Cause, Consequence, and Control of Ag Vacancies in BaAg2–xAs2

Kyveryga, Victoria; Yox, Philip; Viswanathan, Gayatri; Sarkar, Arka; Wang, Lin-Lin; Kovnir, Kirill

doi:10.1021/acs.inorgchem.4c03006

Title: Cause, Consequence, and Control of Ag Vacancies in BaAg_2–xAs₂

Journal Article · 04 October 2024 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.4c03006 · OSTI ID:2475187

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Iowa State University, Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)
Iowa State University, Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States); Colorado School of Mines, Golden, CO (United States)
Ames Laboratory (AMES), Ames, IA (United States)

The impact of transition metal (Ag) deficiencies on the structural and transport properties of ThCr₂Si₂-type arsenides are investigated. We experimentally confirm a partial occupancy of Ag in BaAg_2–xAs₂, which can be predictably controlled within 0.053(5) ≤ x ≤ 0.19(1) by varying the quenching temperature during the crystal growth. Density functional theory calculations reveal that substoichiometric concentrations of Ag lower the density of states at the Fermi level, providing an electronic cause for the tendency of Ag to form vacancies. Furthermore, this vacancy concentration is linked to a characteristic kink in electrical resistivity that can be substantially shifted from 22 to 125 K and is established as the metric of a low-temperature structural phase transition (SPT) in BaAg_2–xAs₂. Along with electrical resistivity, the Seebeck coefficient and heat capacity for selected BaAg_2–xAs₂ samples are presented, which also exhibit anomalies due to the SPT.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-07CH11358; SC0023509; AC02-06CH11357

OSTI ID:: 2475187

Report Number(s):: IS-J--11,455

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 43 Vol. 63; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Crystal structure
Crystals
Defects in solids
Diffraction
Fluxes

Title: Cause, Consequence, and Control of Ag Vacancies in BaAg2–xAs2

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Title: Cause, Consequence, and Control of Ag Vacancies in BaAg_2–xAs₂