The Band Excitation Method in Scanning Probe Microscopy for Rapid Mapping of Energy Dissipation on the Nanoscale

Mapping energy transformation pathways and dissipation on the nanoscale and understanding the role of local structure on dissipative behavior is a challenge for imaging in areas ranging from electronics and information technologies to efficient energy production. Here we develop a novel Scanning Probe Microscopy (SPM) technique in which the cantilever is excited and the response is recorded over a band of frequencies simultaneously rather than at a single frequency as in conventional SPMs. This band excitation (BE) SPM allows very rapid acquisition of the full frequency response at each point (i.e. transfer function) in an image and in particular enables the direct measurement of energy dissipation through the determination of the Q-factor of the cantilever-sample system. The BE method is demonstrated for force-distance and voltage spectroscopies and for magnetic dissipation imaging with sensitivity close to the thermomechanical limit. The applicability of BE for various SPMs is analyzed, and the method is expected to be universally applicable to all ambient and liquid SPMs.Comment: 32 pages, 9 figures, accepted for publication in Nanotechnolog

Direct Measurement of Periodic Electric Forces in Liquids

The electric forces acting on an atomic force microscope tip in solution have been measured using a microelectrochemical cell formed by two periodically biased electrodes. The forces were measured as a function of lift height and bias amplitude and frequency, providing insight into electrostatic interactions in liquids. Real-space mapping of the vertical and lateral components of electrostatic forces acting on the tip from the deflection and torsion of the cantilever is demonstrated. This method enables direct probing of electrostatic and convective forces involved in electrophoretic and dielectroforetic self-assembly and electrical tweezer operation in liquid environments

Electromechanical Imaging of Biological Systems with Sub-10 nm Resolution

Electromechanical imaging of tooth dentin and enamel has been performed with sub-10 nm resolution using piezoresponse force microscopy. Characteristic piezoelectric domain size and local protein fiber ordering in dentin have been determined. The shape of a single collagen fibril in enamel is visualized in real space and local hysteresis loops are measured. Because of the ubiquitous presence of piezoelectricity in biological systems, this approach is expected to find broad application in high-resolution studies of a wide range of biomaterials.Comment: 12 pages, 4 figures, submitted for publication in Appl. Phys. Let

Probing the role of single defects on the thermodynamics of electric-field induced phase transitions

The kinetics and thermodynamics of first order transitions is universally controlled by defects that act as nucleation sites and pinning centers. Here we demonstrate that defect-domain interactions during polarization reversal processes in ferroelectric materials result in a pronounced fine structure in electromechanical hysteresis loops. Spatially-resolved imaging of a single defect center in multiferroic BiFeO3 thin film is achieved, and the defect size and built-in field are determined self-consistently from the single-point spectroscopic measurements and spatially-resolved images. This methodology is universal and can be applied to other reversible bias-induced transitions including electrochemical reactions.Comment: 34 pages,4 figures, high quality figures are available upon request, submitted to Phys. Rev. Let

Fabrication, Dynamics, and Electrical Properties of Insulated SPM Probes for Electrical and Electromechanical Imaging in Liquids

Insulated cantilever probes with a high aspect ratio conducting apex have been fabricated and their dynamic and electrical properties analyzed. The cantilevers were coated with silicon dioxide and a via was fabricated through the oxide at the tip apex and backfilled with tungsten to create an insulated probe with a conducting tip. The stiffness and Q-factor of the cantilevers increased after the modifications and their resonances shifted to higher frequencies. The coupling strength between the cantilever and the coating are determined. The applications to conductive and electromechanical imaging of ferroelectric domains are illustrated, and a probe apex repair process is demonstrated.Comment: 3 fig

The Role of Nonlinear Dynamics in Quantitative Atomic Force Microscopy

Various methods of force measurement with the Atomic Force Microscope (AFM) are compared for their ability to accurately determine the tip-surface force from analysis of the nonlinear cantilever motion. It is explained how intermodulation, or the frequency mixing of multiple drive tones by the nonlinear tip-surface force, can be used to concentrate the nonlinear motion in a narrow band of frequency near the cantilevers fundamental resonance, where accuracy and sensitivity of force measurement are greatest. Two different methods for reconstructing tip-surface forces from intermodulation spectra are explained. The reconstruction of both conservative and dissipative tip-surface interactions from intermodulation spectra are demonstrated on simulated data.Comment: 25 pages (preprint, double space) 7 figure

Spatially Resolved Mapping of Local Polarization Dynamics in an Ergodic Phase of Ferroelectric Relaxor

Spatial variability of polarization relaxation kinetics in relaxor ferroelectric 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 is studied using time-resolved Piezoresponse Force Microscopy. Local relaxation attributed to the reorientation of polar nanoregions is shown to follow stretched exponential dependence, exp(-(t/tau)^beta), with beta~~0.4, much larger than the macroscopic value determined from dielectric spectra (beta~~0.09). The spatial inhomogeneity of relaxation time distributions with the presence of 100-200 nm "fast" and "slow" regions is observed. The results are analyzed to map the Vogel-Fulcher temperatures on the nanoscale.Comment: 23 pages, 4 figures, supplementary materials attached; to be submitted to Phys. Rev. Let

Towards local electromechanical probing of cellular and biomolecular systems in a liquid environment

Electromechanical coupling is ubiquitous in biological systems with examples ranging from simple piezoelectricity in calcified and connective tissues to voltage-gated ion channels, energy storage in mitochondria, and electromechanical activity in cardiac myocytes and outer hair cell stereocilia. Piezoresponse force microscopy (PFM) has originally emerged as a technique to study electromechanical phenomena in ferroelectric materials, and in recent years, has been employed to study a broad range of non-ferroelectric polar materials, including piezoelectric biomaterials. At the same time, the technique has been extended from ambient to liquid imaging on model ferroelectric systems. Here, we present results on local electromechanical probing of several model cellular and biomolecular systems, including insulin and lysozyme amyloid fibrils, breast adenocarcinoma cells, and bacteriorhodopsin in a liquid environment. The specific features of SPM operation in liquid are delineated and bottlenecks on the route towards nanometer-resolution electromechanical imaging of biological systems are identified.Comment: 37 pages (including refs), 8 figure

Decoupling Mesoscale Functional Response in PLZT across the Ferroelectric-Relaxor Phase Transition with Contact Kelvin Probe Force Microscopy and Machine Learning

Relaxor ferroelectrics exhibit a range of interesting material behavior, including high electromechanical response, polarization rotations, as well as temperature and electric field-driven phase transitions. The origin of this unusual functional behavior remains elusive due to limited knowledge on polarization dynamics at the nanoscale. Piezoresponse force microscopy and associated switching spectroscopy provide access to local electromechanical properties on the micro- and nanoscale, which can help to address some of these gaps in our knowledge. However, these techniques are inherently prone to artefacts caused by signal contributions emanating from electrostatic interactions between tip and sample. Understanding functional behavior of complex, disordered systems like relaxor materials with unknown electromechanical properties therefore requires a technique that allows distinguishing between electromechanical and electrostatic response. Here, contact Kelvin probe force microscopy (cKPFM) is used to gain insight into the evolution of local electromechanical and capacitive properties of a representative relaxor material lead lanthanum zirconate across the phase transition from a ferroelectric to relaxor state. The obtained multidimensional data set was processed using an unsupervised machine learning algorithm to detect variations in functional response across the probed area and temperature range. Further analysis showed the formation of two separate cKPFM response bands below 50 °C, providing evidence for polarization switching. At higher temperatures only one band is observed, indicating an electrostatic origin of the measured response. In addition, the junction potential difference, which was extracted from the cKPFM data, becomes independent of the temperature in the relaxor state. The combination of this multidimensional voltage spectroscopy technique and machine learning allows to identify the origin of the measured functional response and to decouple ferroelectric from electrostatic phenomena necessary to understand the functional behavior of complex, disordered systems like relaxor materials. © 2018 American Chemical Society