Ultrafast Dynamics of Rydberg Excitons and Their Optically Induced Charged Complexes in Encapsulated WSe₂ Monolayers

Quantum confinement and reduced dielectric screening lead to strong excitonic effects in atomically thin transition metal dichalcogenides (TMDs). Encapsulation of TMD monolayers in hexagonal boron nitride (hBN) unveils the excitonic Rydberg series below the free particle bandgap. The nonequilibrium response and the dynamics of these higher order exciton states and their multiparticle complexes remain almost unexplored. Here we use ultrafast pump-probe optical microscopy to measure the dynamics of excited-state (2s) excitons in hBN-encapsulated monolayer WSe₂. 2s excitons form through an ultrafast relaxation process from high-energy states and exhibit longer decay dynamics than ground state excitons due to their higher spatial extension. We detect light-induced formation of 2s trions with significant oscillator strength and faster decay dynamics than 2s excitons, attributed to an intra-excitonic Auger effect causing an additional decay channel. Our results shed light on the dynamics of excited state excitons in TMDs and their interactions with free carriers.