Pyroelectric and piezoelectric scanning microscopy applied to reveal the bipolar state of 4-iodo-4 '-nitrobiphenyl (INBP)

Two recent scanning probe techniques were applied to investigate the bipolar twin state of 4-iodo-4'-nitrobiphenyl (INBP) crystals. Solution grown crystals of INBP show typically a morphology which does not express that of a mono-domain polar structure (Fdd2, mm2). From previous X-ray diffraction a twinning volume ratio of similar to 70 : 30 is now explained by two unipolar domains (Flack parameter: 0.075(29)) of opposite orientation of the molecular dipoles, joined by a transition zone showing a width of similar to 140 mm. Scanning pyroelectric microscopy (SPEM) demonstrates a continuous transition of the polarization P from +P into -P across the zone. Application of piezoelectric force microscopy (PFM) confirms unipolar alignment of INBP molecules down to a resolution of similar to 20 nm. A previously proposed real structure for INBP crystals built from lamellae with antiparallel alignment is thus rejected. Anomalous X-ray scattering was used to determine the absolute molecular orientation in the two domains. End faces of the polar axis 2 are thus made up by NO2 groups. Using a previously determined negative pyroelectric coefficient pc leads to a confirmation also by a SPEM analysis. Calculated values for functional group interactions (D...A), (A...A), (D...D) and the stochastic theory of polarity formation allow us to predict that NO2 groups should terminate corresponding faces. Following the present analysis, INBP may represent a first example undergoing dipole reversal upon growth to end up in a bipolar state.

Mapping piezoelectric nonlinearity in the Rayleigh regime using band excitation piezoresponse force microscopy

Band excitation piezoresponse force microscopy enables local investigation of the nonlinear piezoelectric behavior of ferroelectric thin films. However, the presence of additional nonlinearity associated with the dynamic resonant response of the tip-surface junction can complicate the study of a material's nonlinearity. Here, the relative importance of the two nonlinearity sources was examined as a function of the excitation function. It was found that in order to minimize the effects of nonlinear tip-surface interactions but achieve good signal to noise level, an optimal excitation function must be used. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3593138]

Imaging domains in BaTiO3 single crystal nanostructures: comparing information from transmission electron microscopy and piezo-force microscopy

This article compares and contrasts information
obtained, using transmission electron microscopy (TEM)
and piezo-force microscopy (PFM), on domain configurations
adopted in single crystal lamellae of BaTiO3, that had
been cut directly from bulk using a focused ion beam
microscope with top and bottom surfaces parallel to
{100}pseudocubic. Both forms of imaging reveal domain
walls parallel to {110}pseudocubic, consistent with sets of 90
domains with dipoles oriented parallel to the two
\001[pseudocubic directions in the plane of the lamellae.
However, the domain width was observed to be dramatically
larger using PFM than it was using TEM. This suggests
significant differences in the surface energy densities
that drive the domain formation in the first place, that could
relate to differences in the boundary conditions in the two
modes of imaging (TEM samples are imaged under high
vacuum, whereas PFM imaging was performed in air).
Attempts were made to map local dipole orientations
directly, using a form of ‘vector’ PFM. However, information
inferred was largely inconsistent with the known
crystallography of the samples, raising concern about the
levels of care needed for accurate interpretation of PFM
images.

Resolution theory, and static and frequency-dependent cross-talk in piezoresponse force microscopy

Probing the functionality of materials locally by means of scanning probe microscopy (SPM) requires a reliable framework for identifying the target signal and separating it from the effects of surface morphology and instrument non-idealities, e.g. instrumental and topographical cross-talk. Here we develop a linear resolution theory framework in order to describe the cross-talk effects, and apply it for elucidation of frequency-dependent cross-talk mechanisms in piezoresponse force microscopy. The use of a band excitation method allows electromechanical/electrical and mechanical/topographic signals to be unambiguously separated. The applicability of a functional fit approach and multivariate statistical analysis methods for identification of data in band excitation SPM is explored.

Real-space mapping of dynamic phenomena during hysteresis loop measurements: Dynamic switching spectroscopy piezoresponse force microscopy

Dynamic switching spectroscopy piezoresponse force microscopy is developed to separate thermodynamic and kinetic effects in local bias-induced phase transitions. The approaches for visualization and analysis of five-dimensional data are discussed. The spatial and voltage variability of relaxation behavior of the a-c domain lead zirconate-titanate surface suggest the interpretation in terms of surface charge dynamics. This approach is applicable to local studies of dynamic behavior in any system with reversible bias-induced phase transitions ranging from ferroelectrics and multiferroics to ionic systems such as batteries, fuel cells, and electroresistive materials. (C) 2011 American Institute of Physics. [doi:10.1063/1.3590919]

Probing charge screening dynamics and electrochemical processes at the solid–liquid interface with electrochemical force microscopy

The presence of mobile ions complicates the implementation of voltage-modulated scanning probe microscopy techniques such as Kelvin probe force microscopy (KPFM). Overcoming this technical hurdle, however, provides a unique opportunity to probe ion dynamics and electrochemical processes in liquid environments and the possibility to unravel the underlying mechanisms behind important processes at the solid–liquid interface, including adsorption, electron transfer and electrocatalysis. Here we describe the development and implementation of electrochemical force microscopy (EcFM) to probe local bias- and time-resolved ion dynamics and electrochemical processes at the solid–liquid interface. Using EcFM, we demonstrate contact potential difference measurements, consistent with the principles of open-loop KPFM operation. We also demonstrate that EcFM can be used to investigate charge screening mechanisms and electrochemical reactions in the probe–sample junction. We further establish EcFM as a force-based imaging mode, allowing visualization of the spatial variability of sample-dependent local electrochemical properties.

Piezoresponse force microscopy of ferroelectric thin films: Frequency dependence of phase imaging

The objective of this work is an evaluation of quantitative measurements of piezoresponse force microscopy for nanoscale characterization of ferroelectric films. To this end, we investigate how the piezoresponse phase difference Delta Phi between c domains depends on the frequency omega of the applied ac field much lower than the cantilever first resonance frequency. The main specimen under study was a 102 nm thick film of Pb(Zr(0.2)Ti(0.8))O(3). For the sake of comparison, a 100 nm thick PbTiO(3) film was also used. From our measurements, we conclude a frequency dependent behavior Delta Phi similar to omega(-1), which can only be partially explained by the presence of adsorbates on the surface. (C) 2008 American Institute of Physics.

Multiferroic domain dynamics in strained strontium titanate

Multiferroicity can be induced in strontium titanate by applying biaxial strain. Using optical second harmonic generation, we report a transition from 4/mmm to the ferroelectric mm2 phase, followed by a transition to a ferroelastic-ferroelectric mm2 phase in a strontium titanate thin film. Piezoelectric force microscopy is used to study ferroelectric domain switching. Second harmonic generation, combined with phase-field modeling, is used to reveal the mechanism of coupled ferroelectric-ferroelastic domain wall motion. These studies have relevance to multiferroics with coupled polar and axial phenomena.

Epitaxial ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films on La0.7Sr0.3MnO3 bottom electrode

Epitaxial (001)-oriented 0.7Pb(Mg_0.33Nb_0.67)O₃-0.3PbTiO₃ (PMN-PT) thin films were deposited by pulsed laser deposition on vicinal SrTiO₃ (001) substrates using La_0.7Sr_0.3MnO₃ as bottom electrode. Detailed microstructural investigations of these films were carried out using X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Polarization-field hysteresis curves were measured at room temperature. Spontaneous polarization P s , remnant polarization P r and coercive voltage V c were found to be 25 μC/cm², 15 μC/cm² and 0.81 V, respectively. Field dependent dielectric constant measurements exhibited butterfly shaped curves, indicating the true ferroelectric nature of these films at room temperature. The dielectric constant and the dielectric loss at 100 kHz were found to be 238 and 0.14, respectively. The local piezoelectric properties of PMN-PT films were investigated by piezoelectric force microscopy and were found to exhibit a local piezoelectric coefficient of 7.8 pm/V.

Piezoelectric properties of PbTiO(3) thin films characterized with piezoresponse force and high resolution transmission electron microscopy

In this paper we investigate the piezoelectric properties of PbTiO(3) thin films grown by pulsed laser deposition with piezoresponse force microscopy and transmission electron microscopy. The as-grown films exhibit an upward polarization, inhomogeneous distribution of piezoelectric characteristics concerning local coercive fields, and piezoelectric coefficient. In fact, the data obtained reveal imprints during piezoresponse force microscopy measurements, nonlinearity in the piezoelectric deformation, and limited polarization reversal. Moreover, transmission electron microscopy shows the presence of defects near the film/substrate interface, which can be associated with the variations of piezoelectric properties.

Local probing of ferroelectric and ferroelastic switching through stress-mediated piezoelectric spectroscopy

Strain effects have a significant role in mediating classic ferroelectric behavior such as polarization switching and domain wall dynamics. These effects are of critical relevance if the ferroelectric order parameter is coupled to strain and is therefore, also ferroelastic. Here, switching spectroscopy piezoresponse force microscopy (SS-PFM) is combined with control of applied tip pressure to exert direct control over the ferroelastic and ferroelectric switching events, a modality otherwise unattainable in traditional PFM. As a proof of concept, stress-mediated SS-PFM is applied toward the study of polarization switching events in a lead zirconate titanate thin film, with a composition near the morphotropic phase boundary with co-existing rhombohedral and tetragonal phases. Under increasing applied pressure, shape modification of local hysteresis loops is observed, consistent with a reduction in the ferroelastic domain variants under increased pressure. These experimental results are further validated by phase field simulations. The technique can be expanded to explore more complex electromechanical responses under applied local pressure, such as probing ferroelectric and ferroelastic piezoelectric nonlinearity as a function of applied pressure, and electro-chemo-mechanical response through electrochemical strain microscopy.

Influence of a Single Grain Boundary on Domain Wall Motion in Ferroelectrics

Epitaxial tetragonal 425 and 611 nm thick Pb(ZrTi)O (PZT) films are deposited by pulsed laser deposition on SrRuO-coated (100) SrTiO 24° tilt angle bicrystal substrates to create a single PZT grain boundary with a well-defined orientation. On either side of the bicrystal boundary, the films show square hysteresis loops and have dielectric permittivities of 456 and 576, with loss tangents of 0.010 and 0.015, respectively. Using piezoresponse force microscopy (PFM), a decrease in the nonlinear piezoelectric response is observed in the vicinity (720-820 nm) of the grain boundary. This region represents the width over which the extrinsic contributions to the piezoelectric response (e.g., those associated with the domain density/configuration and/or the domain wall mobility) are influenced by the presence of the grain boundary. Transmission electron microscope (TEM) images collected near and far from the grain boundary indicate a strong preference for (101)/(1-01) type domain walls at the grain boundary, whereas (011)/(01-1) and (101)/(1-01) are observed away from this region. It is proposed that the elastic strain field at the grain boundary interacts with the ferro-electric/elastic domain structure, stabilizing (101)/(1-01) rather than (011)/(01-1) type domain walls, which inhibits domain wall motion under applied field and decreases non-linearity. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mask assisted fabrication of nanoislands of BiFeO3 by ion beam milling

We report on a low-damage method for direct and rapid fabrication of arrays of epitaxial BiFeO3(BFO) nanoislands. An array of aluminium dots is evaporated through a stencil mask on top of an epitaxial BiFeO3 thin film. Low energy focused ion beam milling of an area several microns wide containing the array-covered film leads to removal of the bismuth ferrite in between the aluminium-masked dots. By chemical etching of the remaining aluminium, nanoscale epitaxial bismuth ferrite islands with diameter ∼250 nm were obtained. Piezoresponse force microscopy showed that as-fabricated structures exhibited good piezoelectric and ferroelectric properties, with polarization state retention of several days.