Black phosphorus (BP) is an emerging two-dimensional material with intriguing physical properties. It is highly anisotropic and highly tunable by means of both the number of monolayers and surface doping. Here, we experimentally investigate and theoretically interpret the near-field properties of a-few-atomic-monolayer nanoflakes of BP. We discover near-field patterns of bright outside fringes and a high surface polarizability of nanofilm BP consistent with its surface-metallic, plasmonic behavior at mid-infrared frequencies <1176 cm-1. We conclude that these fringes are caused by the formation of a highly polarizable layer at the BP surface. This layer has a thickness of ~1 nm and exhibits plasmonic behavior. We estimate that it contains free carriers in a concentration of n≈1.1 × 1020 cm-3. Surface plasmonic behavior is observed for 10-40 nm BP thicknesses but absent for a 4-nm BP thickness. This discovery opens up a new field of research and potential applications in nanoelectronics, plasmonics and optoelectronics.
Keywords: black phosphorus; infrared spectroscopy; metallic surface layer; near-field nanoscopy; two-dimensional materials.