Biexciton and Singlet Trion Upconvert Exciton Photoluminescence in a MoSe₂ Monolayer Supported by Acoustic and Optical K-Valley Phonons

Transition metal dichalcogenide monolayers represent unique platforms for studying both electronic and phononic interactions as well as intra- and intervalley exciton complexes. Here, we investigate the upconversion of exciton photoluminescence in MoSe2 monolayers. Within the nominal transparency window of MoSe2 the exciton emission is enhanced for resonantly addressing the spin-singlet negative trion and neutral biexciton at a few tens of meV below the neutral exciton transition. We identify that the A'(1) optical phonon at the K valley provides the energy gain in the upconversion process at the trion resonance, while ZA(K) phonons with their spin- and valley-switching properties support the biexciton driven upconversion of the exciton emission. Interestingly, the latter upconversion process yields unpolarized exciton photoluminescence, while the former also leads to circularly polarized emission. Our study highlights high-order exciton complexes interacting with optical and acoustic K-valley phonons and upconverting light into the bright exciton.