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.

Electrochemical reactivity and proton transport mechanisms in nanostructured ceria.

Electrochemical reactivity and ionic transport at the nanoscale are essential in many energy applications. In this study, time-resolved Kelvin probe force microscopy (tr-KPFM) is utilized for surface potential mapping of nanostructured ceria, in both space and time domains. The fundamental mechanisms of proton injection and transport are studied as a function of environmental conditions and the presence or absence of triple phase boundaries. Finite element modeling is used to extract physical parameters from the experimental data, allowing not only quantification of the observed processes, but also decoupling of their contributions to the measured signal. The constructed phase diagrams of the parameters demonstrate a thermally activated proton injection reaction at the triple phase boundary, and two transport processes that are responsible for the low-temperature proton conductivity of nanostructured ceria.

CuInP2S6 Room Temperature Layered Ferroelectric.

We explore ferroelectric properties of cleaved 2-D flakes of copper indium thiophosphate, CuInP2S6 (CITP), and probe size effects along with limits of ferroelectric phase stability, by ambient and ultra high vacuum scanning probe microscopy. CITP belongs to the only material family known to display ferroelectric polarization in a van der Waals, layered crystal at room temperature and above. Our measurements directly reveal stable, ferroelectric polarization as evidenced by domain structures, switchable polarization, and hysteresis loops. We found that at room temperature the domain structure of flakes thicker than 100 nm is similar to the cleaved bulk surfaces, whereas below 50 nm polarization disappears. We ascribe this behavior to a well-known instability of polarization due to depolarization field. Furthermore, polarization switching at high bias is also associated with ionic mobility, as evidenced both by macroscopic measurements and by formation of surface damage under the tip at a bias of 4 V-likely due to copper reduction. Mobile Cu ions may therefore also contribute to internal screening mechanisms. The existence of stable polarization in a van-der-Waals crystal naturally points toward new strategies for ultimate scaling of polar materials, quasi-2D, and single-layer materials with advanced and nonlinear dielectric properties that are presently not found in any members of the growing "graphene family".

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.

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.

Open loop Kelvin probe force microscopy with single and multi-frequency excitation.

Conventional Kelvin probe force microscopy (KPFM) relies on closed loop (CL) bias feedback for the determination of surface potential (SP). However, SP measured by CL-KPFM has been shown to be strongly influenced by the choice of measurement parameters due to non-electrostatic contributions to the input signal of the bias feedback loop. This often leads to systematic errors of several hundred mV and can also result in topographical crosstalk. Here, open loop (OL)-KPFM modes are investigated as a means of obtaining a quantitative, crosstalk free measurement of the SP of graphene grown on Cu foil, and are directly contrasted with CL-KPFM. OL-KPFM operation is demonstrated in both single and multi-frequency excitation regimes, yielding quantitative SP measurements. The SP difference between single and multilayer graphene structures using OL-KPFM was found to be 63 ± 11 mV, consistent with values previously reported by CL-KPFM. Furthermore, the same relative potential difference between Al2O3-coated graphene and Al2O3-coated Cu was observed using both CL and OL techniques. We observed an offset of 55 mV between absolute SP values obtained by OL and CL techniques, which is attributed to the influence of non-electrostatic contributions to the input of the bias feedback used in CL-KPFM.

Collective dynamics underpins Rayleigh behavior in disordered polycrystalline ferroelectrics.

Nanoscale and mesoscopic disorder and associated local hysteretic responses underpin the unique properties of spin and cluster glasses, phase-separated oxides, polycrystalline ferroelectrics, and ferromagnets alike. Despite the rich history of the field, the relationship between the statistical descriptors of hysteresis behavior such as Preisach density, and micro and nanostructure has remained elusive. By using polycrystalline ferroelectric capacitors as a model system, we now report quantitative nonlinearity measurements in 0.025-1 microm(3) volumes, approximately 10(6) times smaller than previously possible. We discover that the onset of nonlinear behavior with thickness proceeds through formation and increase of areal density of micron-scale regions with large nonlinear response embedded in a more weakly nonlinear matrix. This observation indicates that large-scale collective domain wall dynamics, as opposed to motion of noninteracting walls, underpins Rayleigh behavior in disordered ferroelectrics. The measurements provide evidence for the existence and extent of the domain avalanches in ferroelectric materials, forcing us to rethink 100-year old paradigms.

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.

Switchable induced polarization in LaAlO3/SrTiO3 heterostructures.

Demonstration of a tunable conductivity of the LaAlO(3)/SrTiO(3) interfaces drew significant attention to the development of oxide electronic structures where electronic confinement can be reduced to the nanometer range. While the mechanisms for the conductivity modulation are quite different and include metal-insulator phase transition and surface charge writing, generally it is implied that this effect is a result of electrical modification of the LaAlO(3) surface (either due to electrochemical dissociation of surface adsorbates or free charge deposition) leading to the change in the two-dimensional electron gas (2DEG) density at the LaAlO(3)/SrTiO(3) (LAO/STO) interface. In this paper, using piezoresponse force microscopy we demonstrate a switchable electromechanical response of the LAO overlayer, which we attribute to the motion of oxygen vacancies through the LAO layer thickness. These electrically induced reversible changes in bulk stoichiometry of the LAO layer are a signature of a possible additional mechanism for nanoscale oxide 2DEG control on LAO/STO interfaces.

Substrate clamping effects on irreversible domain wall dynamics in lead zirconate titanate thin films.

The role of long-range strain interactions on domain wall dynamics is explored through macroscopic and local measurements of nonlinear behavior in mechanically clamped and released polycrystalline lead zirconate-titanate (PZT) films. Released films show a dramatic change in the global dielectric nonlinearity and its frequency dependence as a function of mechanical clamping. Furthermore, we observe a transition from strong clustering of the nonlinear response for the clamped case to almost uniform nonlinearity for the released film. This behavior is ascribed to increased mobility of domain walls. These results suggest the dominant role of collective strain interactions mediated by the local and global mechanical boundary conditions on the domain wall dynamics. The work presented in this Letter demonstrates that measurements on clamped films may considerably underestimate the piezoelectric coefficients and coupling constants of released structures used in microelectromechanical systems, energy harvesting systems, and microrobots.

Exploring mesoscopic physics of vacancy-ordered systems through atomic scale observations of topological defects.

Vacancy-ordered transition metal oxides have multiple similarities to classical ferroic systems including ferroelectrics and ferroelastics. The expansion coefficients for corresponding Ginzburg-Landau-type free energies are readily accessible from bulk phase diagrams. Here, we demonstrate that the gradient and interfacial terms can quantitatively be determined from the atomically resolved scanning transmission electron microscopy data of the topological defects and interfaces in model lanthanum-strontium cobaltite. With this knowledge, the interplay between ordering, chemical composition, and mechanical effects at domain walls, interfaces and structural defects can be analyzed.

Synthesis and electroplating of high resolution insulated carbon nanotube scanning probes for imaging in liquid solutions.

High resolution and isolated scanning probe microscopy (SPM) is in demand for continued development of energy storage and conversion systems involving chemical reactions at the nanoscale as well as an improved understanding of biological systems. Carbon nanotubes (CNTs) have large aspect ratios and, if leveraged properly, can be used to develop high resolution SPM probes. Isolation of SPM probes can be achieved by depositing a dielectric film and selectively etching at the apex of the probe. In this paper the fabrication of a high resolution and isolated SPM tip is demonstrated using electron beam induced etching of a dielectric film deposited onto an SPM tip with an attached CNT at the apex.

Electromechanical and elastic probing of bacteria in a cell culture medium.

Rapid phenotype characterization and identification of cultured cells, which is needed for progress in tissue engineering and drug testing, requires an experimental technique that measures physical properties of cells with sub-micron resolution. Recently, band excitation piezoresponse force microscopy (BEPFM) has been proven useful for recognition and imaging of bacteria of different types in pure water. Here, the BEPFM method is performed for the first time on physiologically relevant electrolyte media, such as Dulbecco's phosphate-buffered saline (DPBS) and Dulbecco's modified Eagle's medium (DMEM). Distinct electromechanical responses for Micrococcus lysodeikticus (Gram-positive) and Pseudomonas fluorescens (Gram-negative) bacteria in DPBS are demonstrated. The results suggest that mechanical properties of the outer surface coating each bacterium, as well as the electrical double layer around them, are responsible for the BEPFM image formation mechanism in electrolyte media.

Symmetry relationship and strain-induced transitions between insulating M1 and M2 and metallic R phases of vanadium dioxide.

The ability to synthesize VO2 in the form of single-crystalline nanobeams and nano- and microcrystals uncovered a number of previously unknown aspects of the metal-insulator transition (MIT) in this oxide. In particular, several reports demonstrated that the MIT can proceed through competition between two monoclinic (insulating) phases M1 and M2 and the tetragonal (metallic) R phase under influence of strain. The nature of such phase behavior has been not identified. Here we show that the competition between M1 and M2 phases is purely lattice-symmetry-driven. Within the framework of the Ginzburg-Landau formalism, both M phases correspond to different directions of the same four-component structural order parameter, and as a consequence, the M2 phase can appear under a small perturbation of the M1 structure such as doping or stress. We analyze the strain-controlled phase diagram of VO2 in the vicinity of the R-M2-M1 triple point using the Ginzburg-Landau formalism and identify and experimentally verify the pathways for strain-control of the transition. These insights open the door toward more systematic approaches to synthesis of VO2 nanostructures in desired phase states and to use of external fields in the control of the VO2 phase states. Additionally, we report observation of the triclinic T phase at the heterophase domain boundaries in strained quasi-two-dimensional VO2 nanoplatelets, and theoretically predict phases that have not been previously observed.

Electric modulation of conduction in multiferroic Ca-doped BiFeO3 films.

Many interesting materials phenomena such as the emergence of high-Tc superconductivity in the cuprates and colossal magnetoresistance in the manganites arise out of a doping-driven competition between energetically similar ground states. Doped multiferroics present a tantalizing evolution of this generic concept of phase competition. Here, we present the observation of an electronic conductor-insulator transition by control of band-filling in the model antiferromagnetic ferroelectric BiFeO3 through Ca doping. Application of electric field enables us to control and manipulate this electronic transition to the extent that a p-n junction can be created, erased and inverted in this material. A 'dome-like' feature in the doping dependence of the ferroelectric transition is observed around a Ca concentration of approximately 1/8, where a new pseudo-tetragonal phase appears and the electric modulation of conduction is optimized. Possible mechanisms for the observed effects are discussed on the basis of the interplay of ionic and electronic conduction. This observation opens the door to merging magnetoelectrics and magnetoelectronics at room temperature by combining electronic conduction with electric and magnetic degrees of freedom already present in the multiferroic BiFeO3.

Conduction at domain walls in oxide multiferroics.

Domain walls may play an important role in future electronic devices, given their small size as well as the fact that their location can be controlled. Here, we report the observation of room-temperature electronic conductivity at ferroelectric domain walls in the insulating multiferroic BiFeO(3). The origin and nature of the observed conductivity are probed using a combination of conductive atomic force microscopy, high-resolution transmission electron microscopy and first-principles density functional computations. Our analyses indicate that the conductivity correlates with structurally driven changes in both the electrostatic potential and the local electronic structure, which shows a decrease in the bandgap at the domain wall. Additionally, we demonstrate the potential for device applications of such conducting nanoscale features.

Suppression of octahedral tilts and associated changes in electronic properties at epitaxial oxide heterostructure interfaces.

Epitaxial oxide interfaces with broken translational symmetry have emerged as a central paradigm behind the novel behaviors of oxide superlattices. Here, we use scanning transmission electron microscopy to demonstrate a direct, quantitative unit-cell-by-unit-cell mapping of lattice parameters and oxygen octahedral rotations across the BiFeO3-La0.7 Sr0.3 MnO3 interface to elucidate how the change of crystal symmetry is accommodated. Combined with low-loss electron energy loss spectroscopy imaging, we demonstrate a mesoscopic antiferrodistortive phase transition near the interface in BiFeO3 and elucidate associated changes in electronic properties in a thin layer directly adjacent to the interface.

Domain wall conductivity in La-doped BiFeO3.

The transport physics of domain wall conductivity in La-doped bismuth ferrite (BiFeO3) has been probed using variable temperature conducting atomic force microscopy and piezoresponse force microscopy in samples with arrays of domain walls in the as-grown state. Nanoscale current measurements are investigated as a function of bias and temperature and are shown to be consistent with distinct electronic properties at the domain walls leading to changes in the observed local conductivity. Our observation is well described within a band picture of the observed electronic conduction. Finally, we demonstrate an additional degree of control of the wall conductivity through chemical doping with oxygen vacancies, thus influencing the local conductive state.

Ferroelectricity in strain-free SrTiO3 thin films.

Biaxial strain is known to induce ferroelectricity in thin films of nominally nonferroelectric materials such as SrTiO3. By a direct comparison of the strained and strain-free SrTiO3 films using dielectric, ferroelectric, Raman, nonlinear optical and nanoscale piezoelectric property measurements, we conclude that all SrTiO3 films and bulk crystals are relaxor ferroelectrics, and the role of strain is to stabilize longer-range correlation of preexisting nanopolar regions, likely originating from minute amounts of unintentional Sr deficiency in nominally stoichiometric samples. These findings highlight the sensitive role of stoichiometry when exploring strain and epitaxy-induced electronic phenomena in oxide films, heterostructures, and interfaces.