Energetics of magnesium, strontium, and barium doped lanthanum gallate perovskites

LaGaO3 perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa1-yMgyO3-delta (LGM), La1-xSrxGa1-yMgyO3-delta (LSGM), and La1-xBaxGa1-yMgyO3-delta (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275 +/- 37, 166 +/- 18 and 138 +/- 12 U/mol of V-O for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling. (C) 2003 Elsevier Inc. All rights reserved.