Triplet Excitation and Electroluminescence from a Supramolecular Monolayer Embedded in a Boron Nitride Tunnel Barrier

We show that ordered monolayers of organic molecules stabilized by hydrogen bonding on the surface of exfoliated few-layer hexagonal boron nitride (hBN) flakes may be incorporated into van der Waals heterostructures with integral few-layer graphene contacts forming a molecular/two-dimensional hybrid tunneling diode. Electrons can tunnel through the hBN/molecular barrier under an applied voltage V_SD, and we observe molecular electroluminescence from an excited singlet state with an emitted photon energy hν > eV_SD, indicating upconversion by energies up to ∼1 eV. We show that tunneling electrons excite embedded molecules into singlet states in a two-step process via an intermediate triplet state through inelastic scattering and also observe direct emission from the triplet state. These heterostructures provide a solid-state device in which spin-triplet states, which cannot be generated by optical transitions, can be controllably excited and provide a new route to investigate the physics, chemistry, and quantum spin-based applications of triplet generation, emission, and molecular photon upconversion.