Opportunities from energy-loss near-edge fine structure analysis to track chemical and structural damage in zircon

Abstract

Zircon (ZrSiO₄) is the oldest-known mineral of Earth and an ubiquitous silicate in geochronology. More specifically, the accumulation of alpha decay damage in zircon over time significantly affects its physical and chemical properties, and can lead to a disturbance of the ages measured in this mineral. Therefore, analytical tools that enable comprehensive structural and chemical information at the nanoscale in this compound are highly sought after. In this context, we explore the electron energy-loss fine structures resulting from the excitation of O 1s and Si 2p core electrons in zircon, which are interpreted from ab initio calculations in a single-particle framework. An excellent agreement is obtained between the experimental and calculated fine structures, emphasizing the large distortion of the final electronic states induced by the core-hole potential. The O-K edge is particularly rich in information, with intense peaks dominated by O $2p$ - Zr $4d$ and O $2p$ - Si $3sp$ hybrids. This work suggests that the near-edge structures from the O $1s$ and Si $2p$ excitations accessible from electron energy-loss spectroscopy or X-ray absorption spectroscopy could be used as tools to follow, interpret and understand structural and chemical modifications in zircon subject to natural radiation damage. We illustrate the potential of this approach through the evolution of near-edge fine structures in a zircon sample that exhibits a locally amorphized zone formed by ultrafast laser excitation.