Modulation of transport properties via S/Br substitution: solvothermal synthesis, crystal structure, and transport properties of Bi13S17Br3. Issue 43 (26th October 2022)

• Record Type: Journal Article
• Authors: Amarasinghe, Dinesh K.; Yox, Philip; Viswanathan, Gayatri; Adeyemi, Adedoyin N.; Kovnir, Kirill
• Is Part Of: Dalton transactions. Volume 51:Issue 43(2022)
• Page Start: 16748
• Page End: 16756
• Publication Date: 2022-10-26
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt02295h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The synthesis, formation mechanism, crystal structure, and transport properties of the bismuth chalcohalide Bi13 S17 Br3 are reported. Abstract : The solvothermal synthetic exploration of the Bi–S–halogen phase space resulted in the synthesis of two bismuth sulfohalides with common structural motifs. Bi13 S18 I2 was confirmed to have the previously reported composition and crystal structure. In contrast, the bromide analogue was shown to have a formula of neither Bi19 S27 Br3 nor Bi13 S18 Br2, in contrast to the previous reports. The composition, refined from single crystal X-ray diffraction and confirmed by elemental analysis, high-resolution powder X-ray diffraction, and total scattering, is close to Bi13 S17 Br3 due to the partial S/Br substitution in the framework. Bi13 S18 I2 and Bi13 S17 Br3 are n -type semiconductors with similar optical bandgaps of ∼0.9 eV but different charge and heat transport properties. Due to the framework S/Br disorder, Bi13 S17 Br3 exhibits lower thermal and electrical conductivities than the iodine-containing analogue. The high Seebeck coefficients and ultralow thermal conductivities indicate that the reported bismuth sulfohalides are promising platforms to develop novel thermoelectric materials.