Effect of structure and composition on the electronic excitation induced amorphization of La2Ti2-xZrxO7 ceramics.

Understanding the response of ceramics operating in extreme environments is of interest for a variety of applications. Ab initio molecular dynamic simulations have been used to investigate the effect of structure and B-site (=Ti, Zr) cation composition of lanthanum-based oxides (La2B2O7) on electronic-excitation-induced amorphization. We find that the amorphous transition in monoclinic layered perovskite La2Ti2O7 occurs for a lower degree of electronic excitation than for cubic pyrochlore La2Zr2O7. While in each case the formation of O2-like molecules drives the structure to an amorphous state, an analysis of the polyhedral connection network reveals that the rotation of TiO6 octahedra in the monoclinic phase can promote such molecule formation, while such octahedral rotation is not possible in the cubic phase. However, once the symmetry of the cubic structure is broken by substituting Ti for Zr, it becomes less resistant to amorphization. A compound made of 50% Ti and 50% Zr (La2TiZrO7) is found to be more resistant in the monoclinic than in the cubic phase, which may be related to the lower bandgap of the cubic phase. These results illustrate the complex interplay of structure and composition that give rise to the radiation resistance of these important functional materials.