Observation of A1g Raman mode splitting in few layer black phosphorus encapsulated with hexagonal boron nitride

We investigate the impact of the encapsulation with hexagonal boron nitride (h-BN) on the Raman spectrum of few layer black phosphorus. The encapsulation results in a significant reduction of the line width of the Raman modes of black phosphorus, due to a reduced phonon scattering rate. We observe a so far elusive peak in the Raman spectra $\sim$4cm$^{-1}$ above the A$_{\text{g}}^1$ mode in trilayer and thicker flakes, which had not been observed experimentally. The newly observed mode originates from the strong black phosphorus inter-layer interaction, which induces a hardening of the surface atoms vibration with respect to the corresponding modes of the inner layers. The observation of this mode suggests a significant impact of h-BN encapsulation on the properties of black phosphorus and can serve as an indicator of the quality of its surface.
Comment: 15 pages, 4 figures just accepted for publication in Nanoscale http://pubs.rsc.org/en/Content/ArticleLanding/2017/NR/C7NR05588A#!divAbstract