Combining Landau Zener Theory and Kinetic Monte Carlo Sampling for Small Polaron Mobility of Doped BiVO4

TL;DR

This study combines Landau-Zener theory and kinetic Monte Carlo simulations from first principles to analyze small polaron mobility in doped and pristine VO4, revealing dopant effects on electron transport and mobility enhancement strategies.

Contribution

It introduces a first-principles approach combining Landau-Zener theory and kinetic Monte Carlo to study polaron mobility in VO4, including dopant interactions and their impact on transport.

Findings

Polaron formation occurs at V in both pristine and doped VO4.

DFT+U and hybrid functionals yield similar hopping barriers and mobilities.

Dopants like Mo and W are 'repulsive' to polarons, enhancing mobility.

Abstract

Transition metal oxides such as \ce{BiVO4} are promising materials as photoelectrodes in solar-to-fuel conversion applications. However, their performance is limited by the low carrier mobility (especially electron mobility) due to the formation of small polarons. Recent experimental studies show improved carrier mobility and conductivity by atomic dopings. We studied the small polaron hopping mobility in pristine and doped \ce{BiVO4} by combining Landau-Zener theory and kinetic Monte Carlo (kMC) simulation fully from first-principles, and investigated the effect of dopant-polaron interactions on the mobility. We found polarons are spontaneously formed at V in both pristine and Mo/W doped \ce{BiVO4}, which can only be described correctly by density function theory (DFT) with the Hubbard correction (DFT+U) or hybrid exchange-correlation functional but not local or semi-local functionals. We found DFT+U and dielectric dependant hybrid functional (DDH) give similar electron hopping barriers, which are also similar between the room temperature monoclinic phase and the tetragonal phase. The calculated electron mobility agrees well with experimental values, which is around $10^{-4}$ cm$^2$V$^{-1}$s$^{-1}$. We found the electron polaron transport in \ce{BiVO4} is neither fully adiabatic nor nonadiabatic, and the first and second nearest neighbor hoppings have significantly different adiabacity in spite of similar hopping barriers. We further computed polaron mobility in the presence of different dopants and showed that Cr substitution of V is an electron trap while Mo and W are "repulsive" centers, mainly due to the minimization of local lattice expansion by dopants and electron polarons. The dopants with "repulsive" interactions to polarons are promising for mobility improvement due to larger wavefunction overlap and delocalization of locally concentrated polarons.