Atomic level structure of Ge-Sb-S glasses: Chemical short range order and long Sb-S bonds

Pethes, Ildikó; Nazabal, Virginie; Ari, Julien; Kaban, I.; Darpentigny, Jacques; Welter, Edmund; Gutowski, Olof; Bureau, Bruno; Messaddeq, Younès; Jóvári, P.

doi:10.1016/j.jallcom.2018.09.334

Cited by 24 publications

(12 citation statements)

References 59 publications

(53 reference statements)

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“…The Sb-S bond length (2.44 Å) is somewhat shorter than that found in Ge-Sb-S glasses by ND (2.48 Å [56]), but agrees with the values obtained by EXAFS for Sb-S systems (2.45-2.46 Å [68]) and by RMC method with EXAFS, ND and XRD measurements for ternary Ge-Sb-S glasses (2.45 Å [57]). (The Sb-S bond length of Kakinuma et al [56] is deduced from the total scattering function of S-deficient Ge-Sb-S glasses, where the presence of Ge-Sb pairs (with bond length around 2.61 -2.65 Å [57,58]) can cause the shift of the peak to higher values.…”

Section: Reverse Monte Carlo Simulationssupporting

confidence: 87%

“…S-S bonds were found in S-rich compositions [52,55,57]. M-M bonds were reported in Sdeficient samples [52,57,58] and in stoichiometric compositions as well [53,55], which shows some chemical disorder.…”

Section: Introductionmentioning

confidence: 94%

“…In Ge-Sb-S glasses [GeS 4/2 ] and [SbS 3/2 ] units are the main building blocks as shown in a lot of studies [52 -57]. S-S bonds were found in S-rich compositions [52,55,57]. M-M bonds were reported in Sdeficient samples [52,57,58] and in stoichiometric compositions as well [53,55], which shows some chemical disorder.…”

Section: Introductionmentioning

confidence: 98%

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The structure of near stoichiometric Ge-Ga-Sb-S glasses: A reverse Monte Carlo study

Pethes

Nazabal

Chahal

et al. 2019

Journal of Non-Crystalline Solids

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The structure of Ge 22 Ga 3 Sb 10 S 65 and Ge 15 Ga 10 Sb 10 S 65 glasses was investigated by neutron diffraction (ND), X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) measurements at the Ge, Ga and Sb K-edges. Experimental data sets were fitted simultaneously in the framework of the reverse Monte Carlo (RMC) simulation technique. Short range order parameters were determined from the obtained large-scale configurations. It was found that the coordination numbers of Ge, Sb and S are around the values predicted by the Mott-rule (4, 3 and 2, respectively). The Ga atoms have on average 4 nearest neighbors. The structure of these stoichiometric glasses can be described by the chemically ordered network model: Ge-S, Ga-S and Sb-S bonds are the most important. Long Sb-S distances (0.3 -0.4 Å higher than the usual covalent bond lengths) are observed, suggesting that Sb atoms can be found in various local environments. 15-16 groups of the periodic table, the total coordination number of the elements (N i ) follows the Mottrule [36]: It is equal to 8-N, where N is the number of electrons in the valence shell of the ith element (e. g. Ge-As-Se [37], Ge-As-Te [38], Ge-Sb-Se [39], Ge-Sb-Te [40]). However glasses containing group 13 elements can deviate from this rule, and the total coordination number of Ga or In can be four instead of three [41 -44]. The structure of several chalcogenide glasses can be described in the framework of the chemically ordered network model (CONM) [45, 46]. This model predicts that M-Ch bonds are preferable, where M denotes the elements from groups 13, 14 or 15, and Ch means the chalcogen element. The structure of the stoichiometric glass can be built from tetrahedral and/or pyramidal units such as [GeCh 4/2 ] or [SbCh 3/2 ]. The M-M and Ch-Ch bonds are present only in non-stoichiometric glasses: M-M bonds in Ch-deficit (Ch-under stoichiometric) compositions and Ch-Ch bonds in Ch-rich (Ch-over stoichiometric) glasses.preparing Ge 22 Ga 3 Sb 10 S 65 and Ge 15 Ga 10 Sb 10 S 65 , i.e. 5N for germanium, gallium, antimony or sulphur.Commercial sulphur was further purified by successive distillations to remove carbon (CO 2 , CS 2 , COS) and hydrates or sulphide hydride (H 2 O, OH, SH) impurities. Then, the required amounts of chemical reagents were put in silica ampoules and pumped under vacuum (10 -4 mbar) for a few hours. The tubes were then sealed and heated at 850°C for 12h in a rocking furnace to ensure the homogenization of the melt. After water quenching, the glass rods were annealed near their glass transition temperatures for 6h. The densities of the samples were determined using a Mettler Toledo XS64 system measuring the weights of the samples in air and water. The density values are shown in Table 1.Neutron diffraction experiments were carried out at the 7C2 diffractometer of LLB (Saclay, France).

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Section: Reverse Monte Carlo Simulationssupporting

confidence: 87%

Section: Introductionmentioning

confidence: 94%

See 1 more Smart Citation

The structure of near stoichiometric Ge-Ga-Sb-S glasses: A reverse Monte Carlo study

Pethes

Nazabal

Chahal

et al. 2019

Journal of Non-Crystalline Solids

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“…3 b. S-deficient [Ge 37 S 63 ] 1-x Sb x films are mainly composed of GeS 4/2 tetrahedral units and, upon addition of pure Sb, Sb–Sb and Sb–Ge bonds are formed with appearance of a small amount of SbS 3/2 pyramids. Therefore, in other words the amorphous network of our S-poor glasses can be depicted as a mix of GeSb 4-m S m tetrahedral motifs (with m = {0, 1, 2, 3, 4}) and few SbGe 3-m-n Sb m S n pyramidal units (with n + m = {0, 1, 2, 3}) in favour of homopolar Sb–Sb and wrong Sb–Ge bonds 39 – 42 .…”

Section: Resultsmentioning

confidence: 94%

Ge–Sb–S–Se–Te amorphous chalcogenide thin films towards on-chip nonlinear photonic devices

Dory

Castro-Chavarria

Verdy

et al. 2020

Sci Rep

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Thanks to their unique optical properties Ge–Sb–S–Se–Te amorphous chalcogenide materials and compounds offer tremendous opportunities of applications, in particular in near and mid-infrared range. This spectral range is for instance of high interest for photonics or optical sensors. Using co-sputtering technique of chalcogenide compound targets in a 200 mm industrial deposition tool, we show how by modifying the amorphous structure of GeSb w S x Se y Te z chalcogenide thin films one can significantly tailor their linear and nonlinear optical properties. Modelling of spectroscopic ellipsometry data collected on the as-deposited chalcogenide thin films is used to evaluate their linear and nonlinear properties. Moreover, Raman and Fourier-transform infrared spectroscopies permitted to get a description of their amorphous structure. For the purpose of applications, their thermal stability upon annealing is also evaluated. We demonstrate that depending on the GeSb w S x Se y Te z film composition a trade-off between a high transparency in near- or mid-infrared ranges, strong nonlinearity and good thermal stability can be found in order to use such materials for applications compatible with the standard CMOS integration processes of microelectronics and photonics.

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“…It is anticipated that a large number of S 2‐ ions were coordinated with the additional Ge 4+ , while the I ‐ as negative charge formed the [Sb–I] bond to compensate the sulfur‐deficient condition, that is, the formation of [SbS x I 3‐x ] units was promoted by the replacement of Ga with Ge element. Therefore, the large radius and highly polarizable I ‐ ions was involved in the formation of glass network leading to a bigger and looser channel for ions’ migration 14‐17 …”

Section: Resultsmentioning

confidence: 99%

Structure promoted electrochemical behavior and chemical stability of AgI‐doped solid electrolyte in sulfide glass system

Jiao

Zhang

et al. 2020

J Am Ceram Soc

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Ion‐conducting chalcogenide glass is a promising solid electrolyte with excellent conductivity and energy density for all‐solid‐state batteries. A suitable ionic channel for carriers in the amorphous network is urgently needed. In this work, the structural evolution of co‐doped metal cations (Ge and Ga) in the glass matrix and its influence on electrochemical behavior were studied using a series of GexGa16‐xSb64S128‐40AgI glass samples. The macroscopic properties of samples were examined by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and Raman tests. The electrochemical behavior of samples was investigated by AC impendence spectroscopy and cyclic voltammetry (CV) measurement. Furthermore, a deliquescence experiment was applied for the chemical stability test of glass samples. The ionic conductivity of samples was developed by adding Ga components. Notably, the electrochemical window of electrolytes was remarkably wide at approximately 5 V. The resistance of samples to humidity was characterized by the decreased Raman peaks. Analysis results show that the Ga‐related bonding structure evidently increased the chemical stability compared with the non‐Ga sample. This work provides an insight into the effective and stable ions transport, especially in the Ge(Ga)SbS glass system. These results promote the further investigation of sulfide solid electrolytes and practical application of all‐solid‐state batteries.

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Atomic level structure of Ge-Sb-S glasses: Chemical short range order and long Sb-S bonds

Cited by 24 publications

References 59 publications

The structure of near stoichiometric Ge-Ga-Sb-S glasses: A reverse Monte Carlo study

The structure of near stoichiometric Ge-Ga-Sb-S glasses: A reverse Monte Carlo study

Ge–Sb–S–Se–Te amorphous chalcogenide thin films towards on-chip nonlinear photonic devices

Structure promoted electrochemical behavior and chemical stability of AgI‐doped solid electrolyte in sulfide glass system

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