This work investigates the effects of oxygen and humidity on black phosphorous (BP) and black arsenic phosphorous (AsxP1−x ) flakes using Raman spectroscopy and in situ electric transport measurements (four-probe resistance and thermoelectric power, TEP). The results show that the incorporation of arsenic into the lattice of BP renders it more stable, with the degradation times for BP, As0.2P0.8, and As0.4P0.6 being 4, 5, and 11 days, respectively. The P-P Raman peak intensities were determined to decrease with exposure to oxygen and moisture. The TEP measurements confirmed that both BP and AsxP1−x are p-type semiconductors with the TEP of As0.4P0.6 stabilizing more slowly than that of BP. In addition, the four-probe resistance of BP and AsxP1−x stabilized significantly faster when exposed to air after being degassed in a vacuum. This was attributed to the charge transfer between the oxygen redox potential of air and the Fermi energy (EF) of the semiconductors.

Structural evolution of Li‐intercalated and pristine black phosphorous (BP) under high‐pressure (up to ≈8 GPa) is studied using in situ Raman spectroscopy. Even though both materials show a monotonic blueshift of the out‐of‐plane vibrational mode (A1g) with pressure, Li‐intercalated BP do not show a blueshift until a threshold pressure (2.4 GPa) is reached to compensate the structural expansion caused by intercalation. However, the in‐plane modes (B2g and A2g) in each sample respond differently. In the mid‐pressure region, they both show redshifts which in Li‐intercalated BP is also followed by abrupt blueshifts. Such behavior indicates pressure‐induced structural reorganizations inside the material. Computational modeling reveals the existence of a process of P─P bond breaking and reforming in the system due to the redistribution of intercalated Li atoms under pressure. This work shows the significance of combined effect of pressure and intercalation on structural changes in the search for new phases of BP and other two‐dimensional (2D) materials.

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 g 1 , B 2 g , and A g 2 ) steadily redshifted as exposure times were increased, with modes B 2 g and A g 2 shifting faster than A g 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.