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Exfoliated black phosphorus has recently emerged as a new two-dimensional crystal that, due to its peculiar and anisotropic crystalline and electronic band structures, may have potentially important applications in electronics, optoelectronics and photonics. Despite the fact that the edges of layered crystals host a range of singular properties whose characterization and exploitation are of utmost importance for device development, the edges of black phosphorus remain poorly characterized. In this work, the atomic structure and the behavior of phonons near different black phosphorus edges are experimentally and theoretically studied using Raman spectroscopy and density functional theory calculations. Polarized Raman results show the appearance of new modes at the edges of the sample, and their spectra depend on the atomic structure of the edges (zigzag or armchair). Theoretical simulations confirm that the new modes are due to edge phonon states that are forbidden in the bulk, and originated from the lattice termination rearrangements.
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The travel of heat in insulators is commonly pictured as a flow of phonons scattered along their individual trajectory. In rare circumstances, momentum-conserving collision events dominate, and thermal transport becomes hydrodynamic. One of these cases, dubbed the Poiseuille flow of phonons, can occur in a temperature window just below the peak temperature of thermal conductivity. We report on a study of heat flow in bulk black phosphorus between 0.1 and 80 K. We find a thermal conductivity showing a faster than cubic temperature dependence between 5 and 12 K. Consequently, the effective phonon mean free path shows a nonmonotonic temperature dependence at the onset of the ballistic regime, with a size-dependent Knudsen minimum. These are hallmarks of Poiseuille flow previously observed in a handful of solids. Comparing the phonon dispersion in black phosphorus and silicon, we showthat the phase space for normal scattering events in black phosphorus is much larger. Our results imply that the most important requirement for the emergence of Poiseuille flowis the facility ofmomentum exchange between acoustic phonon branches. Proximity to a structural transition can be beneficial for the emergence of this behavior in clean systems, even when they do not exceed silicon in purity.
Phosphorus atomic chains, the utmost-narrow nanostructures of black phosphorus (BP), are highly relevant to the in-depth development of BP into one-dimensional (1D) regime. In this contribution, we report a top-down route to prepare atomic chains of BP via electron beam sculpting inside a transmission electron microscope (TEM). The growth and dynamics (i.e. rupture and edge migration) of 1D phosphorus chains are experimentally captured for the first time. Furthermore, the dynamic behaviors and associated energetics of the as-formed phosphorus chains are further corroborated by density functional theory (DFT) calculations. The 1D counterpart of BP will serve as a novel platform and inspire further exploration of the versatile properties of BP.
Black phosphorus presents a very anisotropic crystal structure, making it a potential candidate for hyperbolic plasmonics, characterized by a permittivity tensor where one of the principal components is metallic and the other dielectric. Here we demonstrate that atomically thin black phosphorus can be engineered to be a hyperbolic material operating in a broad range of the electromagnetic spectrum from the entire visible spectrum to ultraviolet. With the introduction of an optical gain, a new hyperbolic region emerges in the infrared. The character of this hyperbolic plasmon depends on the interplay between gain and loss along the two crystalline directions.
In a semimetal, both electron and hole carriers contribute to the density of states at the Fermi level. The small band overlaps and multi-band effects give rise to many novel electronic properties, such as relativistic Dirac fermions with linear dispersion, titanic magnetoresistance and unconventional superconductivity. Black phosphorus has recently emerged as an exceptional semiconductor with high carrier mobility and a direct, tunable bandgap. Of particular importance is the search for exotic electronic states in black phosphorus, which may amplify the materials potential beyond semiconductor devices. Here we show that a moderate hydrostatic pressure effectively suppresses the band gap and induces a Lifshitz transition from semiconductor to semimetal in black phosphorus; a colossal magnetoresistance is observed in the semimetallic phase. Quantum oscillations in high magnetic field reveal the complex Fermi surface topology of the semimetallic black phosphorus. In particular, a Dirac-like fermion emerges at around 1.2 GPa, which is continuously tuned by external pressure. The observed semi-metallic behavior greatly enriches black phosphoruss material property, and sets the stage for the exploration of novel electronic states in this material. Moreover, these interesting behaviors make phosphorene a good candidate for the realization of a new two-dimensional relativistic electron system, other than graphene.
We report operating temperatures and heating coefficients measured in a multi-layer black phosphorus device as a function of injected electrical power. By combining micro-Raman spectroscopy and electrical transport measurements, we have observed a linear temperature increase up to 600K at a power dissipation rate of 0.896Kmu m^3/mW. By further increasing the bias voltage, we determined the threshold power and temperature for electrical breakdown and analyzed the fracture in the black phosphorus layer that caused the device failure by means of scanning electron microscopy and atomic force microscopy. The results will benefit the research and development of electronics and optoelectronics based on novel two-dimensional materials.
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