M. B. Okatan

Band Excitation in Scanning Probe Microscopy: Recognition and Functional Imaging

Field confinement at the junction between a biased scanning probe microscopes tip and solid surface enables local probing of various bias-induced transformations, such as polarization switching, ionic motion, and electrochemical reactions. The nanoscale size of the biased region, smaller or comparable to that of features such as grain boundaries and dislocations, potentially allows for the study of kinetics and thermodynamics at the level of a single defect. In contrast to classical statistically averaged approaches, this approach allows one to link structure to functionality and deterministically decipher associated mesoscopic and atomistic mechanisms. Furthermore, responses measured as a function of frequency and bias can serve as a fingerprint of local material functionality, allowing for local recognition imaging of inorganic and biological systems. This article reviews current progress in multidimensional scanning probe microscopy techniques based on band excitation time and voltage spectroscopies, including discussions on data acquisition, dimensionality reduction, and visualization, along with future challenges and opportunities for the field.

Highly mobile ferroelastic domain walls in compositionally graded ferroelectric thin films

Domains and domain walls are critical in determining the response of ferroelectrics, and the ability to controllably create, annihilate, or move domains is essential to enable a range of next-generation devices. Whereas electric-field control has been demonstrated for ferroelectric 180° domain walls, similar control of ferroelastic domains has not been achieved. Here, using controlled composition and strain gradients, we demonstrate deterministic control of ferroelastic domains that are rendered highly mobile in a controlled and reversible manner. Through a combination of thin-film growth, transmission-electron-microscopy-based nanobeam diffraction and nanoscale band-excitation switching spectroscopy, we show that strain gradients in compositionally graded PbZr1-xTixO3 heterostructures stabilize needle-like ferroelastic domains that terminate inside the film. These needle-like domains are highly labile in the out-of-plane direction under applied electric fields, producing a locally enhanced piezoresponse. This work demonstrates the efficacy of novel modes of epitaxy in providing new modalities of domain engineering and potential for as-yet-unrealized nanoscale functional devices.

Co-registered Topographical, Band Excitation Nanomechanical, and Mass Spectral Imaging Using a Combined Atomic Force Microscopy/Mass Spectrometry Platform

The advancement of a hybrid atomic force microscopy/mass spectrometry imaging platform demonstrating the co-registered topographical, band excitation nanomechanical, and mass spectral imaging of a surface using a single instrument is reported. The mass spectrometry-based chemical imaging component of the system utilized nanothermal analysis probes for pyrolytic surface sampling followed by atmospheric pressure chemical ionization of the gas-phase species produced with subsequent mass analysis. The basic instrumental setup and operation are discussed, and the multimodal imaging capability and utility are demonstrated using a phase-separated polystyrene/poly(2-vinylpyridine) polymer blend thin film. The topography and band excitation images showed that the valley and plateau regions of the thin film surface were comprised primarily of one of the two polymers in the blend with the mass spectral chemical image used to definitively identify the polymers at the different locations. Data point pixel size for the topography (390 nm × 390 nm), band excitation (781 nm × 781 nm), and mass spectrometry (690 nm × 500 nm) images was comparable and submicrometer in all three cases, but the data voxel size for each of the three images was dramatically different. The topography image was uniquely a surface measurement, whereas the band excitation image included information from an estimated 20 nm deep into the sample and the mass spectral image from 110 to 140 nm in depth. Because of this dramatic sampling depth variance, some differences in the band excitation and mass spectrometry chemical images were observed and were interpreted to indicate the presence of a buried interface in the sample. The spatial resolution of the chemical image was estimated to be between 1.5 and 2.6 μm, based on the ability to distinguish surface features in that image that were also observed in the other images.

Single-domain multiferroic BiFeO3 films.

The strong coupling between antiferromagnetism and ferroelectricity at room temperature found in BiFeO3 generates high expectations for the design and development of technological devices with novel functionalities. However, the multi-domain nature of the material tends to nullify the properties of interest and complicates the thorough understanding of the mechanisms that are responsible for those properties. Here we report the realization of a BiFeO3 material in thin film form with single-domain behaviour in both its magnetism and ferroelectricity: the entire film shows its antiferromagnetic axis aligned along the crystallographic b axis and its ferroelectric polarization along the c axis. With this we are able to reveal that the canted ferromagnetic moment due to the Dzyaloshinskii–Moriya interaction is parallel to the a axis. Furthermore, by fabricating a Co/BiFeO3 heterostructure, we demonstrate that the ferromagnetic moment of the Co film does couple directly to the canted moment of BiFeO3.

Kelvin probe force microscopy in liquid using electrochemical force microscopy

Summary Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid–gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe–sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.

Deterministic arbitrary switching of polarization in a ferroelectric thin film.

Ferroelectrics have been used as memory storage devices, with an upper bound on the total possible memory levels generally dictated by the number of degenerate states allowed by the symmetry of the ferroelectric phase. Here, we introduce a new concept for storage wherein the polarization can be rotated arbitrarily, effectively decoupling it from the crystallographic symmetry of the ferroelectric phase on the mesoscale. By using a Bi5Ti3FeO15-CoFe2O4 film and via Band-Excitation Piezoresponse Force Microscopy, we show the ability to arbitrarily rotate polarization, create a spectrum of switched states, and suggest the reason for polarization rotation is an abundance of sub-50 nm nanodomains. Transmission electron microscopy-based strain mapping confirms significant local strain undulations imparted on the matrix by the CoFe2O4 inclusions, which causes significant local disorder. These experiments point to controlled tuning of polarization rotation in a standard ferroelectric, and hence the potential to greatly extend the attainable densities for ferroelectric memories.

Fundamental limitation to the magnitude of piezoelectric response of ⟨001⟩pc textured K0.5Na0.5NbO3 ceramic

⟨001⟩pc textured K0.5Na0.5NbO3 (KNN) ceramic was found to exhibit a 65% improvement in the longitudinal piezoelectric response as compared to its random counterpart. Piezoresponse force microscopy study revealed the existence of larger 180° and non-180° domains for textured ceramic as compared to the random ceramic. Improvement in piezoresponse by the development of ⟨001⟩pc texture is discussed in terms of the crystallographic nature of KNN and domain morphology. A comparative analysis performed with a rhombohedral composition suggested that the improvement in longitudinal piezoresponse of polycrystalline ceramics by the development of ⟨001⟩pc texture is determined by the crystal structure.

Quantitative 3D-KPFM imaging with simultaneous electrostatic force and force gradient detection.

Kelvin probe force microscopy (KPFM) is a powerful characterization technique for imaging local electrochemical and electrostatic potential distributions and has been applied across a broad range of materials and devices. Proper interpretation of the local KPFM data can be complicated, however, by convolution of the true surface potential under the tip with additional contributions due to long range capacitive coupling between the probe (e.g. cantilever, cone, tip apex) and the sample under test. In this work, band excitation (BE)-KPFM is used to negate such effects. In contrast to traditional single frequency KPFM, multifrequency BE-KPFM is shown to afford dual sensitivity to both the electrostatic force and the force gradient detection, analogous to simultaneous amplitude modulated and frequency modulated KPFM imaging. BE-KPFM is demonstrated on a Pt/Au/SiO(x) test structure and electrostatic force gradient detection is found to lead to an improved lateral resolution compared to electrostatic force detection. Finally, a 3D-KPFM imaging technique is developed. Force volume (FV) BE-KPFM allows the tip-sample distance dependence of the electrostatic interactions (force and force gradient) to be recorded at each point across the sample surface. As such, FVBE-KPFM provides a much needed pathway towards complete tip-sample capacitive de-convolution in KPFM measurements and will enable quantitative surface potential measurements with nanoscale resolution.

Breaking the limits of structural and mechanical imaging of the heterogeneous structure of coal macerals

The correlation between local mechanical (elasto-plastic) and structural (composition) properties of coal presents significant fundamental and practical interest for coal processing and for the development of rheological models of coal to coke transformations. Here, we explore the relationship between the local structural, chemical composition, and mechanical properties of coal using a combination of confocal micro-Raman imaging and band excitation atomic force acoustic microscopy for a bituminous coal. This allows high resolution imaging (10s of nm) of mechanical properties of the heterogeneous (banded) architecture of coal and correlating them to the optical gap, average crystallite size, the bond-bending disorder of sp(2) aromatic double bonds, and the defect density. This methodology allows the structural and mechanical properties of coal components (lithotypes, microlithotypes, and macerals) to be understood, and related to local chemical structure, potentially allowing for knowledge-based modeling and optimization of coal utilization processes.

Electrical domain morphologies in compositionally graded ferroelectric films.

We present a nonlinear thermodynamic formalism coupled with an electrostatic analysis of uniaxial n-layered compositionally graded heteroepitaxial ferroelectric films and extend this formalism to continuously graded ferroelectric films. We show that the domain morphology and its subsequent evolution in the presence of an electric field are determined by the spontaneous polarisation of the film induced through the compositional grading. The results for compositionally graded epitaxial (001) (Ba,Sr)TiO(3) and (001) Pb(Zr,Ti)O(3) films on (001)SrTiO(3) demonstrate that, while the domain morphologies in these two films are different in appearance, the dielectric displacement and the dielectric permittivity of such graded ferroelectric films exhibit a strong nonlinear behaviour which results in a high dielectric tunability. These findings indicate that it is possible to design specific domain structures that will yield desirable dielectric properties by controlling the strength of the compositional grading in the films.