Photon Upconversion of Defect-Bound Excitons in hBN-Encapsulated MoS₂ Monolayer

Atomic defects associated with vacancies in two-dimensional transition metal dichalcogenide monolayers efficiently trap charged carriers and strongly localize excitons. Defects in semiconducting monolayers are seldomly utilized for enhancing optical phenomena, although they may provide resonant intermediate states within the energy band gap for applications with multiphoton excitations, like highly efficient and thermally robust photon upconversion. In an MoS₂ monolayer encapsulated by hBN with high defect and resident electron densities, we observe an upconversion of localized exciton (X_L) emission with a huge energy gain of up to 290 meV. The upconverted X_L emission is robust up to temperatures of about 120 K and exhibits a sublinear or a nearly linear laser power dependence for the energy gain of about 100 meV and above 200 meV, respectively. The upconversion mechanism is explained by a cooperative energy transfer process between the photocreated and resident electrons, in which hybridized pairs of single sulfur vacancies likely act as real intermediate states. Additionally, we find a weak upconversion of the neutral exciton photoluminescence with an energy gain of about 350 meV for quasi-resonant excitation of the X_L exciton. It is attributed to a two-step, two-photon absorption.