Structural chemical processes at the synthesis of chalcogenide glasses

Kuznetsov, S. L.; Михайлов, М. Н.; Pecheritsyn, I. M.; Turkina, E. Yu.

doi:10.1016/s0022-3093(97)00093-8

Cited by 14 publications

(11 citation statements)

References 5 publications

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“…The energetic balance of this reaction is left‐shifted attaining 40 kJ mol −1 (estimation with ± 10 kJ mol −1 accuracy), as follows from comparison of mean molar bond energies calculated from standard atomization enthalpies of relevant compounds (Table ) . Under nonequilibrium conditions (such as rapid quenching from high enough temperatures ), this reaction is stretched in the opposite right direction, thus meaning a large number of “wrong” homonuclear bonds (improper to As 2 S 3 stoichiometry of the As–S system) and other structural defects like miscoordinated atoms. It is worth mentioning that similar hetero‐to‐homonuclear disproportionality balance in other ChGs is only slightly changed, being 35, 65, and 40 kJ mol −1 for binary As–Se, Ge–S, and Ge–Se glasses, respectively.…”

Section: Resultsmentioning

confidence: 99%

On the energetic criterion for destructive clustering of metallic nanoparticles in chalcogenide and oxide glassy matrices

Shpotyuk

Cebulski²

2015

Physica Status Solidi (b)

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The principal difference in the origin of high-order optical nonlinearities caused by metallic nanoparticles embedded destructively in oxide-and chalcogenide-type glassy matrices is justified from the viewpoint of a chemical-bond approach. The numerical x-criterion is introduced to describe this difference in terms of energetic barrier between the mean molar bond energies character for inner chemical interaction of destructed components of a host glassy matrix and guest implanted atoms such as Cu, Ag, and Au. It is confirmed that destructive clustering of metallic nanoparticles is possible in hard dielectric media like oxide glasses possessing a strong negative x-criterion.

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Section: Resultsmentioning

confidence: 99%

On the energetic criterion for destructive clustering of metallic nanoparticles in chalcogenide and oxide glassy matrices

Shpotyuk

Cebulski²

2015

Physica Status Solidi (b)

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“…The energetic balance of this reaction (1) is leftshifted attaining 40 kJ/mol for g-As 2 S 3 , as it follows from comparison of mean molar bond energies calculated from standard atomization enthalpies of relevant chemical compounds gathered in Table 1 (such estimation is appreciated within an error-bar of ±10 kJ/mol). Under non-equilibrium conditions (like rapid quenching from high temperatures exceeding the boiling point of As 2 S 3 [9,[27][28][29][30]), this reaction can stretch towards right side, thus meaning a great amount of "wrong" homonuclear bonds in the As-S alloy (not typical for stoichiometry of As-S system) and other structural defects, such as charged miscoordinated atoms [9]. With transition to g-As 2 Se 3 , the energetic balance of hetero-to-homo-nuclear bonding (1) is only slightly reduced reaching 35 kJ/mol.…”

Section: Chemical Bonding Disproportionality In a Glassmentioning

confidence: 99%

Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding

Shpotyuk¹

2017

Semicond. Phys. Quantum Electron. Optoelectron.

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Principal difference in origin of high-order optical non-linearities caused by metallic nanoparticles such as Cu, Ag and Au embedded destructively in oxide-and chalcogenide-type glassy matrices has been analyzed from the viewpoint of semiempirical chemical bond approach. The numerical criterion has been introduced to describe this difference in terms of mean molar bond energies character for chemical interaction between unfettered components of destructed host glassy matrix and embedded guest atoms. It has been shown that "soft" covalent-bonded networks of chalcogenide glasses of As/Ge-S/Se systems differ essentially from glass-forming oxides like silica by impossibility to accommodate agglomerates of metallic nanoparticles. In contrast, such nanostructurized entities can be well stabilized in Cu-, Ag-or Auembedded oxide glasses in full accordance with numerous experimental evidences. Recent unsubstantiated speculations trying to ascribe this ability to fully-saturated covalent matrices of chalcogenide glasses like As 2 S 3 are analyzed and criticized as the misleading and inconclusive ones.

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“…In late 1990s, Mikhailov et al . published the study of AsSI units in As‐S‐I glasses by means of dissolution, extraction and crystallization.…”

Section: Introductionmentioning

confidence: 99%

“…In late 1990s, Mikhailov et al 13 published the study of AsSI units in As-S-I glasses by means of dissolution, extraction and crystallization. The presence of AsI 3 molecules in the solution after extraction in CCl 4 clearly indicates the presence of AsI 3 molecules in the As-S-I glass matrix.…”

Section: Introductionmentioning

confidence: 99%

Determination of AsSI‐SbSI glasses short‐range structure via Raman spectroscopy, XPS and XRD

Kurushkin

Markov

Семенча

et al. 2017

Int J of Appl Glass Sci

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The ability to predict the influence of dopants (such as antimony) on the shortrange structure of As-S-I glasses has the potential to help design glasses with modified properties. In the present work, the short-range structure of As-Sb-S-I glasses has been investigated along AsSI-SbSI section of fixed sulfur and iodine concentrations and equivalent arsenic by antimony substitution. At high arsenic content (As:Sb≥2:1) antimony substitutes arsenic in AsI 3 molecules justified by Raman spectroscopy and XPS. Further antimony introduction (As:Sb<2:1) leads to the substitution of arsenic by antimony in -S-As-S-polymeric chains, leading to SbSI crystallization justified by XRD. The resulting two-dimensional schematic diagrams represent the AsSI-SbSI glasses short-range structure and show the mechanism of arsenic by antimony substitution.

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Structural chemical processes at the synthesis of chalcogenide glasses

Cited by 14 publications

References 5 publications

On the energetic criterion for destructive clustering of metallic nanoparticles in chalcogenide and oxide glassy matrices

On the energetic criterion for destructive clustering of metallic nanoparticles in chalcogenide and oxide glassy matrices

Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding

Determination of AsSI‐SbSI glasses short‐range structure via Raman spectroscopy, XPS and XRD

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