Near-edge x-ray absorption fine-structure study of ion-beam-induced phase transformation in Gd2(Ti1−yZry)2O7

Abstract

The structural and electronic properties of Gd2(Ti1−yZry)2O7 (y=0–1) pyrochlores following a 2.0-MeV Au2+ ion-beam irradiation (∼5.0×1014Au2+∕cm2) have been investigated by Ti2p and O1s near-edge x-ray absorption fine structure (NEXAFS). The irradiation of Gd2(Ti1−yZry)2O7 leads to the phase transformation from the ordered pyrochlore structure (Fd3m) to the defect fluorite structure (Fm3m) regardless of Zr concentration. Irradiated Gd2(Ti1−yZry)2O7 with y⩽0.5 are amorphous, although significant short-range order is present. Contrasting to this behavior, compositions with y⩾0.75 retain crystallinity in the defect fluorite structure following irradiation. The local structures of Zr4+ in the irradiated Gd2(Ti1−yZry)2O7 with y⩾0.75 determined by NEXAFS are the same as in the cubic fluorite-structured yttria-stabilized zirconia (Y–ZrO2), thereby providing conclusive evidence for the phase transformation. The TiO6 octahedra present in Gd2(Ti1−yZry)2O7 are completely modified by ion-beam irradiation to TiOx polyhedra, and the Ti coordination is increased to eight with longer Ti–O bond distances. The similarity between cation sites and the degree of disorder in Gd2Zr2O7 facilitate the rearrangement and relaxation of Gd, Zr, and O ions∕defects. This inhibits amorphization during the ion-beam-induced phase transition to the radiation-resistant defect fluorite structure, which is in contrast to the ordered Gd2Ti2O7.