Physicochemical, optical properties and stability against crystallization of GaxGey-xS100-y (x=0–8; y = 40–42) glasses
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).
References (53)
- et al.
Pr3+-doped Ge-Ga-S glasses for 1.3 mm optical fiber amplifiers
J. Non-Cryst. Solids
(1995) - et al.
Near-IR emission of Er3+ ions in CsCl-Ga-Ge-S glasses excited by visible light
Opt. Mater.
(2017) - et al.
Local motifs in GeS2–Ga2S3 glasses
J. Alloys Compd
(2016) - et al.
The effect of compositional variations on the properties of rare-earth doped Ge-S-I chalcohalide glasses
J. Non-Cryst. Solids
(1997) - et al.
Compositional dependence of the 1.3 μm emission and energy transfer mechanism in Ge-Ga-S glasses doped with Pr3+
J. Non-Cryst. Solids
(1999) - et al.
Preparation and properties of Ge-Ga-S glasses for laser hosts
J. Non-Cryst. Solids
(1997) - et al.
Physicochemical, structural and fluorescence properties of Er-doped Ge-S-Ga glasses
J. Phys. Chem. Solids
(2003) - et al.
Coreclad Pr(3+)doped Ga(In)GeAsSe Glass Fibers for MidIR Radiation Sources
J. NonCryst. Solids
(2020) - et al.
Modeling and experimental determination of physical properties of GexGaySe1-x-y chalcogenide glasses II: Optical and thermal properties
J.Non-Cryst. Solids
(2019) - et al.
Preparation and investigation of GaxGe25As15Se60-x (x=1÷5) glasses
Opt. Mater.
(2017)
Sulfur as the source of hydrogen impurity and heterogeneous inclusions in the Ge-Ga-S glasses
J. Non-Cryst. Solids
Distribution of elements in Ge–Se bulk glasses and optical fibers detected by inductively coupled plasma atomic emission spectrometry
J. Phys. Chem. Solids
Heterophase inclusions as a source of non-selective optical losses in high-purity chalcogenide and tellurite glasses for fiber optics
J. Non-Cryst. Solids
Crystallization behavior of (GeTe4)x(GaTe3)100-x glasses for far-infrared optics applications
J. Alloys Compd
Study of characteristic temperatures and nonisothermal crystallization kinetics in As-Se-Te glass system
Solid State Sci
Kinetics of crystal growth of germanium disulfide in Ge0.38S0.62 chalcogenide glass
J. Non-Cryst. Solids
Preparation of optical fibers based on Ge-Sb-S glass system
Opt. Mater.
The study of phase formation processes in GeSx:Bi (1 < x < 2) chalcogenide glasses
J. Non-Cryst. Solids
The glass transition and crystallization of germanium-sulfur glasses
J. Non-Cryst. Solids
Controllable Formation of the Crystalline Phases in Ge-Ga-S Chalcogenide Glass-Ceramics
J. Am. Ceram. Soc
Glass transition kinetics and crystallization mechanism in Ge–Ga–S–CsCl chalcohalide glasses
J. Non-Cryst. Solids
Evidence of network demixingin GeS2-Ga2S3 chalcogenideglasses: A phase transformation study
J. Solid State Chem.
Preparation of high-purity chalcogenide glasses
Correlation between physical, optical and structure properties of sulfide glasses in the system Ge-Sb-S
Mater. Chem. Phys.
Preparation and investigation of the properties of Ge25-xGaxTe75-yIy Glass System (x = 5, 10, 15, y = 0–6)
J. Non-Cryst. Solids
Structural investigations of GeS2-Ga2S3-CdS chalcogenide glasses using Raman spectroscopy
Solid State Commun
Cited by (6)
Phase formation during crystallization of melts and glasses of the Ga<inf>x</inf>Ge<inf>40-x</inf>S<inf>60</inf> system
2023, Journal of Non-Crystalline SolidsFlexible composition-dependent third-order optical nonlinearity of chalcogenide glasses within a Ge-Ga-S ternary system
2023, Journal of Non-Crystalline SolidsInvestigation of phase separation as a source of optical losses in IR glasses for fiber optics
2023, Journal of Non-Crystalline SolidsPreparation of high-purity chalcogenide glasses containing gallium(III) sulfide
2022, Journal of Non-Crystalline SolidsCitation Excerpt :Despite the multi-step method, the prepared samples are characterized by a deviation of the macro-composition from the preset values at the level of the traditional method. This is the most important requirement for the method of preparing sulfide glasses, since their properties are sensitive to the ratio of components, especially to the sulfur content [23]. The developed glass synthesis has the following main advantages in comparison with known methods:
Structure of Ge<inf>x</inf>Ga<inf>8</inf>S<inf>92–x</inf> glasses studied by high-resolution X-ray photoelectron spectroscopy and Raman scattering
2023, Wuli Xuebao/Acta Physica Sinica