Antiadiabatic Small Polaron Formation in the Charge Transfer Insulator ErFeO3

TL;DR

This study uses transient XUV spectroscopy to observe antiadiabatic small polaron formation in ErFeO3, revealing a longer formation timescale and emphasizing the role of electron correlations and lattice dynamics in polaron behavior.

Contribution

First experimental observation of antiadiabatic small polaron formation in ErFeO3, demonstrating the importance of electron correlations and lattice dynamics in polaron transport.

Findings

Polaron formation takes several picoseconds, longer than in other materials.

Electron hopping integral exceeds reorganization energy, confirming antiadiabaticity.

Dynamical electron correlations are crucial for understanding small polaron behavior.

Abstract

Small polaron formation is dominant across a range of condensed matter systems. Small polarons are usually studied in terms of ground-state transport and thermal fluctuations, but small polarons can also be created impulsively by photoexcitation. The temporal response of the lattice and local electron correlations can then be separated, such as with transient XUV spectroscopy. To date, photoexcited small polaron formation has only been measured to be adiabatic. The reorganization energy of the polar lattice is large enough that the first electron-optical phonon scattering event creates a small polaron without significant carrier thermalization. Here, we use transient XUV spectroscopy to measure antiadiabatic polaron formation by frustrating the iron-centered octahedra in a rare-earth orthoferrite lattice. The small polaron is measured to take several picoseconds to form over multiple coherent charge hopping events between neighboring Fe3+-Fe2+ sites, a timescale that is more than an order of magnitude longer compared to previous materials. The measured interplay between optical phonons, electron correlations, and on-site lattice deformation give a clear picture of how antiadiabatic small polaron transport would occur in the material. The measurements also confirm the prediction of the Holstein and Hubbard-Holstein model that the electron hopping integral must be larger than the reorganization energy to achieve antiadiabaticity. Moreover, the measurements emphasize the importance of considering dynamical electron correlations, and not just changes in the lattice geometry, for controlling small polarons in transport or photoexcited applications.