Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C 60 monolayer. Scanning tunneling microscopy reveals the C 60 lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C 60 and BP reduce the inter-C 60 distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C 60 acquires an effective mass of 0.53–0.70 m e ( m e is the mass of free electrons), and has carrier mobility of ~200 to 440 cm 2 V −1 s −1 . The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.

We reveal the unique electronic characteristics of the conduction band (CB) of black phosphorus (BP) by combining low-temperature scanning tunneling microscopy/spectroscopy (STM/STS), density functional theory calculations, analytic fitting, and model simulations. We discover that the differential conductance spectrum, which represents the local density of states (LDOS) of BP, exhibits a linear character over a large energy range in the unoccupied electronic state region. Combining theoretical calculations, we demonstrate that the linear character right above the conduction band minimum originates from a specific combination of the anisotropic band dispersions of BP's CB. In particular, the wave function of BP's CB possesses a pronounced density between BP layers and extends into the vacuum significantly, which is in sharp contrast to those of adjacent bands. This makes the CB dominate STS signals even when the energy is sufficiently high to involve other bands, and maintains the linearity of the STS spectrum over a wide energy range. The fact that the CB provides linear DOS and possesses pronounced wave function density in BP interlayers provides new insights for engineering the electronic structures and properties of BP and BP based materials.