Core-level signature of long-range density-wave order and short-range excitonic correlations probed by transient XUV broadband spectroscopy

Advances in attosecond core-level spectroscopies have successfully unlocked the fastest dynamics involving high-energy electrons. Yet, these techniques are not conventionally regarded as an appropriate probe for low-energy quasiparticle interactions that govern the ground state of quantum materials, nor for studying long-range order because of their limited sensitivity to local charge environments. Here, by employing a unique cryogenic attosecond beamline, we identified clear core-level signatures of long-range charge-density-wave (CDW) formation in a quasi-2D excitonic insulator candidate 1T-TiSe₂, even though equilibrium photoemission and absorption measurements of the same core levels showed no spectroscopic singularity at the phase transition. Leveraging the high time resolution and intrinsic sensitivity to short-range charge excitations in attosecond core-level absorption, we observed compelling time-domain evidence for excitonic correlations in the normal-state of the material, whose presence has been subjected to a long-standing debate in equilibrium experiments because of interfering phonon fluctuations in a similar part of the phase space. Our findings support the scenario that short-range excitonic fluctuations prelude long-range order formation in the ground state, providing important insights in the mechanism of exciton condensation in a quasi-low-dimensional system. These results further demonstrate the importance of a simultaneous access to long- and short- range order with underlying dynamical processes spanning a multitude of time- and energy-scales, making attosecond spectroscopy an indispensable tool for both understanding the equilibrium phase diagram and for discovering novel, nonequilibrium states in strongly correlated materials.