Defect-related Anomalous Mobility of Small polarons in Oxides: the Case of Congruent Lithium Niobate

TL;DR

This paper investigates how defect states in lithium niobate cause deviations from normal diffusion in small polaron mobility, revealing anomalous transport behaviors in defect-rich ferroelectric oxides.

Contribution

It introduces a formalism for modeling polaron transport considering defect trapping, combining a switching diffusion model with a mobile-immobile approach, validated by Monte Carlo simulations.

Findings

Free polarons follow normal diffusion laws.

Bound polarons exhibit anomalous diffusion behavior.

The model accurately describes mixed free and bound polaron transport.

Abstract

Polarons play a major role in the description of optical, electrical and dielectrical properties of several ferroelectric oxides. The motion of those particles occur by elementary hops among the material lattice sites. In order to compute macroscopic transport parameters such as charge mobility, normal diffusion laws are generally assumed. In this paper we show that when defect states able to trap the polarons for long times are considered, significant deviations from the normal diffusion behaviour arise. As an example of this behavior, we consider here the case of lithium niobate (LN), a prototypical system, having interacting polaron types. Our analysis considers the case of a stoichiometric LN containing a certain concentration of small electron polarons hopping on regular Nb sites and compares it to the material in congruent composition, which is characterized by a large concentration of antisite defects. While in the first case the charge carriers are free polarons hopping on a regular Nb sublattice, in the second case a fraction of polarons is trapped on antisite defects. Thus a range of different hopping possibilities arises, depending on the type of starting and destination sites. We develop a formalism encompassing all these microscopic processes in the framework of a switching diffusion model which can be well approximated by a mobile-immobile transport model providing explicit expressions for the polaron mobility. Starting from the Marcus-Holstein model for the polaron hopping frequency we verify by means of a Monte Carlo approach the diffusion/mobility of the different polarons showing that, while free polarons obey the laws for normal diffusion as expected, bound polarons follow an anomalous diffusion behaviour and that in the case of the congruent crystal where mixed free and bound polaron transport is involved, our expressions indeed provide a satisfactory description.