Light-induced trion-exciton competition revealed by ultrafast photoemission

Abstract

Strong Coulomb interactions in low-dimensional quantum materials give rise to emergent bound states such as excitons and trions. Trions are conventionally secondary excitations, requiring both optical excitation and charge doping. In quasi-one-dimensional Ta$_2$NiS$_5$, however, an exceptionally large binding energy exceeding the single-particle band gap stabilizes an equilibrium trion gas under surface doping alone. Here, using time- and angle-resolved photoemission spectroscopy, we show that trions can also be generated purely optically, without external charge. Following photoexcitation of pristine Ta$_2$NiS$_5$ we observe a bright, momentum-localized, in-gap feature with a slow, fluence-dependent relaxation. Rate-equation modeling identifies it as a mixed population of trions and excitons, with the trions formed via an unconventional single-particle pathway that requires no photoexcited hole. The trion-exciton composition is controlled by pump fluence, with trions dominating the late-time relaxation. In surface doped samples, the same model with unchanged rates reproduces the full dynamics, linking the light-induced trions to their equilibrium counterparts through pump-induced dissociation and recapture. These results establish trARPES as a direct probe of charged quasiparticles far from equilibrium and open routes to optical control of neutral and charged excitations in correlated materials.