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

Papandrew, Alexander B.; Li, Q.; Okatan, M. Baris; Jesse, Stephen; Hartnett, Chris; Kalinin, Sergei V.; Vasudevan, Rama K.

doi:10.1039/c5nr04809e

Cited by 7 publications

(3 citation statements)

References 33 publications

(32 reference statements)

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“…This modulation voltage vibrates the tip into the sample (or sample into tip), and the amplitude and phase of the resulting lever oscillations are decoupled, in a similar way to PFM. Combining CR-AFM with voltage spectroscopy has shown it is possible to explore local bias-induced phenomena ranging from purely bias induced elastic softening to surface electrochemical processes [91,112].…”

Section: Contrast In Vm-afmmentioning

confidence: 99%

Towards nanoscale electrical measurements in liquid by advanced KPFM techniques: a review

et al. 2018

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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 the 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. Finally, 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.

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Section: Contrast In Vm-afmmentioning

confidence: 99%

Towards nanoscale electrical measurements in liquid by advanced KPFM techniques: a review

et al. 2018

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“…In parallel, acoustic detection , of phase transitions and electrochemical reactions with SPM has been recently demonstrated, where the changes in contact resonant frequency are monitored as a function of some stimulus. For instance, Papandrew et al directly observed changes in the elastic modulus of a proton conductor at high temperature after application of bias when in the superionic phase. Similarly, Li et al have observed elastic softening before an onset of a structural phase transition in BiFeO 3 thin films, which has also been explored by other groups .…”

Section: Morphology and Single-point Current–voltage Investigation Of...mentioning

confidence: 99%

Nanoscale Probing of Elastic–Electronic Response to Vacancy Motion in NiO Nanocrystals

et al. 2017

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Measuring the diffusion of ions and vacancies at nanometer length scales is crucial to understanding fundamental mechanisms driving technologies as diverse as batteries, fuel cells, and memristors; yet such measurements remain extremely challenging. Here, we employ a multimodal scanning probe microscopy (SPM) technique to explore the interplay between electronic, elastic, and ionic processes via first-order reversal curve I-V measurements in conjunction with electrochemical strain microscopy (ESM). The technique is employed to investigate the diffusion of oxygen vacancies in model epitaxial nickel oxide (NiO) nanocrystals with resistive switching characteristics. Results indicate that opening of the ESM hysteresis loop is strongly correlated with changes to the resonant frequency, hinting that elastic changes stem from the motion of oxygen (or cation) vacancies in the probed volume of the SPM tip. These changes are further correlated to the current measured on each nanostructure, which shows a hysteresis loop opening at larger (∼2.5 V) voltage windows, suggesting the threshold field for vacancy migration. This study highlights the utility of local multimodal SPM in determining functional and chemical changes in nanoscale volumes in nanostructured NiO, with potential use to explore a wide variety of materials including phase-change memories and memristive devices in combination with site-correlated chemical imaging tools.

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“…However, emergence of amplitude based feedback and multiple frequency methods such as band excitation 188,190 has allowed to separate the electromechanical signal and resonant frequency both in imaging and spectroscopic PFM, as originally demonstrated by Maksymovych. 355 In the case of electrochemical reactions, Papandrew et al 356 noted the strong change in resonant frequency during bias application in CsHSO4 (CHS), coincident with reduction currents. CHS is a proton conductor at high temperature (above 140°C), but the changes in elastic modulus with voltage were absent in the room-temperature phase, or when non-catalytic probes were utilized, suggesting acoustic detection can be used as an effective probe of electrochemical reactions.…”

Section: D Acoustic Detectionmentioning

confidence: 99%

Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale

Vasudevan

Balke

Maksymovych

et al. 2017

Applied Physics Reviews

264

206

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Ferroelectric materials have remained one of the foci of condensed matter physics and materials science for over 50 years. In the last 20 years, the development of voltage-modulated scanning probe microscopy techniques, exemplified by Piezoresponse force microscopy (PFM) and associated time-and voltage spectroscopies, opened a pathway to explore these materials on a single-digit nanometer level. Consequently, domain structures, walls and polarization dynamics can now be imaged in real space. More generally, PFM has allowed studying electromechanical coupling in a broad variety of materials ranging from ionics to biological systems. It can also be anticipated that the recent Nobel prize 1 in molecular electromechanical machines will result in rapid growth in interest in PFM as a method to probe their behavior on single device and device assembly levels. However, the broad introduction of PFM also resulted in a growing number of reports on nearly-ubiquitous presence of ferroelectric-like phenomena including remnant polar states and electromechanical hysteresis loops in materials which are non-ferroelectric in the bulk, or in cases where size effects are expected to suppress ferroelectricity. While in certain cases plausible physical mechanisms can be suggested, there is remarkable similarity in observed behaviors, irrespective of the materials system. In this review, we summarize the basic principles of PFM, briefly discuss the features of ferroelectric surfaces salient to PFM imaging and spectroscopy, and summarize existing reports on ferroelectric-like responses in non-classical ferroelectric materials. We further discuss possible mechanisms behind observed behaviors, and possible experimental strategies for their identification.3

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

Cited by 7 publications

References 33 publications

Towards nanoscale electrical measurements in liquid by advanced KPFM techniques: a review

Towards nanoscale electrical measurements in liquid by advanced KPFM techniques: a review

Nanoscale Probing of Elastic–Electronic Response to Vacancy Motion in NiO Nanocrystals

Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale

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