Black phosphorus consists of stacked layers of phosphorene, a two-dimensional semiconductor with promising device characteristics. We report the realization of a widely tunable band gap in few-layer black phosphorus doped with potassium using an in situ surface doping technique. Through band structure measurements and calculations, we demonstrate that a vertical electric field from dopants modulates the band gap, owing to the giant Stark effect, and tunes the material from a moderate-gap semiconductor to a band-inverted semimetal. At the critical field of this band inversion, the material becomes a Dirac semimetal with anisotropic dispersion, linear in armchair and quadratic in zigzag directions. The tunable band structure of black phosphorus may allow great flexibility in design and optimization of electronic and optoelectronic devices.

Two-dimensional (2D) crystals have emerged as a class of materials with tunable carrier density. Carrier doping to 2D semiconductors can be used to modulate many-body interactions and to explore novel composite particles. The Holstein polaron is a small composite particle of an electron that carries a cloud of self-induced lattice deformation (or phonons), which has been proposed to play a key role in high-temperature superconductivity and carrier mobility in devices. Here we report the discovery of Holstein polarons in a surface-doped layered semiconductor, MoS, in which a puzzling 2D superconducting dome with the critical temperature of 12 K was found recently. Using a high-resolution band mapping of charge carriers, we found strong band renormalizations collectively identified as a hitherto unobserved spectral function of Holstein polarons. The short-range nature of electron-phonon (e-ph) coupling in MoS can be explained by its valley degeneracy, which enables strong intervalley coupling mediated by acoustic phonons. The coupling strength is found to increase gradually along the superconducting dome up to the intermediate regime, which suggests a bipolaronic pairing in the 2D superconductivity.

We report the realization of novel symmetry-protected Dirac fermions in a surface-doped two-dimensional (2D) semiconductor, black phosphorus. The widely tunable band gap of black phosphorus by the surface Stark effect is employed to achieve a surprisingly large band inversion up to ∼0.6  eV. High-resolution angle-resolved photoemission spectra directly reveal the pair creation of Dirac points and their movement along the axis of the glide-mirror symmetry. Unlike graphene, the Dirac point of black phosphorus is stable, as protected by space-time inversion symmetry, even in the presence of spin-orbit coupling. Our results establish black phosphorus in the inverted regime as a simple model system of 2D symmetry-protected (topological) Dirac semimetals, offering an unprecedented opportunity for the discovery of 2D Weyl semimetals.