Vapor-Phase Intercalation of Cesium into Black Phosphorous

• Published in: Journal of physical chemistry. C Vol. 125; no. 49; pp. 27440 - 27448
• Main Authors: Abu, Usman O, Musa, Md Rajib Khan, Rajapakse, Manthila, Karki, Bhupendra, Vithanage, Dinushika, Yu, Ming, Sumanasekera, Gamini, Jasinski, Jacek B
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16.12.2021
• Subjects: C: Physical Properties of Materials and Interfaces; Cesium; Diffraction; Intercalation; Layers; MATERIALS SCIENCE; NANOSCIENCE AND NANOTECHNOLOGY; Two dimensional materials
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.1c08574

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 (Ag 1, B2g , and Ag 2) steadily redshifted as exposure times were increased, with modes B2g and Ag 2 shifting faster than Ag 1. 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. Density functional theory (DFT) calculations were used to delve deeper into understanding Cs intercalation on the structural evolution of BP.