Gate-Tunable Giant Stark Effect in Few-Layer Black Phosphorus

Two-dimensional black phosphorus (BP) has sparked enormous research interest due to its high carrier mobility, layer-dependent direct bandgap and outstanding in-plane anisotropic properties. BP is one of the few two-dimensional materials where it is possible to tune the bandgap over a wide energy range from the visible up to the infrared. In this article, we report the observation of a giant Stark effect in electrostatically gated few-layer BP. Using low-temperature scanning tunnelling microscopy, we observed that in few-layer BP, when electrons are injected, a monotonic reduction of the bandgap occurs. The injected electrons compensate the existing defect-induced holes and achieve up to 35.5% bandgap modulation in the light-doping regime. When probed by tunnelling spectroscopy, the local density of states in few-layer BP shows characteristic resonance features arising from layer-dependent sub-band structures due to quantum confinement effects. The demonstration of an electrical gate-controlled giant Stark effect in BP paves the way to designing electro-optic modulators and photodetector devices that can be operated in a wide electromagnetic spectral range

Resolving the Spatial Structures of Bound Hole States in Black Phosphorus

Understanding the local electronic properties of individual defects and dopants in black phosphorus (BP) is of great importance for both fundamental research and technological applications. Here, we employ low-temperature scanning tunnelling microscope (LT-STM) to probe the local electronic structures of single acceptors in BP. We demonstrate that the charge state of individual acceptors can be reversibly switched by controlling the tip-induced band bending. In addition, acceptor-related resonance features in the tunnelling spectra can be attributed to the formation of Rydberg-like bound hole states. The spatial mapping of the quantum bound states shows two distinct shapes evolving from an extended ellipse shape for the 1s ground state to a dumbbell shape for the 2p_<i>x</i> excited state. The wave functions of bound hole states can be well-described using the hydrogen-like model with anisotropic effective mass, corroborated by our theoretical calculations. Our findings not only provide new insight into the many-body interactions around single dopants in this anisotropic two-dimensional material but also pave the way to the design of novel quantum devices

Ultrafast Electrochemical Expansion of Black Phosphorus toward High-Yield Synthesis of Few-Layer Phosphorene

To bridge the gap between laboratory research and commercial applications, it is vital to develop scalable methods to produce large quantities of high-quality and solution-processable few-layer phosphorene (FLBP). Here, we report an ultrafast cathodic expansion (in minutes) of bulk black phosphorus in the nonaqueous electrolyte of tetraalkylammonium salts that allows for the high-yield (>80%) synthesis of nonoxidative few-layer BP flakes with high crystallinity in ambient conditions. Our detailed mechanistic studies reveal that cathodic intercalation and subsequent decomposition of solvated cations result in the ultrafast expansion of BP toward the high-yield production of FLBP. The FLBPs thus obtained show negligible structural deterioration, excellent electronic properties, great solution processability, and high air stability, which allows us to prepare stable BP inks (2 mg/mL) in low-boiling point solvents for large-area inkjet printing and fabrication of optoelectronic devices

Ultrafast Electrochemical Expansion of Black Phosphorus toward High-Yield Synthesis of Few-Layer Phosphorene

To bridge the gap between laboratory research and commercial applications, it is vital to develop scalable methods to produce large quantities of high-quality and solution-processable few-layer phosphorene (FLBP). Here, we report an ultrafast cathodic expansion (in minutes) of bulk black phosphorus in the nonaqueous electrolyte of tetraalkylammonium salts that allows for the high-yield (>80%) synthesis of nonoxidative few-layer BP flakes with high crystallinity in ambient conditions. Our detailed mechanistic studies reveal that cathodic intercalation and subsequent decomposition of solvated cations result in the ultrafast expansion of BP toward the high-yield production of FLBP. The FLBPs thus obtained show negligible structural deterioration, excellent electronic properties, great solution processability, and high air stability, which allows us to prepare stable BP inks (2 mg/mL) in low-boiling point solvents for large-area inkjet printing and fabrication of optoelectronic devices