Charge Versus Energy Transfer in Atomically Thin Graphene-Transition Metal Dichalcogenide van der Waals Heterostructures

Made from stacks of two-dimensional materials, van der Waals heterostructures exhibit unique lightmatter interactions and are promising for novel optoelectronic devices. The performance of such devices is governed by near-field coupling through, e.g., interlayer charge and/or energy transfer. New concepts and experimental methodologies are needed to properly describe two-dimensional heterointerfaces. Here, we report an original study of interlayer charge and energy transfer in atomically thin metal-semiconductor [i.e., graphene-transition metal dichalcogenide (TMD, here molybdenum diselenide, MoSe 2)] heterostructures using a combination of microphotoluminescence and Raman scattering spectroscopies. The photoluminescence intensity in graphene/MoSe2 is quenched by more than 2 orders of magnitude and rises linearly with the incident photon flux, demonstrating a drastically shortened (about 1 ps) room-temperature MoSe2 exciton lifetime. Key complementary insights are provided from a comprehensive analysis of the graphene and MoSe2 Raman modes, which reveals net photoinduced electron transfer from MoSe2 to graphene and hole accumulation in MoSe2. Remarkably, the steady-state Fermi energy of graphene saturates at 290 +/- 15 meV above the Dirac point. This reproducible behavior is observed both in ambient air and in vacuum and is discussed in terms of intrinsic factors (i.e., band offsets) and environmental effects. In this saturation regime, balanced photoinduced flows of electrons and holes may transfer to graphene, a mechanism that effectively leads to energy transfer. Using a broad range of incident photon fluxes and diverse environmental conditions, we find that the presence of net photoinduced charge transfer has no measurable impact on the near-unity photoluminescence quenching efficiency in graphene/MoSe2. This absence of correlation strongly suggests that energy transfer to graphene (either in the form of electron exchange or dipole-dipole interaction) is the dominant interlayer coupling mechanism between atomically thin TMDs and graphene.