Electrical properties of A-site Ca-doped LaNb1-xAsxO4-δ ceramics

The electrical properties of A-site Ca-doped LaNbO4 with the addition of As in the B-site, have been investigated. Total, grain- and specific grain boundary electric conductivities in different oxygen partial pressure, and water vapour partial pressure were determined. Additional conductivity measurements were performed in nitrogen, to suppress the possible p-type conductivity, focusing on protonic conductivity. The maximum measured total conductivity was recorded for La0.99Ca0.01Nb0.9As0.1O4-δ at 800 °C, which was equal to 1.2·10−4 S·cm−1 in H2O- humidified air, and 2.2·10−5 S·cm−1 in H2O- humidified N2. From the deconvoluted data, the lowest activation energies for grain conduction were obtained in both atmospheres for La0.99Ca0.01Nb0.7As0.3O4-δ. In the temperature range 400 °C – 550 °C it was 0.23 eV and 0.13 eV respectively for H2O- humidified air and H2O- humidified N2. The results show that the increasing arsenic amount mainly influences the activation energies, whereas the calcium addition slightly improves the grain conductivity. The pO2 experiments revealed that in oxidizing atmospheres, electron holes contribute to the conductivity. The high proton transfer numbers were obtained for each sample, peaking at tH+ = 0.91 for LaNb0.7As0.3O4 at 400 °C. Interestingly, even at elevated temperatures relatively high values are obtained where tH+ = 0.87 was recorded at 800 °C for La0.99Ca0.01Nb0.9As0.1O4-δ. •A- and B-site doped lanthanum orthoniobates are triple-conducting materials.•Electron holes give a contribution to the total conductivity in oxidizing atmospheres.•The proton transfer numbers are between tH+ = 0.93 and 0.78.•Arsenic influences the activation energies, and calcium addition primarily improves the total conductivity.