We investigate the excitonic species in WS2 monolayers transferred onto III–V semiconductor substrates with different surface treatments. When the III–V substrates were covered with amorphous native oxides, negatively charged excitons dominated the spectral weight in low-temperature near-resonance photoluminescence (PL) measurements. However, when the native oxides of the III–V substrates were reduced, neutral excitons began to dominate the spectral weight, indicating a reduction in the electron density in the WS2 monolayers. The removal of the native oxides enhanced the electron transfer from the WS2 monolayer to the III–V substrate. In addition, an additional shoulder-like PL feature appeared ∼50 meV below the emission of neutral excitons, which can be attributed to the emission of localized excitons. When the III–V substrate surface was passivated by sulfur after the reduction of the native oxides, neutral excitons still dominated the spectral weight. However, the low-energy PL shoulder disappeared again, suggesting the effective delocalization of excitons through substrate surface passivation. Surface engineering of the semiconductor substrates for two-dimensional (2D) materials can provide a novel approach to control the carrier density of the 2D materials, implement deterministic carrier localization or delocalization for the 2D materials, and facilitate the interlayer transfer of charge, spin, and valley currents. These findings open the avenue for novel device concepts and phenomena in mixed-dimensional semiconductor heterostructures.
