Understanding the relaxation and recombination processes of excited states in two-dimensional (2D)/three-dimensional (3D) semiconductor heterojunctions is essential for developing efficient optical and (opto)electronic devices, which integrate van der Waals 2D materials with more conventional 3D ones. In this work, we unveil the carrier dynamics and charge transfer in a monolayer of WSe2 on a GaAs substrate. We use time-resolved differential reflectivity to study the charge relaxation processes involved in the junction and how they change when compared to an electrically decoupled heterostructure, WSe2/hBN/GaAs. We observe that the monolayer in direct contact with the GaAs substrate presents longer optically excited carrier lifetimes (3.5 ns) when compared with the hBN-isolated region (1 ns), consistent with a strong reduction of radiative decay and a fast charge transfer of a single polarity. Through low-temperature measurements, we find evidence of a type-II band alignment for this heterostructure with an exciton dissociation that accumulates electrons in GaAs and holes in WSe2. The type-II band alignment and fast photoexcited carrier dissociation shown here indicate that WSe2/GaAs is a promising junction for advanced photovoltaic and other optoelectronic devices, making use of the best properties of van der Waals (2D) and conventional (3D) semiconductors.
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