Vapor-Phase Intercalation of Cesium into Black Phosphorous

Abu, Usman O.; Musa, Md Rajib Khan; Rajapakse, Manthila; Karki, Bhupendra; Vithanage, Dinushika; Yu, Ming; Sumanasekera, Gamini; Jasinski, Jacek B.

doi:10.1021/acs.jpcc.1c08574

Vapor-Phase Intercalation of Cesium into Black Phosphorous

Journal Article · Wed Dec 01 04:00:00 EST 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c08574· OSTI ID:1834141

Abu, Usman O. ^[1]; Musa, Md Rajib Khan ^[2]; Rajapakse, Manthila ^[2]; ^[2]; Vithanage, Dinushika ^[2]; Yu, Ming ^[2]; Sumanasekera, Gamini ^[2]; ^[2]

Univ. of Louisville, KY (United States); University of Louisville
Univ. of Louisville, KY (United States)

Cesium vapors were charged into black phosphorous (BP) flakes at varied times and at a temperature gradient of 150 °C. The X-ray diffraction (XRD) measurements of these samples suggest a reduction in the strength of van der Waal interactions between BP layers leading to the loss of coherence of out-of-plane peaks. At the same time, the three main Raman modes of BP (A_g¹, B_{2_g}, and A_g²) steadily redshifted as exposure times were increased, with modes B_{2_g} and A_g² shifting faster than A_g¹. After initial rapid downshifts of active BP phonon modes, this intercalation strategy showed its limits following prolonged exposure times. Saturation of BP flakes by Cs vapors ensued and the kinetics was fitted with an exponential decay function. Furthermore, the thermoelectric power (TEP) of cesiated BP exhibited an inversion in sign from positive to negative around 400 K, lending credence to the transformation of as-prepared BP which is a p-type semiconductor to an n-type equivalent due to Cs atom intercalation driven shifting of the Fermi level toward the conduction band of BP and the donation of electrons from Cs. Furthermore, density functional theory (DFT) calculations were used to delve deeper into understanding Cs intercalation on the structural evolution of BP.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Louisville, KY (United States)

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

Grant/Contract Number:: SC0019348

OSTI ID:: 1834141

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 49 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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