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Fundamental mechanisms of energy storage, corrosion, sensing, and multiple biological functionalities are directly coupled to electrical processes and ionic dynamics at solid–liquid interfaces. In many cases, these processes are spatially inhomogeneous taking place at grain boundaries, step edges, point defects, ion channels, etc and possess complex time and voltage dependent dynamics. This necessitates time-resolved and real-space probing of these phenomena. In this review, we discuss the applications of force-sensitive voltage modulated scanning probe microscopy (SPM) for probing electrical phenomena at solid–liquid interfaces. We first describe the working principles behind electrostatic and Kelvin probe force microscopies (EFM & KPFM) at themore » gas–solid interface, review the state of the art in advanced KPFM methods and developments to (i) overcome limitations of classical KPFM, (ii) expand the information accessible from KPFM, and (iii) extend KPFM operation to liquid environments. We briefly discuss the theoretical framework of electrical double layer (EDL) forces and dynamics, the implications and breakdown of classical EDL models for highly charged interfaces or under high ion concentrations, and describe recent modifications of the classical EDL theory relevant for understanding nanoscale electrical measurements at the solid–liquid interface. We further review the latest achievements in mapping surface charge, dielectric constants, and electrodynamic and electrochemical processes in liquids. Lastly, we outline the key challenges and opportunities that exist in the field of nanoscale electrical measurements in liquid as well as providing a roadmap for the future development of liquid KPFM.« less

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 systemsmore » 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. As a result, 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.« less

Polarization switching in ferroelectric materials underpins a multitude of applications ranging from nonvolatile memories to data storage to ferroelectric lithography. While traditionally considered to be a functionality of the material only, basic theoretical considerations suggest that switching is expected to be intrinsically linked to changes in the electrochemical state of the surface. Hence, the properties and dynamics of the screening charges can affect or control the switching dynamics. Despite being recognized for over 50 years, analysis of these phenomena remained largely speculative. Here, we explore polarization switching on the prototypical LiNbO₃ surface using the combination of contact mode Kelvin probemore » force microscopy and chemical imaging by time-of-flight mass-spectrometry and demonstrate pronounced chemical differences between the domains. Here, these studies provide a consistent explanation to the anomalous polarization and surface charge behavior observed in LiNbO₃ and point to new opportunities in chemical control of polarization dynamics in thin films and crystals via control of surface chemistry, complementing traditional routes via bulk doping, and substrate-induced strain and tilt systems.« less

Metal thiophosphates are gaining attention in the context of quasi-two-dimensional van der Waals functional materials. Alkali thiophosphates are investigated as ion conductors for solid electrolytes, and transition-metal thiophosphates are explored as a new class of ferroelectric materials. For the latter, a representative copper indium thiophosphate is ferrielectric at room temperature and, despite low polarization, exhibits giant negative electrostrictive coefficients. In this work, we reveal that ionic conductivity in this material enables localized extraction of Cu ions from the lattice with a biased scanning probe microscopy tip, which is surprisingly reversible. The ionic conduction is tracked through local volume changes withmore » a scanning probe microscopy tip providing a current-free probing technique, which can be explored for other thiophosphates of interest. Nearly 90 nm-tall crystallites can be formed and erased reversibly on the surface of this material as a result of ionic motion, the size of which can be sensitively controlled by both magnitude and frequency of the electric field, as well as the ambient temperature. These experimental results and density functional theory calculations point to a remarkable resilience of CuInP₂S₆ to large-scale ionic displacement and Cu vacancies, in part enabled by the metastability of Cu-deficient phases. Moreover, we have found that the piezoelectric response of CuInP₂S₆ is enhanced by about 45% when a slight ionic modification is carried out with applied field. This new mode of modifying the lattice of CuInP₂S₆, and more generally ionically conducting thiophosphates, posits new prospects for their applications in van der Waals heterostructures, possibly in the context of catalytic or electronic functionalities.« less

Here, the preferential deposition of metal nanoparticles onto periodically poled lithium niobate surfaces, whereby photogenerated electrons accumulate in accordance with local electric fields and reduce metal ions from solution, is known to depend on the intensity and wavelength of the illumination and the concentration of the solution used. Here, it is shown that for identical deposition conditions (wavelength, intensity, concentration), post-poling annealing for 10 h at 200 °C modifies the surface reactivity through the reorientation of internal defect fields. Whereas silver nanoparticles deposit preferentially on the ⁺z domains on unannealed crystals, the deposition occurs preferentially along 180 degrees domain wallsmore » for annealed crystals. In neither case is the deposition selective; limited deposition occurs also on the unannealed ^-z domain surface and on both annealed domain surfaces. The observed behavior is attributed to a relaxation of the poling-induced defect frustration mediated by Li⁺ ion mobility during annealing, which affects the accumulation of electrons, thereby changing the surface reactivity. The evolution of the defect field with temperature is corroborated using Raman spectroscopy.« less

Controlling ferroelectric switching in Mg doped lithium niobate (Mg: LN) is of fundamental importance for optical device and domain wall electronics applications that require precise domain patterns. Stable ferroelectric switching has been previously observed in undoped LN layers above proton exchanged (PE) phases that exhibit reduced polarization, whereas PE layers have been found to inhibit lateral domain growth. Here, Mg doping, which is known to significantly alter ferroelectric switching properties including coercive field and switching currents, is shown to inhibit domain nucleation and stability in Mg: LN above buried PE phases that allow for precise ferroelectric patterning via domain growthmore » control. Furthermore, piezoresponse force microscopy (PFM) and switching spectroscopy PFM reveal that the voltage at which polarization switches from the "up" to the "down" state increases with increasing thickness in pure Mg: LN, whereas the voltage required for stable back switching to the original "up" state does not exhibit this thickness dependence. This behavior is consistent with the presence of an internal frozen defect field. The inhibition of domain nucleation above PE interfaces, observed in this study, is a phenomenon that occurs in Mg: LN but not in undoped samples and is mainly ascribed to a remaining frozen polarization in the PE phase that opposes polarization reversal. This reduced frozen depolarization field in the PE phase also influences the depolarization field of the Mg: LN layer above due to the presence of uncompensated polarization charge at the PE-Mg: LN boundary. Furthermore, these alterations in internal electric fields within the sample cause long-range lattice distortions in Mg: LN via electromechanical coupling, which were corroborated with complimentary Raman measurements.« less

Mg doped lithium niobate (Mg:LN) exhibits several advantages over undoped LN such as resistance to photorefraction, lower coercive fields, and p-type conductivity that is particularly pronounced at domain walls and opens up a range of applications, e.g., in domain wall electronics. Engineering of precise domain patterns necessitates well founded knowledge of switching kinetics, which can differ significantly from that of undoped LN. In this work, the role of humidity and sample composition in polarization reversal has been investigated under application of the same voltage waveform. Control over domain sizes has been achieved by varying the sample thickness and initial polarizationmore » as well as atmospheric conditions. Additionally, local introduction of proton exchanged phases allows for inhibition of domain nucleation or destabilization, which can be utilized to modify domain patterns. In polarization dependent current flow, attributed to charged domain walls and band bending, it the rectifying ability of Mg: LN in combination with suitable metal electrodes that allow for further tailoring of conductivity is demonstrated.« less