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

Although strong modulation of interfacial electron concentrations by the relative acidity of surface additives is suggested, direct observation of corresponding changes in surface conductivity, crucial for understanding the role of local space charge, is lacking. Here, a model platform comprising well-aligned mixed ionic-electronic conducting Pr_0.2Ce_0.8O_2-δ nanowire arrays (PCO_NA) is introduced to show that acidity-modulated heterointerfaces predict electron depletion or accumulation, resulting in tunable electrical properties. Three orders of magnitude increased PCO_NA conductivity are confirmed with basic Li₂O infiltration. Moreover, the relative acidity of the insulating substrate supporting the PCO_NA strongly influences its electronic properties as well. This strategy is further validated in purely ionic-conducting nanostructured ceria as well as PCO_NA. It is suggested 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.