Laser-driven ultrafast impedance spectroscopy for measuring complex ion hopping processes

Superionic conductors, or solid-state ion-conductors that surpass 0.01 S/cm in conductivity, can enable more energy dense batteries, robust artificial ion pumps, and optimized fuel cells. However, tailoring superionic conductors require precise knowledge of ion migration mechanisms that are still not well understood, due to limitations set by available spectroscopic tools. Most spectroscopic techniques do not probe ion hopping on its inherent picosecond timescale, nor the many-body correlations between the migrating ions, lattice vibrational modes, and charge screening clouds--all of which are posited to greatly enhance ionic conduction. Here, we develop an ultrafast technique that measures the time-resolved change in impedance upon light excitation which triggers selective ion-coupled correlations. We apply our proposed technique to study a solid-state Li+ conductor Li0.5La0.5TiO3 (LLTO). We compare the relative change in impedance of LLTO before and after a UV to THz frequency excitation to map the corresponding ion-many-body-interaction correlations. We also develop a cost-effective, non-time-resolved laser-driven impedance method that is more accessible for lab-scale adoption. From both our techniques, we determine that electronic screening and phonon-mode interactions dominate the ion migration pathway of LLTO. Although we only present one case study, our technique can also probe O2-, H+, or other ion and charge carrier transport phenomena where ultrafast correlations control transport. Furthermore, the temporal relaxation of the measured impedance can distinguish ion transport effects caused by many-body correlations, optical heating, correlation, and memory behavior.