Oleg S. Ovchinnikov

Mapping Octahedral Tilts and Polarization Across a Domain Wall in BiFeO3 from Z-Contrast Scanning Transmission Electron Microscopy Image Atomic Column Shape Analysis

Oxygen octahedral tilts underpin the functionality of a large number of perovskite-based materials and heterostructures with competing order parameters. We show how a precise analysis of atomic column shapes in Z-contrast scanning transmission electron microscopy images can reveal polarization and octahedral tilt behavior across uncharged and charged domain walls in BiFeO(3). This method is capable of visualizing octahedral tilts to much higher thicknesses than phase contrast imaging. We find that the octahedral tilt transition across a charged domain wall is atomically abrupt, while the associated polarization profile is diffuse (1.5-2 nm). Ginzburg-Landau theory then allows the relative contributions of polarization and the structural order parameters to the wall energy to be determined.

First-Order Reversal Curve Probing of Spatially Resolved Polarization Switching Dynamics in Ferroelectric Nanocapacitors

Spatially resolved polarization switching in ferroelectric nanocapacitors was studied on the sub-25 nm scale using the first-order reversal curve (FORC) method. The chosen capacitor geometry allows both high-veracity observation of the domain structure and mapping of polarization switching in a uniform field, synergistically combining microstructural observations and probing of uniform-field polarization responses as relevant to device operation. A classical Kolmogorov-Avrami-Ishibashi model has been adapted to the voltage domain, and the individual switching dynamics of the FORC response curves are well approximated by the adapted model. The comparison with microstructures suggests a strong spatial variability of the switching dynamics inside the nanocapacitors.

Atomic-level sculpting of crystalline oxides: toward bulk nanofabrication with single atomic plane precision

The atomic-level sculpting of 3D crystalline oxide nanostructures from metastable amorphous films in a scanning transmission electron microscope (STEM) is demonstrated. Strontium titanate nanostructures grow epitaxially from the crystalline substrate following the beam path. This method can be used for fabricating crystalline structures as small as 1-2 nm and the process can be observed in situ with atomic resolution. The fabrication of arbitrary shape structures via control of the position and scan speed of the electron beam is further demonstrated. Combined with broad availability of the atomic resolved electron microscopy platforms, these observations suggest the feasibility of large scale implementation of bulk atomic-level fabrication as a new enabling tool of nanoscience and technology, providing a bottom-up, atomic-level complement to 3D printing.

Towards 3D Mapping of BO6 Octahedron Rotations at Perovskite Heterointerfaces, Unit Cell by Unit Cell

The rich functionalities in the ABO3 perovskite oxides originate, at least in part, from the ability of the corner-connected BO6 octahedral network to host a large variety of cations through distortions and rotations. Characterizing these rotations, which have significant impact on both fundamental aspects of materials behavior and possible applications, remains a major challenge at heterointerfaces. In this work, we have developed a unique method to investigate BO6 rotation patterns in complex oxides ABO3 with unit cell resolution at heterointerfaces, where novel properties often emerge. Our method involves column shape analysis in ABF-STEM images of the ABO3 heterointerfaces taken in specific orientations. The rotating phase of BO6 octahedra can be identified for all three spatial dimensions without the need of case-by-case simulation. In several common rotation systems, quantitative measurements of all three rotation angles are now possible. Using this method, we examined interfaces between perovskites with distinct tilt systems as well as interfaces between tilted and untilted perovskites, identifying an unusual coupling behavior at the CaTiO3/LSAT interface. We believe this method will significantly improve our knowledge of complex oxide heterointerfaces.

Spatially resolved probing of Preisach density in polycrystalline ferroelectric thin films

Applications of the ferroelectric materials for the information storage necessitate the understanding of local switching behavior on the level of individual grains and microstructural elements. In particular, implementation of multilevel neuromorphic elements requires the understanding of history-dependent polarization responses. Here, we introduce the spatially resolved approach for mapping local Preisach densities in polycrystalline ferroelectrics based on first-order reversal curve (FORC) measurements over spatially resolved grid by piezoresponse force spectroscopy using tip-electrode. The band excitation approach allowed effective use of cantilever resonances to amplify weak piezoelectric signal and also provided insight in position-, voltage-, and voltage history-dependent mechanical properties of the tip-surface contact. Several approaches for visualization and comparison of the multidimensional data sets formed by FORC families or Preisach densities at each point are introduced and compared. The relationship between switching behavior and microstructure is analyzed.

Ferroelastic domain wall dynamics in ferroelectric bilayers

High-performance piezoelectric devices based on ferroelectric materials rely heavily on ferroelastic domain wall switching. Here we present visual evidence for the local mechanisms that underpin domain wall dynamics in ferroelastic nanodomains. State-of-the-art band excitation switching spectroscopy piezoforce microscopy (PFM) reveals distinct origins for the reversible and irreversible components of ferroelastic domain motion. Extrapolating the PFM images to case for uniform fields, we posit that, while reversible switching is essentially a linear motion of the ferroelastic domains, irreversible switching takes place via domain wall twists. Critically, real-time images of in situ domain dynamics under an external bias reveal that the reversible component leads to reduced coercive voltages. Finally, we show that junctions representing three-domain architecture represent facile interfaces for ferroelastic domain switching, and are likely responsible for irreversible processes in the uniform fields. The results presented here thus provide (hitherto missing) fundamental insight into the correlations between the physical mechanisms that govern ferroelastic domain behavior and the observed functional response in domain-engineered thin film ferroelectric devices.

Local measurements of Preisach density in polycrystalline ferroelectric capacitors using piezoresponse force spectroscopy

Polarization switching in polycrystalline ferroelectric capacitors is explored using piezoresponse force microscopy (PFM) based first-order reversal curve (FORC) measurements. The band excitation method facilitates decoupling the electromechanical responses from variations in surface elastic properties. A simulated annealing method is developed to estimate the Preisach densities from PFM FORC data. Microscopic and macroscopic Preisach densities are compared, illustrating good agreement between the two.

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.

Mapping Disorder in Polycrystalline Relaxors: A Piezoresponse Force Microscopy Approach

Relaxors constitute a large class of ferroelectrics where disorder is introduced by doping with ions of different size and valence, in order to maximize their useful properties in a broad temperature range. Polarization disorder in relaxors is typically studied by dielectric and scattering techniques that do not allow direct mapping of relaxor parameters, such as correlation length or width of the relaxation time spectrum. In this paper, we introduce a novel method based on measurements of local vibrations by Piezoresponse Force Microscopy (PFM) that detects nanoscale polarization on the relaxor surface. Random polarization patterns are then analyzed via local Fast Fourier Transform (FFT) and the FFT PFM parameters, such as amplitude, correlation radius and width of the spectrum of spatial correlations, are mapped along with the conventional topography. The results are tested with transparent (Pb, La) (Zr, Ti)O3 ceramics where local disorder is due to doping with La3+. The conclusions are made about the distribution of the defects responsible for relaxor behavior and the role of the grain boundaries in the macroscopic response.

Adaptive probe trajectory scanning probe microscopy for multiresolution measurements of interface geometry

An adaptive scanning method in scanning probe microscopy (SPM) is developed for studies of surfaces with a highly-non-uniform information density such as nanowires or interfaces in disordered media. In path-engineered SPM, the surface is pre-scanned to locate features, and a secondary scan is acquired with the pixel density concentrated in the vicinity of the objects of interest. Here, we demonstrate this approach for piezoresponse force microscopy, and develop approaches for fractal and self-affine characterization of domain interfaces. The relationship between the variational roughness, structure factor, and correlation functions is established and resolution effects on these parameters are determined.