Structural and optical study of the phase transitions in Lead Hafnate, PbHfO₃

Lead Hafnate undergoes two structural phase transitions as a function of temperature. The first occurs at about 163⁰C, consisting of a transition from an antiferroelectric orthorhombic Pbam structure [1] to another antiferroelectric orthorhombic phase with an as-yet undetermined space group. The second is to a paraelectric cubic Pm3m structure at 209⁰C. Dielectric spectroscopy measurements on a single crystal have shown a distinct temperature hysteresis at the orthorhombic to orthorhombic transition [2]. Recently, dielectric measurements on a ceramic sample have shown a much larger temperature hysteresis and following x-ray diffraction measurements, it is suggested that the second orthorhombic phase is in space group A2mm and undergoes another transition to a tetragonal P4mm structure before the cubic transition [3]. We report on the results of an investigation of a PbHfO₃ crystal using a combination of high-resolution x-ray diffraction and birefringence imaging measurements with the Metripol system. These measurements have been performed as a function of temperature from the room-temperature orthorhombic structure to the high-temperature cubic structure. The results are discussed both in the context of the published work and fundamental understanding of the origin of antiferroelectricity.

X-Ray induced Photostriction in Bismuth Ferrite

In a material with both a piezoelectric effect and the capability to form a photocurrent, photostriction can be observed - the deformation of the crystal by light. When studying photostriction, a potential method is to use x-rays to probe the unit cell in response to another light source as a stimulus, such as a laser or a diode. Given that x-rays are also photons it is plausible that they themselves produce some effect. An experiment was carried out to investigate how significant the effects of the x-rays are in producing photostriction in the absence of any other source of illumination. The material studied in this example was bismuth iron oxide, BiFeO3. A thin film with electrodes was used and it was found that the photocurrent generated by a laboratory x-ray source on the sample was of comparable level to that of a laser or diode used in the study of the bulk photoelectric effect. Using a novel, time dependent crystallographic approach, the intrinsic effect of synchrotron x-ray light on a photoferroelectric thin film has been investigated. Furthermore, we have simultaneously collected diffraction and photoelectric data, and the correlation between the electronic and structural properties will be discussed. These results could suggest that caution is necessary when interpreting photostriction data obtained with the use of x-rays.