Understanding Polaronic Transport in Anatase TiO2 Films by Combining Precise Synthesis and First-Principles Many-Body Theory

Abstract

In complex oxides, charge carriers often couple strongly with lattice vibrations to form polarons-entangled electron-phonon quasiparticles whose transport properties remain difficult to characterize. Experimental access to intrinsic polaronic transport requires ultraclean samples, while theoretical descriptions demand methods beyond low-order perturbation theory. Here, we combine the growth of high-quality oxygen-vacancy-doped anatase TiO2 films by hybrid molecular beam epitaxy (MBE) with a first-principles electron-phonon diagrammatic Monte Carlo (FEP-DMC) framework recently developed for accurate polaron predictions. Our films exhibit record-high electron mobility for anatase TiO2, in excellent agreement with FEP-DMC calculations conducted prior to experiment, which predict a room-temperature mobility of 45 +/- 15 cm2V-1s-1 and a mobility-temperature scaling of mobility proportional to T^(-1.9 +/- 0.077). Microscopic analysis using scanning transmission electron microscopy and X-ray photoelectron spectroscopy reveals the role of oxygen vacancies in modulating transport at lower temperatures. FEP-DMC further provides quantitative insight into polaron formation energy, phonon cloud distribution, lattice distortion around the polaron, and the polaronic contribution to mobility. Together, these results establish a predictive theory-experiment workflow to characterize polarons and provide a microscopic understanding of large-polaron transport in anatase TiO2, with broader implications for complex oxides and other polaronic materials.