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.

Band excitation in scanning probe microscopy: recognition and functional imaging.

Field confinement at the junction between a biased scanning probe microscope's 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.

Domain wall geometry controls conduction in ferroelectrics.

A new paradigm of domain wall nanoelectronics has emerged recently, in which the domain wall in a ferroic is itself an active device element. The ability to spatially modulate the ferroic order parameter within a single domain wall allows the physical properties to be tailored at will and hence opens vastly unexplored device possibilities. Here, we demonstrate via ambient and ultrahigh-vacuum (UHV) scanning probe microscopy (SPM) measurements in bismuth ferrite that the conductivity of the domain walls can be modulated by up to 500% in the spatial dimension as a function of domain wall curvature. Landau-Ginzburg-Devonshire calculations reveal the conduction is a result of carriers or vacancies migrating to neutralize the charge at the formed interface. Phase-field modeling indicates that anisotropic potential distributions can occur even for initially uncharged walls, from polarization dynamics mediated by elastic effects. These results are the first proof of concept for modulation of charge as a function of domain wall geometry by a proximal probe, thereby expanding potential applications for oxide ferroics in future nanoscale electronics.

Deep data analysis via physically constrained linear unmixing: universal framework, domain examples, and a community-wide platform.

Many spectral responses in materials science, physics, and chemistry experiments can be characterized as resulting from the superposition of a number of more basic individual spectra. In this context, unmixing is defined as the problem of determining the individual spectra, given measurements of multiple spectra that are spatially resolved across samples, as well as the determination of the corresponding abundance maps indicating the local weighting of each individual spectrum. Matrix factorization is a popular linear unmixing technique that considers that the mixture model between the individual spectra and the spatial maps is linear. Here, we present a tutorial paper targeted at domain scientists to introduce linear unmixing techniques, to facilitate greater understanding of spectroscopic imaging data. We detail a matrix factorization framework that can incorporate different domain information through various parameters of the matrix factorization method. We demonstrate many domain-specific examples to explain the expressivity of the matrix factorization framework and show how the appropriate use of domain-specific constraints such as non-negativity and sum-to-one abundance result in physically meaningful spectral decompositions that are more readily interpretable. Our aim is not only to explain the off-the-shelf available tools, but to add additional constraints when ready-made algorithms are unavailable for the task. All examples use the scalable open source implementation from https://github.com/ramkikannan/nmflibrary that can run from small laptops to supercomputers, creating a user-wide platform for rapid dissemination and adoption across scientific disciplines.

Ultrafast current imaging by Bayesian inversion.

Spectroscopic measurements of current-voltage curves in scanning probe microscopy is the earliest and one of the most common methods for characterizing local energy-dependent electronic properties, providing insight into superconductive, semiconductor, and memristive behaviors. However, the quasistatic nature of these measurements renders them extremely slow. Here, we demonstrate a fundamentally new approach for dynamic spectroscopic current imaging via full information capture and Bayesian inference. This general-mode I-V method allows three orders of magnitude faster measurement rates than presently possible. The technique is demonstrated by acquiring I-V curves in ferroelectric nanocapacitors, yielding >100,000 I-V curves in <20 min. This allows detection of switching currents in the nanoscale capacitors, as well as determination of the dielectric constant. These experiments show the potential for the use of full information capture and Bayesian inference toward extracting physics from rapid I-V measurements, and can be used for transport measurements in both atomic force and scanning tunneling microscopy.

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.

Giant elastic tunability in strained BiFeO3 near an electrically induced phase transition.

Elastic anomalies are signatures of phase transitions in condensed matters and have traditionally been studied using various techniques spanning from neutron scattering to static mechanical testing. Here, using band-excitation elastic/piezoresponse spectroscopy, we probed sub-MHz elastic dynamics of a tip bias-induced rhombohedral-tetragonal phase transition of strained (001)-BiFeO3 (rhombohedral) ferroelectric thin films from ∼10(3) nm(3) sample volumes. Near this transition, we observed that the Young's modulus intrinsically softens by over 30% coinciding with two- to three-fold enhancement of local piezoresponse. Coupled with phase-field modelling, we also addressed the influence of polarization switching and mesoscopic structural heterogeneities (for example, domain walls) on the kinetics of this phase transition, thereby providing fresh insights into the morphotropic phase boundary in ferroelectrics. Furthermore, the giant electrically tunable elastic stiffness and corresponding electromechanical properties observed here suggest potential applications of BiFeO3 in next-generation frequency-agile electroacoustic devices, based on the utilization of the soft modes underlying successive ferroelectric phase transitions.

Electrocatalysis-induced elasticity modulation in a superionic proton conductor probed by band-excitation atomic force microscopy.

Variable temperature band-excitation atomic force microscopy in conjunction with I-V spectroscopy was used to investigate the crystalline superionic proton conductor CsHSO4 during proton exchange induced by a Pt-coated conductive scanning probe. At a sample temperature of 150 °C and under an applied bias <1 V, reduction currents of up to 1 nA were observed. Simultaneously, we show that the electrochemical reactions are accompanied by a reversible decrease in the elastic modulus of CsHSO4, as seen by a contact resonance shift, and find evidence for superplasticity during scanning. These effects were not observed in the room-temperature phase of CsHSO4 or in the case of catalytically inactive conductive probes, proving the utility of this technique for monitoring electrochemical processes on the nanoscale, as well as the use of local contact stiffness as a sensitive indicator of electrochemical reactions.

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.

Higher order harmonic detection for exploring nonlinear interactions with nanoscale resolution.

Nonlinear dynamics underpin a vast array of physical phenomena ranging from interfacial motion to jamming transitions. In many cases, insight into the nonlinear behavior can be gleaned through exploration of higher order harmonics. Here, a method using band excitation scanning probe microscopy (SPM) to investigate higher order harmonics of the electromechanical response, with nanometer scale spatial resolution is presented. The technique is demonstrated by probing the first three harmonics of strain for a Pb(Zr(1-x)Ti(x))O3 (PZT) ferroelectric capacitor. It is shown that the second order harmonic response is correlated with the first harmonic response, whereas the third harmonic is not. Additionally, measurements of the second harmonic reveal significant deviations from Rayleigh-type models in the form of a much more complicated field dependence than is observed in the spatially averaged data. These results illustrate the versatility of n(th) order harmonic SPM detection methods in exploring nonlinear phenomena in nanoscale materials.

Controlling magnetoelectric coupling by nanoscale phase transformation in strain engineered bismuth ferrite.

The magnetoelectric coupling in multiferroic materials is promising for a wide range of applications, yet manipulating magnetic ordering by electric field proves elusive to obtain and difficult to control. In this paper, we explore the prospect of controlling magnetic ordering in misfit strained bismuth ferrite (BiFeO(3), BFO) films, combining theoretical analysis, numerical simulations, and experimental characterizations. Electric field induced transformation from a tetragonal phase to a distorted rhombohedral one in strain engineered BFO films has been identified by thermodynamic analysis, and realized by scanning probe microscopy (SPM) experiment. By breaking the rotational symmetry of a tip-induced electric field as suggested by phase field simulation, the morphology of distorted rhombohedral variants has been delicately controlled and regulated. Such capabilities enable nanoscale control of magnetoelectric coupling in strain engineered BFO films that is difficult to achieve otherwise, as demonstrated by phase field simulations.