Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

Morozovska, Anna N.; Eliseev, Eugene A.; Balke, Nina; Kalinin, Sergei V.

doi:10.1063/1.3460637

Cited by 147 publications

(189 citation statements)

References 75 publications

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“…248,257 The original description of ESM mechanism considered purely diffusional dynamics with fast voltage controlled generation-recombination of ionic species on the surface and near surface regions. 258 Subsequently, the model was extended to include both migration transport [259][260][261] and electrostrictive effects. 118,262,263 Finally, it was shown that ESM mechanism can be present even in the absence of a surface reaction.…”

Section: B Electrochemical Strain Microscopy (Esm)mentioning

confidence: 99%

“…Here, the reaction in the tip-surface junction is assumed to result in the generation and recombination of ionic species that subsequently are transported in the solid. For purely diffusional transport, the analytical solution was developed for 1D 247 and rotationally invariant 3D cases 258 and approximate solutions were developed for the anisotropic case. 327 In this case, surface displacement is proportional to βDion/√ω, where Dion is the diffusion constant of the mobile species, β is the Vegard coefficient, and ω is frequency.…”

Section: Ferroelectric Switchingmentioning

confidence: 99%

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

Vasudevan

Balke

Maksymovych

et al. 2017

Applied Physics Reviews

270

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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Section: B Electrochemical Strain Microscopy (Esm)mentioning

confidence: 99%

Section: Ferroelectric Switchingmentioning

confidence: 99%

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

Vasudevan

Balke

Maksymovych

et al. 2017

Applied Physics Reviews

270

206

View full text Add to dashboard Cite

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“…A schematic of processes below the tip is shown in Figure 2. Detailed description of the ESM response formation mechanism was given by Morozovska et al 7 Dynamics of the ESM response reflects instant changes of Li þ concentration, and therefore, serves as the signature of the Li þ mobility. It can be measured locally as a function of time by using ESM time spectroscopy.…”

Section: Electrochemical Strain Microscopymentioning

confidence: 99%

“…Alternatively, novel method called electrochemical strain microscopy (ESM) 7 is able to probe transport properties of ionically conducting materials at the scale down to a few nm, thus allow better understanding of functionality and degradation mechanisms. Up to now, it has been implemented in multi-frequency band excitation 8 and DART 9 modes on a number of lithium and oxygen conducting materials.…”

Section: Introductionmentioning

confidence: 99%

Li transport in fresh and aged LiMn2O4 cathodes via electrochemical strain microscopy

Luchkin

Romanyuk

Ivanov

et al. 2015

Journal of Applied Physics

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Transport properties of Li þ mobile ions in fresh and aged LiMn 2 O 4 battery cathodes were studied at the nanoscale via electrochemical strain microscopy (ESM), time spectroscopy, and voltage spectroscopy mapping. Both Vegard and plausible non-Vegard contributions to the ESM signal were identified in electrochemical hysteresis loops obtained on fresh and aged samples. In the fresh cathodes, the Vegard contribution dominates the signal, while in the aged samples different shape of hysteresis loops indicates an additional plausible non-Vegard contribution. Non-uniform spatial distribution of the electrochemical loop opening in LiMn 2 O 4 particles studied in the aged samples indicates stronger variation of the Li diffusion coefficient at the microscale as compared to the fresh specimens. Time spectroscopy measurements revealed a suppression of the local Li diffusivity in aged samples. The mechanisms of the cathode aging are discussed in the context of observed nanoscale ESM response. V C 2015 AIP Publishing LLC. [http://dx

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“…61 The measured dynamic strains provide information on the degree of transformation, were it the size of grown domain, 62 or the degree of intercalation, etc., enabling these processes to be probed in nanoscale volumes. The unique aspect of PFM, and in certain cases ESM, is that the signal is independent of the tip-surface contact radius [63][64][65][66] and hence is quantitative, enabling a broad spectrum of spectroscopic techniques.…”

Section: Dynamic Hysteresis Measurements In Pfmmentioning

confidence: 99%

Dynamic piezoresponse force microscopy: Spatially resolved probing of polarization dynamics in time and voltage domains

Kumar

Wada

Funakubo

et al. 2012

Journal of Applied Physics

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An approach for probing dynamic phenomena during hysteresis loop measurements in piezoresponse force microscopy (PFM) is developed. Dynamic PFM (D-PFM) necessitates development of 5-dimensional (5D) data acquisition protocols and associated methods for analysis and visualization of multidimensional data. Using a combination of multivariate statistical analysis and phenomenological fitting, we explore dynamic behavior during polarization switching in model ferroelectric films with dense ferroelastic domain structures and in ferroelectric capacitors. In polydomain films, multivariate analysis of the switching data suggests that ferroelectric and ferroelastic components can be decoupled and time dynamics can be explored. In capacitors, a strong correlation between polarization dynamics and microstructure is observed. The future potential of D-PFM for probing time-dependent hysteretic phenomena in ferroelectrics and ionic systems is discussed.

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Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

Cited by 147 publications

References 75 publications

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

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

Li transport in fresh and aged LiMn2O4 cathodes via electrochemical strain microscopy

Dynamic piezoresponse force microscopy: Spatially resolved probing of polarization dynamics in time and voltage domains

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