Evolution of structure and transport properties of the BaCuP clathrate-I framework with the introduction of Ga

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Sarkar, Arka
Viswanathan, Gayatri
Yox, Philip
Harycki, Stasia
Cerasoli, Frank T.
Wang, Jian
Perras, Frédéric A.
Gundlach-Graham, Alexander
Donadio, Davide
Kovnir, Kirill

Arka Sarkar, Gayatri Viswanathan, Philip Yox, Stasia Harycki, Frank T. Cerasoli, Jian Wang, Frédéric A. Perras, Alexander Gundlach-Graham, Davide Donadio, and Kirill Kovnir , "Evolution of structure and transport properties of the Ba8Cu16P30 clathrate-I framework with the introduction of Ga", Appl. Phys. Lett. 120, 191901 (2022) https://doi.org/10.1063/5.0093646


Two type-I clathrates were synthesized by introducing Ga into the framework of the BaCuP type-I clathrate. The introduction of minute amounts of Ga, 1.9% Ga/Mtotal (where  = Cu + Ga), resulted in the disturbance of the completely ordered superstructure of BaCuP. BaCuGaP crystallizes in a partially ordered orthorhombic clathrate-I superstructure with five out of 15 framework sites being jointly occupied by metal+phosphorus. Increasing the Ga content resulted in all framework sites being occupied by metal + phosphorus in the archetype cubic clathrate-I crystal structure of BaCuGaP with 8.2% Ga/. A combination of energy dispersive x-ray spectroscopy, inductively coupled plasma mass spectroscopy, and single crystal x-ray diffraction was used to determine the structures alongside the compositions. The positional disorder was verified by 31P solid state NMR spectroscopy. Characterization of the transport properties indicated that the Ga-substituted samples exhibit higher Seebeck coefficients and electrical resistivities compared to its pristine counterpart, in line with the expected reduction of the hole concentration due to Ga/Cu substitution. Moderate improvements in the thermoelectric power factor and overall figure-of-merit were observed for samples with 6.9% and 3.8% Ga/ as compared to those for the pristine BaCuP clathrate. Band structure calculations shed light on how Ga substitution affects the electronic structure and thermoelectric properties of studied clathrates.

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