Realization of higher coordinated Er in high-pressure cotunnite phase of Er$_2$Ti$_2$O$_7$

TL;DR

This study investigates the pressure-induced phase transition of Er2Ti2O7 from cubic pyrochlore to orthorhombic cotunnite, revealing increased coordination of Er3+ ions and structural disordering upon high-pressure treatment.

Contribution

It provides the first detailed experimental and theoretical analysis of the high-pressure cotunnite phase of Er2Ti2O7 and its structural stability and defect mechanisms.

Findings

Phase transition initiated at ~40 GPa

Cotunnite phase stable above ~53 GPa

Coordination number of Er3+ increases from 8 to 9

Abstract

In this article we report the structural stability of Er$_2$Ti$_2$O$_7$ cubic pyrochlore with pressure using x-ray diffraction, Raman spectroscopy, photoluminescence, x-ray absorption and ab-initio calculations. Our studies establish a phase transformation in Er$_2$Ti$_2$O$_7$ from ambient cubic phase to high-pressure orthorhombic (cotunnite) phase, initiated at ~40 GPa. The transformation is sluggish and it does not complete even at the highest measured pressure in our study i.e. ~60.0 GPa. This is further supported by the first principle calculations which reveal that cotunnite phase is energetically more stable than the ambient phase above ~53 GPa. After complete release of pressure, the high-pressure cotunnite phase is retained while the fraction of untransformed pyrochlore phase becomes amorphous. Furthermore, the EXAFS data of the recovered sample at L3 edge of Er3+ ion show an increase in the coordination number of cations from eight at ambient to nine in the high-pressure phase. The mechanism of structural transformation is explained in terms of accumulation of cation antisite defects and subsequent disordering of cations and anions in their respective sublattice. The amorphization of the pyrochlore phase upon release is interpreted as the inability of accommodating the point defects at ambient conditions, which are formed in the pyrochlore lattice under compression.