Boosting and Balancing Electron and Hole Mobility in Single- and Bilayer WSe₂ Devices via Tailored Molecular Functionalization

WSe2 is a layered ambipolar semiconductor enabling hole and electron transport, which renders it a suitable active component for logic circuitry. However, solid-state devices based on single- and bilayer WSe2 typically exhibit unipolar transport and poor electrical performance when conventional SiO2 dielectric and Au electrodes are used. Here, we show that silane-containing functional molecules form ordered monolayers on the top of the WSe2 surface, thereby boosting its electrical performance in single- and bilayer field-effect transistors. In particular, by employing SiO2 dielectric substrates and top Au electrodes, we measure unipolar mobility as high as μh = 150 cm2 V–1 s–1 and μe = 17.9 cm2 V–1 s–1 in WSe2 single-layer devices when ad hoc molecular monolayers are chosen. Additionally, by asymmetric double-side functionalization with two different molecules, we provide opposite polarity to the top and bottom layer of bilayer WSe2, demonstrating nearly balanced ambipolarity at the bilayer limit. Our results indicate that the controlled functionalization of the two sides of the WSe2 mono- and bilayer flakes with highly ordered molecular monolayers offers the possibility to simultaneously achieve energy level engineering and defect functionalization, representing a path toward deterministic control over charge transport in 2D materials.