Friedrich, Daniel and Schlosser, Marc and Pfitzner, Arno (2017) Interconversion of One-Dimensional Thiogallates Cs-2[Ga-2(S-2)(2-x),S2+x] (x=0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions. CRYSTAL GROWTH & DESIGN, 17 (9). pp. 4887-4892. ISSN 1528-7483, 1528-7505
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The potential of cesium polysulfide-flux reactions for the synthesis of chalcogenogallates was investigated by using X-ray diffraction and Raman spectroscopy. An investigation of possible factors influencing the product formation revealed that only the polysulfide content x in the Cs2Sx melts has an influence on the crystalline reaction product. From sulfur-rich melts (x > 7), CsGaS3 is formed, whereas sulfur-poor melts (x < 7) lead to the formation of Cs2Ga2S5- In situ investigations using high-temperature Raman spectroscopy revealed that the crystallization of these solids takes place upon cooling of the melts. Upon heating, CsGaS3 and Cs2Ga2S5 release gaseous sulfur due to the degradation of S-2(2-) units. This decomposition of CsGaS3 to Cs2Ga2S5 and finally to CsGaS2-mC16 was further studied in situ by using high-temperature X-ray powder diffraction. A combination of the polysulfide reaction route and the high-temperature decomposition leads to the possibility of the directed interconversion of these thiogallates. The presence of disulfide units in the anionic substructures of these thiogallates has a significant influence on the electronic band structures and their optical properties. This influence was studied by using UV/vis-diffuse reflectance spectroscopy and DFT simulations, revealing a trend of smaller band gaps with increasing S-2(2-) content.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | STRUCTURAL-CHARACTERIZATION; METAL POLYCHALCOGENIDES; CRYSTAL-STRUCTURES; COMPOUND; ANIONS; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Arno Pfitzner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Dec 2018 13:15 |
| Last Modified: | 20 Feb 2019 07:43 |
| URI: | https://pred.uni-regensburg.de/id/eprint/1279 |
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