. Fadeeva: Investigation. L.A. Ketkova: Investigation, Writing - review & editing. M.F. Churbanov: Conceptualization, Writing - review & editing. V.S. Shiryaev: Conceptualization, Writing - review & editing.

Declaration of Competing Interest

We wish to confirm that there are no known conflicts of interest associated with this publication and there has been no significant financial support for this work that could have influenced its outcome.

We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us.

We confirm that we

Acknowledgments

This work was supported by the Russian Science Foundation (Russia, Grant no. 18-73-10083).

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