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Strain dependent properties of bismuth ferrite lead titanate probed by piezoresponse force microscopy

Tim Burnett1, Tim Stevenson2, Tim Comyn2, Markys Cain1 and Andrew Bell2
1

National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK 2Institute for Materials Research, University of Leeds, Leeds, LS2 9JT, UK

Solid solutions of multiferroic BiFeO3 doped with ferroelectric PbTiO3 (BFPT) have been prepared by conventional mixed oxide processing to produce polycrystalline ceramics throughout the xBiFeO3-(1-x)PbTiO3 compositional range [1]. Sintered ceramics are shown to exhibit mixed tetragonal (P4mm) and rhombohedral (R3c) phase perovskite distortions from 0.4x<0.75, where at x~0.75 a morphotropic phase boundary (MPB) exists and compositions x>0.75 are entirely rhombohedral. Neutron diffraction experiments have led to the explanation that the phase coexistence across this large range is attributed to compensation of the

internal strain [2]. At the MPB the tetragonal strain induced upon cooling through the ferroelectric Curie point from cubic, to the tetragonal phase is a colossal 17%. This drives a further partial transformation to the lower volume (approximately 4% volume reduction) rhombohedral phase as a mechanism to relive the resultant stress. In this work the ferroelectric domain structure has been probed at room temperature using piezoresponse force microscopy (PFM) at a range of compositions across the MPB. This work presents a first look at the complex domain structure of this material.

XRD of as sintered pellets for the three compositions probed with PFM. Note that the 7030 composition is mixed phase with ~26% tetragonal phase, the 6535 composition shows only a trace of rhombohedral and the 8020 composition only a trace of tetragonal phase.

Comparison of XRD of as sintered, annealed and disintegrated pellets compared to Synchrotron data. This high the phase dependency on the internal stress. A qualitative measure of the strain can be gleaned from the peak broadness, which is greatest in the as sintered pellet and at a minimum for the disintegrated pellet. This is quantified in the adjacent table which also highlights the huge strain >15% and the changing fraction of tetragonal and rhombohedral phases.

7030
Topography (a), Vertical Piezoresponse Phase (b) and Vertical Piezoresponse Amplitude (c) for a 7030XRD ceramic, the grain size is approximately 1m. Magnified regions of the vertical amplitude highlight the suspected tetragonal domain morphologies.

XRD of annealed pellet shows that it a mixture of tetragonal and rhombohedral phases. Inset images show discrete regions of what appear to be tetragonal domains. Many of the domains appear extremely distorted and disambiguation between rhombohedral and tetragonal domains is difficult. This is likely due in equal part to the high degree of strain in the ceramic as well as the energetic equivalence of the two phases-hence low domain wall energy.

8020
Topography (a), Vertical Piezoresponse Phase (b) and Vertical Piezoresponse Amplitude (c) for a 8020XRD ceramic, the grain size is approximately 5m, but these images are focused within a single grain). Magnified regions highlight the extremely small scale of the domains.

6535
a b
Topography (a), Vertical Piezoresponse Phase (b) and Vertical Piezoresponse Amplitude (c) for a 6535XRD ceramic, the grain size is approximately 5m.

XRD of an as sintered 8020 pellet (Fig 1) shows that the phase is essentially single phase rhombohedral, the domain configuration supports this. The two forms of the rhombohedral domain are most intriguing and may indicate regions of higher and lower internal stress. Inset images show the minute scale of these domains with which are resolved at <20 nm2. It is maybe surprising that domains of this size are stable. (NB: the complexity and multiscale nature of these domains makes excellent test of PFM resolution.)

XRD of an as sintered 6535 pellet (Fig 1) shows that the phase is essentially single phase tetragonal and the domain configuration supports this. Rectolinear domains are observed throughout this sample and the high degree of strain can be seen in the topography image as the strain relieved at the free surface.

[1]

Comyn T. P. et al Materials Letters, 58, 30, 3844-3846, 2004

[2]

Comyn T. P. et al. Applied Physics Letters, 93, 23, 232901, 2009

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Queens Printer and Controller of HMSO, 2011.

The BFPT system represents a complex mixed phase system at MPB compositions, this can be identified through XRD and PFM studies. All compositions suggest a strong correlation between the domain configurations observed and the XRD data. The strain dependence of the tetragonal and rhombohedral phases makes it likely that the surface is not exactly the same as the bulk or even the micron depths penetrated

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Conclusion

by XRD and this is being investigated further. These preliminary results suggest very stable domain structures based on the size and complexity. One possible explanation is that the ferroelastic domain walls are pinned very strongly at defects compared to systems with lower internal stress. The crystallographic nature of these samples is being investigated further with electron backscatter diffraction (EBSD) and glancing angle x-ray studies.