Two-Dimensional and Three-Dimensional Tetrel-Arsenide Frameworks Templated by Li and Cs Cations

Mark, Justin; Woo, Katherine E.; Zhu, Weidi; Ji, Bingheng; Lee, Shannon J.; Adeyemi, Adedoyin N.; Sen, Sabyasachi; Kovnir, Kirill

doi:10.1021/acs.chemmater.1c01053

Two-Dimensional and Three-Dimensional Tetrel-Arsenide Frameworks Templated by Li and Cs Cations

Journal Article · Thu Jun 10 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c01053· OSTI ID:1798868

^[1]; Woo, Katherine E. ^[1]; Zhu, Weidi ^[2]; Ji, Bingheng ^[3]; ^[1]; Adeyemi, Adedoyin N. ^[3]; ^[2]; ^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States)
Univ. of California, Davis, CA (United States)
Iowa State Univ., Ames, IA (United States)

Two new ternary tetrel pnictide phases, Li_1.08Ge_4.92As₇ and Cs_0.11Zn_0.05Si_0.95As, have been synthesized. Both compounds crystallize in new structure types, which demonstrate the flexibility of Ge(Si)–As layers when accommodating electropositive cations of various sizes. Li_1.08Ge_4.92As₇ displays a Ge-As layer motif that has not been observed in ternary Ge-As systems, while Cs_0.11Zn_0.05Si_0.95As exhibits a 3D framework composed of fragments of the 2D parent-phase SiAs. For Li_1.08Ge_4.92As₇, a combination of computational modeling and solid-state ⁷Li MAS NMR was used to establish the correct crystal structure with one mixed occupied Ge/Li site. The compositions of the phases were confirmed through energy-dispersive X-ray spectroscopy. Transport properties and UV–Vis spectroscopy reveal both reported compounds to be semiconductors. Cs_0.11Zn_0.05Si_0.95As shows high thermal stability with congruent melting at 1300 K and an exceptionally low thermal conductivity of 0.5 W m^–1 K^–1 at 300 K. Temperature-dependent Li-ion hopping dynamics in Li_1.08Ge_4.92As₇ was characterized using ⁷Li solid-state NMR.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1798868

Report Number(s):: IS-J--10,521

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 12 Vol. 33; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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