High Pressure Crystal and Magnetic Phase Transitions in Multiferroic Bi0.9La0.1FeO3

The crystal and magnetic structures of multiferroic Bi0.9La0.1FeO3 have been studied using high resolution neutron powder diffraction in the pressure range 0-8 GPa. Two structural phase transitions are observed. The first, at similar to 1 GPa, transforms the polar R3c structure to an antipolar PbZrO3-like root 2a(p) x 2 root 2a(p) x 2a(p) perovskite superstructure; the second, at similar to 5 GPa, results in a smaller, root 2a(p) x root 2a(p) x 2a(p) unit cell and a structure described with Ibmm (nonstandard setting of Imma) symmetry, in which the a(-)a(-)b(0) octahedral tilt system is retained and the antipolar cation displacements lost. Accompanying the changes in the nuclear structure, the antiferromagnetic spin structure evolves from a cycloid, with a modulation length, lambda approximate to 770 angstrom, to collinear arrangements with the moments aligned along the b-axis (Pbam) and the a-axis (Ibmm) of the orthorhombic unit cells. In comparison with BiFeO3 the transition from a rhombohedral to an orthorhombic structure is suppressed by similar to 3 GPa, reflecting the dilution of the stereochemically active bismuth lone pair by lanthanum. A correlation between the cell contraction of Bi1-xLaxFeO3 (0.0 <= x <= 0.3) induced by chemical pressure and hydrostatic pressure on BiFeO3 is determined, with substitution of 1 mol % of La approximately equivalent to application of 0.05 GPa. Bi0.9La0.1FeO3 is found to have a higher bulk modulus than BiFeO3.