"A2TiO5 (A = Dy, Gd, Er, Yb) at High Pressure"

Sulgiye Park: Dylan R. Rittman, Cameron L. Tracy, Karena W. Chapman , Fuxiang Zhang, Changyong Park , Sergey N. Tkachev, Eric O’Quinn, Jacob Shamblin, Maik Lang, Wendy L. Mao, and Rodney C. Ewing; Inorg Chem, 02/09/18.

Additional Authors: Dylan R. Rittman, Cameron L. Tracy, Karena W. Chapman , Fuxiang Zhang, Changyong Park , Sergey N. Tkachev, Eric O’Quinn, Jacob Shamblin, Maik Lang, Wendy L. Mao, and Rodney C. Ewing

Abstract:

The structural evolution of lanthanide A2TiO5 (A = Dy, Gd, Yb, Er) at high pressure is investigated using synchrotron X-ray diffraction. The effects of A-site cation size and of the initial structure are systematically examined by varying the composition of the isostructural lanthanide titanates and the structure of dysprosium titanate polymorphs (orthorhombic, hexagonal, and cubic), respectively. All samples undergo irreversible high-pressure phase transformations, but with different onset pressures depending on the initial structure. While each individual phase exhibits different phase transformation histories, all samples commonly experience a sluggish transformation to a defect cotunnite-like (Pnma) phase for a certain pressure range. Orthorhombic Dy2TiO5 and Gd2TiO5 form P21am at pressures below 9 GPa and Pnma above 13 GPa. Pyrochlore-type Dy2TiO5 and Er2TiO5 as well as defect-fluorite-type Yb2TiO5 form Pnma at ∼21 GPa, followed by Im3̅m. Hexagonal Dy2TiO5 forms Pnma directly, although a small amount of remnants of hexagonal Dy2TiO5 is observed even at the highest pressure (∼55 GPa) reached, indicating kinetic limitations in the hexagonal Dy2TiO5 phase transformations at high pressure. Decompression of these materials leads to different metastable phases. Most interestingly, a high-pressure cubic X-type phase (Im3̅m) is confirmed using high-resolution transmission electron microscopy on recovered pyrochlore-type Er2TiO5. The kinetic constraints on this metastable phase yield a mixture of both the X-type phase and amorphous domains upon pressure release. This is the first observation of an X-type phase for an A2BO5 composition at high pressure.