Spectroscopy of buried states in black phosphorus with surface doping

Electrostatic gating or alkali metal evaporation can be successfully employed to tune the interface of layered black phosphorus (BP) from a semiconductor to a 2D Dirac semimetal. Although Angle Resolved Photoelectron Spectroscopy (ARPES) experiments have captured the collapse of the band gap in the inversion layer, a quantitative estimation of band structure evolution has been hindered by the short escape depth and matrix elements of the probed photoelectrons. Here, we precisely monitor the evolution of electronic states using time-resolved ARPES at a photon energy of 6.3 eV. The probing depth of laser-based ARPES is long enough to observe the buried electronic states originating from the valence band maximum. Our data shows that the band gap has a maximal value of 0.32 eV in the pristine sample, and that it shrinks down monotonically by increasing the carrier concentration in the topmost layer. Most interestingly, the band velocity of the valence band increases by a factor of two along the armchair direction, surpassing the value reported in graphene on silicon carbide (SiC). This control of band structure via external gating will be of interest with regard to the design of optoelectronic devices.