Charge‐Transfer‐Mediated Exciton Dynamics in Van der Waals Antiferromagnet NiPS₃

Abstract2D van der Waals antiferromagnets have emerged as excellent candidates for studying novel low‐dimensional magnetism. The recently discovered spin–orbit‐entangled excitonic bound state appearing below the Néel temperature of 150 K in 2D antiferromagnetic NiPS3 (the so‐called Zhang–Rice (ZR) exciton) has drawn considerable attention in terms of exploring the strong correlation of spins, orbitals, and charges in a localized many‐body state. However, the formation mechanism of ZR excitons remains unclear, and its ultrafast dynamics have yet to be fully explored. Here, utilizing broadband transient reflectivity spectroscopy, the strong correlation between the charge‐transfer state excitation and the dynamic evolution of ZR excitons is investigated. Through systematic tuning of the pumping photon energy across the charge‐transfer state in NiPS3, the results reveal a short radiative lifetime of tens of picoseconds and a long nonradiative lifetime of up to nanoseconds for ZR excitons following an ultrafast charge transfer of ≈2 ps from the charge‐transfer state. The findings provide evidence of charge‐transfer‐induced ZR excitonic states in NiPS3, where the intriguing phenomena of strongly coupled spins and charges can be explored.