Ion Jump Dynamics in Nanoscopic Subvolumes Analyzed by Electrostatic Force Spectroscopy

Schirmeisen, André; Taskiran, Ahmet; Bracht, H.; Roling, Bernhard

doi:10.1524/zpch.2010.0016

Cited by 6 publications

(7 citation statements)

References 38 publications

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“…The change in the spectrum's knee with increasing light intensity is in qualitative agreement with the light-dependent R s used to explain the Fig. 1 iments the response of ions to a step-change in tip voltage is tracked in real time through a shift in cantilever frequency [37][38][39][40][41][42]. EFM has been used to follow the time evolution of photocapacitance in response to illumination [43][44][45][46].…”

Section: Introductionsupporting

confidence: 70%

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Lagrangian and Impedance-Spectroscopy Treatments of Electric Force Microscopy

2019

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Scanning probe microscopy is often extended beyond simple topographic imaging to study electrical forces and sample properties, with the most widely used experiment being frequency-modulated Kelvin probe force microscopy. The equations commonly used to interpret this frequency-modulated experiment, however, rely on two hidden assumptions. The first assumption is that the tip charge oscillates in phase with the cantilever motion to keep the tip voltage constant. The second assumption is that any changes in the tip-sample interaction happen slowly. Starting from an electro-mechanical model of the cantilever-sample interaction, we use Lagrangian mechanics to derive coupled equations of motion for the cantilever position and charge. We solve these equations analytically using perturbation theory, and, for verification, numerically. This general approach rigorously describes scanned probe experiments even in the case when the usual assumptions of fast tip charging and slowly changing samples properties are violated. We develop a Magnus-expansion approximation to illustrate how abrupt changes in the tip-sample interaction cause abrupt changes in the cantilever amplitude and phase. We show that feedback-free time-resolved electric force microscopy cannot uniquely determine sub-cycle photocapacitance dynamics. We then use first-order perturbation theory to relate cantilever frequency shift and dissipation to the sample impedance even when the tip charge oscillates out of phase with the cantilever motion. Analogous to the treatment of impedance spectroscopy in electrochemistry, we apply this approximation to determine the cantilever frequency shift and dissipation for an arbitrary sample impedance in both local dielectric spectroscopy and broadband local dielectric spectroscopy experiments. The general approaches we develop provide a path forward for rigorously modeling the coupled motion of the cantilever position and charge in the wide range of electrical scanned probe microscopy experiments where the hidden assumptions of the conventional equations are violated or inapplicable. arXiv:1807.01219v2 [cond-mat.mes-hall]

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Section: Introductionsupporting

confidence: 70%

“…In Fig. 2 iments the response of ions to a step-change in tip voltage is tracked in real time through a shift in cantilever frequency [37][38][39][40][41][42]. EFM has been used to follow the time evolution of photocapacitance in response to illumination [43][44][45][46].…”

Section: Signi Cant Sample Impedancementioning

confidence: 99%

Lagrangian and Impedance-Spectroscopy Treatments of Electric Force Microscopy

2019

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“…This variation is most likely due to elastic coherency strain arising from large concentration gradients (due to phase separation during crystallization), which has been shown to significantly affect local chemical potential and collective ionic diffusivity. , The full transition from the characteristic relaxation time of the center grain to that of the outer grain occurs over ∼1 μm. This ∼1 μm variation across this boundary is also observed in the Kelvin probe force microscopy (KPFM) image (see Figure S3), indicating that the long length-scale variation is intrinsic to the sample and not the resolution limit of the technique, which has previously been reported as <100 nm …”

supporting

confidence: 67%

“…The time-domain electrostatic force spectroscopy technique was originally developed by Schirmeisen et al where a step potential is applied between a conductive AFM tip and sample and the measured interaction (i.e., change in cantilever resonance frequency) is recorded over time. This technique has been successfully used to measure Li + transport in LiAlSiO 4 with varying degrees of crystallinity, K + transport in K 2 O·2CaO·4SiO 2 (KCS) glass, and Na + transport in Na 2 O·GeO 2 (NG) glass samples. ,− The electric field generated inside the bulk is perpendicular to the surface in the region directly under the tip (Figure A), which causes ions to move as they attempt to shield the internal field. As charge builds up on the surface directly beneath the AFM tip, the electric field at the tip increases.…”

mentioning

confidence: 99%

Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy

et al. 2017

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One of the main challenges in improving fast charging lithium-ion batteries is the development of suitable active materials for cathodes and anodes. Many materials suffer from unacceptable structural changes under high currents and/or low intrinsic conductivities. Experimental measurements are required to optimize these properties, but few techniques are able to spatially resolve ionic transport properties at small length scales. Here we demonstrate an atomic force microscope (AFM)-based technique to measure local ionic transport on LiFePO to correlate with the structural and compositional analysis of the same region. By comparing the measured values with density functional theory (DFT) calculations, we demonstrate that Coulomb interactions between ions give rise to a collective activation energy for ionic transport that is dominated by large phase boundary hopping barriers. We successfully measure both the collective activation energy and the smaller single-ion bulk hopping barrier and obtain excellent agreement with values obtained from our DFT calculations.

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“…Time‐domain electrostatic force spectroscopy (TD‐EFS) has been used to characterize the dynamics of ion transport beneath the surface of battery materials . In this measurement, frequency shift caused by the electrostatic force between ions and the biased tip is recorded as a function of time, which directly reflects the dynamic ionic conduction behavior.…”

Section: Energy Storage Devicesmentioning

confidence: 99%

Functional Scanning Force Microscopy for Energy Nanodevices

et al. 2018

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Energy nanodevices, including energy conversion and energy storage devices, have become a major cross-disciplinary field in recent years. These devices feature long-range electron and ion transport coupled with chemical transformation, which call for novel characterization tools to understand device operation mechanisms. In this context, recent developments in functional scanning force microscopy techniques and their application in thin-film photovoltaic devices and lithium batteries are reviewed. The advantages of scanning force microscopy, such as high spatial resolution, multimodal imaging, and the possibility of in situ and in operando imaging, are emphasized. The survey indicates that functional scanning force microscopy is making significant contributions in understanding materials and interfaces in energy nanodevices.

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Ion Jump Dynamics in Nanoscopic Subvolumes Analyzed by Electrostatic Force Spectroscopy

Cited by 6 publications

References 38 publications

Lagrangian and Impedance-Spectroscopy Treatments of Electric Force Microscopy

Lagrangian and Impedance-Spectroscopy Treatments of Electric Force Microscopy

Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy

Functional Scanning Force Microscopy for Energy Nanodevices

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