Rapid Characterization of Point Defects in Solid-State Ion Conductors Using Raman Spectroscopy, Machine-Learning Force Fields, and Atomic Raman Tensors

The successful design of solid-state photo- and electrochemical devices depends on the careful engineering of point defects in solid-state ion conductors. Characterization of point defects is critical to these efforts, but the best-developed techniques are difficult and time-consuming. Raman spectroscopy─with its exceptional speed, flexibility, and accessibility─is a promising alternative. Raman signatures arise from point defects due to local symmetry breaking and structural distortions. Unfortunately, the assignment of these signatures is often hampered by a shortage of reference compounds and corresponding reference spectra. This issue can be circumvented by calculation of defect-induced Raman signatures from first principles, but this is computationally demanding. Here, we introduce an efficient computational procedure for the prediction of point defect Raman signatures in solid-state ion conductors. Our method leverages machine-learning force fields and "atomic Raman tensors", i.e., polarizability fluctuations due to motions of individual atoms. We find that our procedure reduces computational cost by up to 80% compared to existing first-principles frozen-phonon approaches. These efficiency gains enable synergistic computational-experimental investigations, in our case allowing us to precisely interpret the Raman spectra of Sr(Ti