Raman spectroscopic analysis of the Ge–As–S chalcogenide glass-forming system

Musgraves, J. David; Wachtel, Peter; Gleason, Benn; Richardson, Kathleen

doi:10.1016/j.jnoncrysol.2013.11.031

Cited by 40 publications

(20 citation statements)

References 13 publications

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“…Density q used in the simulation, calculated d i first (i ¼ 1) and second (i ¼ 2) neighbour peak positions (in Å ) of the partial pair correlation function g ij (r), together with obtained first minimum r m of each g ij ðrÞ, and corresponding calculated coordination numbers n ij . Note that the distances in Si 20 Te 80 are compared to the experimental data of Si 19 increased differences appear, and which underscore larger structural differences, including on the local structure.…”

Section: A Structural Modelmentioning

confidence: 96%

“…This allows filtering out unnecessary details, which ultimately do not affect the compositional trends, while focusing only on the key microscopic physics governing the thermal and mechanical properties. This approach has enabled accurate predictions of glass compositions, where elastic phase transitions can be expected, 17,18 and many other physical properties that have a bearing on these elastic phase transitions have also been investigated in a large number of binary or ternary sulphides [19][20][21][22][23] and selenides, [24][25][26][27][28] as well as oxides [29][30][31][32][33] and even commercial glasses. [34][35][36][37] According to rigidity theory, [14][15][16] the GFR and glassforming ability are determined by comparing the number of atomic degrees of freedom n L per atom with the number of interatomic force field constraints n c arising from bondstretching (BS) and bond-bending (BB) interactions, which constrain 17,18,38,39 the network structure at a molecular level.…”

Section: Introductionmentioning

confidence: 99%

“…Building on these elegant ideas, there has been a vast body of experimental studies, in this context, on sulfide [19][20][21][22][23] and selenide [24][25][26][27][28] network glasses, and most of them have shown that anomalies are found in compositional studies at the location of the isostatic criterion, i.e., when n c ¼ 3, a result that has been associated by Phillips 38 and Thorpe 17,18 with a mean-field flexible to stressed rigid transition occurring at a network mean coordination number r ¼ 2:4, e.g., at x ¼ 20% Ge content 49,50 in Ge x Se 1Àx .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

Gunasekera

Boolchand

Micoulaut

2014

Journal of Applied Physics

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Amorphous GexSixTe1−2x glasses are studied as a function of composition by a combination of experimental and theoretical methods, allowing for a full description of the network structure in relationship with physico-chemical properties. Calorimetric and thermal measurements reveal that such glasses display an anomalous behavior across a range of compositions xc1=7.5% and <x<xc2=9%, in which is manifested a deep minimum in molar volume, non-reversing enthalpy, and liquid fragility. These anomalies allow defining an intermediate phase, where network rigidity onsets as the content x of Group IV atoms (Ge, Si) are increased. The structural manifestation of these anomalies is understood from 119Sn Mössbauer spectroscopy and First Principles Molecular Dynamics at selected compositions (Ge20Te80, Si20Te80, and Ge10Si10Te80). The numerical models reveal the quite different roles played by the modifier or network cross-linker Ge or Si atoms, Si being more tetrahedral in sp3 geometry, whereas Mössbauer spectroscopy shows that the nature of chemical bonding is dramatically changed around x≃ 8%. The precise evolution of the local structure and chemical bonding ultimately allows understanding the origin of the intermediate phase in these complex tellurides.

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Section: A Structural Modelmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

Gunasekera

Boolchand

Micoulaut

2014

Journal of Applied Physics

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“…Owing to the transformation of mode V 2 to V 4 , the amplitude of this band is possibly broadened which is consistent with the increasing quantity of [GaS 4 ] units. There are reports indicated that pyramid units [SbS 3 ] and tetrahedron structure [GaS 4 ] are vibrated in the ~290 and ~340 cm −1 bands4142, with the vibrations of metal–metal bonds of S 3 Ga–GaS 3 type at ~265 cm −1 4143. Therefore, the peak at ~300 cm −1 was attributed to the superimposed bands of [GaS 4 ] and [SbS 3 ] units.…”

Section: Resultsmentioning

confidence: 99%

Effect of gallium environment on infrared emission in Er3+-doped gallium– antimony– sulfur glasses

Jiao

et al. 2017

Sci Rep

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Gallium-based Ga–Sb–S sulfide glasses was elaborated and studied. A relationship between the structure, composition, and optical properties of the glass has been established. The effects of the introduction of Ga on the structure using infrared and Raman spectroscopies and on the Er3+-doped IR emission have been discussed. The results show that incorporation of Ga induced the dissociation of [SbS3] pyramids units and the formation of tetrahedral [GaS4] units. The dissolved rare earth ions are separated around the Ga–S bonding and the infrared emission quenching are controlled. Moreover, continuous introduction of Er ions into the glass forms more Er–S bonds through the further aggregation surrounding the [GaS4] units. In return, the infrared emission intensity decreased with excessive Er ion addition. This phenomenon is correlated with the recurrence concentration quenching effect induced by the increase of [GaS4] units.

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“…All glasses were fabricated in 25 g batches, using standard chalcogenide glass melt‐quench protocol, described in full detail elsewhere, with a melt temperature of 700°C and an annealing temperature of T g – 40°C . Multiple (3) 2‐mm‐thick slices were cut from each resulting glass boule for polishing.…”

Section: Methodsmentioning

confidence: 99%

Refractive Index and Thermo‐Optic Coefficients of Ge‐As‐Se Chalcogenide Glasses

Gleason

Richardson

Sisken

et al. 2016

Int J of Appl Glass Sci

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Seventeen glasses in the Ge-As-Se ternary glass-forming region have been fabricated and analyzed to provide input for optical design data and to establish composition-and structure-based relationships to aide development of novel chalcogenide glasses with tailored optical functionality. While known that Ge addition to binary As-Se glasses enhances the mean coordination number (MCN) of the network and results in increased T g and decreased CTE, this work highlights the impact on optical properties, specifically mid-wave (k = 4.515 lm) index and thermo-optic coefficient (dn/dT). Trends in property changes were correlated with an excess or deficiency of chalcogen content in the glassy network as compared to stoichiometric compositions. Transitions in key optical properties were observed with the disappearance of Se-Se homopolar bonds and creation of As-As homopolar bonds which are associated with the Se-rich and Se-deficient regions near the stoichiometry, respectively. A second transition was observed with the creation of GeSe ethane-like structures, which are only present in strongly Se-deficient networks. Fitting dn/dT values with a simplified version of the thermal Lorentz-Lorenz formulation yielded a linear relation between the quantity (n À3 •dn/dT) and the CTE, which can be used to predict compositions with the near-zero dn/dT required for athermal optical systems.

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Raman spectroscopic analysis of the Ge–As–S chalcogenide glass-forming system

Cited by 40 publications

References 13 publications

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

Effect of gallium environment on infrared emission in Er3+-doped gallium– antimony– sulfur glasses

Refractive Index and Thermo‐Optic Coefficients of Ge‐As‐Se Chalcogenide Glasses

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