Controlling electronic properties of hexagonal manganites through aliovalent doping and thermoatmospheric history

The family of hexagonal manganites is studied intensively for its multiferroicity, magnetoelectric coupling, improper ferroelectricity, functional domain walls, and topology-related scaling behaviors. It is established that these physical properties are codetermined by the cation sublattices and that aliovalent doping can readily be leveraged to modify them. The doping, however, also impacts the anion defect chemistry and semiconducting properties, which makes the system highly sensitive to the synthesis and processing conditions. Here, we study the electronic properties of $\mathrm{YMn}{\mathrm{O}}_{3}$ as a function of aliovalent cation doping and thermoatmospheric history, combining density functional theory calculations with thermopower and thermogravimetric measurements. We show that the charge-carrier concentration and transport properties can be controlled via both aliovalent cation dopants and anion defects, enabling reversible switching between $n$-type and $p$-type conductivity. This tunability is of importance for envisaged applications of hexagonal manganites in, e.g., next-generation capacitors and domain-wall nanoelectronics, or as catalysts or electrodes in fuel cells or electrolyzers. Furthermore, our approach is transferrable to other transition-metal oxides, providing general guidelines for controlling their semiconducting properties.