Acidity-Mediated Metal Oxide Heterointerfaces: Roles of Substrates and Surface Modification

TL;DR

This study demonstrates how surface acidity and substrate properties can significantly modulate the electrical conductivity of nanostructured metal oxides through heterointerface engineering and surface modifications.

Contribution

Introduces a model platform using PCO nanowire arrays to directly observe acidity-induced changes in surface conductivity and heterointerface charge modulation.

Findings

Conductivity increased three orders of magnitude with basic Li₂O infiltration.

Substrate acidity influences electronic properties of nanostructured oxides.

Conductivity changes are due to space charge potentials and grain boundary effects.

Abstract

Although strong modulation of interfacial electron concentrations by the relative acidity of surface additives has been suggested, direct observation of corresponding changes in surface conductivity, crucial for understanding the role of local space charge, has been lacking. Here, we introduce a model platform comprising well-aligned mixed ionic-electronic conducting $\mathrm{Pr}_{0.2}\mathrm{Ce}_{0.8}\mathrm{O}_{2-\delta}$ nanowire arrays ($\mathrm{PCO}_{\mathrm{NA}}$) to show that acidity-modulated heterointerfaces predict electron depletion or accumulation, resulting in tunable electrical properties. We confirm three orders of magnitude increased $\mathrm{PCO}_{\mathrm{NA}}$ conductivity with basic $\mathrm{Li}_{2}\mathrm{O}$ infiltration. Moreover, the relative acidity of the insulating substrate supporting the $\mathrm{PCO}_{\mathrm{NA}}$ strongly influences its electronic properties as well. This strategy is further validated in purely ionic-conducting nanostructured ceria as well as $\mathrm{PCO}_{\mathrm{NA}}$. We suggest that observed conductivity changes stem not only from acidity-mediated space charge potentials at heterointerfaces but also from grain boundaries, chemically-modulated by cation in-diffusion. These findings have broad implications for how substrate and surface treatment choices can alter the conductive properties of nanostructured functional oxides.