Now showing 1 - 10 of 11
  • Publication
    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 sp2 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.
      474Scopus© Citations 17
  • Publication
    Decoupling Mesoscale Functional Response in PLZT across the Ferroelectric-Relaxor Phase Transition with Contact Kelvin Probe Force Microscopy and Machine Learning
    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 systems 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. 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.
      224Scopus© Citations 8
  • Publication
    Dual harmonic Kelvin probe force microscopy at the graphene-liquid interface
    Kelvin probe force microscopy (KPFM) is a powerful technique for the determination of the contact potential difference (CPD) between an atomic force microscope tip and a sample under ambient and vacuum conditions. However, for many energy storage and conversion systems, including graphene-based electrochemical capacitors, understanding electrochemical phenomena at the solid¿liquid interface is paramount. Despite the vast potential to provide fundamental insight for energy storage materials at the nanoscale, KPFM has found limited applicability in liquid environments to date. Here, using dual harmonic (DH)-KPFM, we demonstrate CPD imaging of graphene in liquid. We find good agreement with measurements performed in air, highlighting the potential of DH-KPFM to probe electrochemistry at the graphene¿liquid interface.
      657Scopus© Citations 49
  • Publication
    Band excitation Kelvin probe force microscopy utilizing photothermal excitation
    (American Institute of Physics, 2015) ; ; ; ;
    A multifrequency open loop Kelvin probe force microscopy (KPFM) approach utilizingphotothermal as opposed to electrical excitation is developed. Photothermal band excitation (PthBE)-KPFM is implemented here in a grid mode on a model test sample comprising a metal-insulator junction with local charge-patterned regions. Unlike the previously described open loop BE-KPFM, which relies on capacitive actuation of the cantilever, photothermal actuation is shown to be highly sensitive to the electrostatic force gradient even at biases close to the contact potential difference (CPD). PthBE-KPFM is further shown to provide a more localized measurement of true CPD in comparison to the gold standard ambient KPFM approach, amplitude modulated KPFM. Finally, PthBE-KPFM data contain information relating to local dielectric properties and electronic dissipation between tip and sample unattainable using conventional single frequency KPFM approaches
      565Scopus© Citations 18
  • Publication
    Quantitative comparison of closed-loop and dual harmonic Kelvin probe force microscopy techniques
    Kelvin probe force microscopy (KPFM) is a widely used technique to map surface potentials at the nanometer scale. In traditional KPFM, a feedback loop regulates the DC bias applied between a sharp conductive probe and a sample to nullify the electrostatic force (closed-loop operation). In comparison, open-loop techniques such as dual harmonic KPFM (DH-KPFM) are simpler to implement, are less sensitive to artefacts, offer the unique ability to probe voltage sensitive materials, and operate in liquid environments. Here, we directly compare the two techniques in terms of their bandwidth and sensitivity to instrumentation artefacts. Furthermore, we introduce a new correction for traditional KPFM termed “setpoint correction,” which allows us to obtain agreement between open and closed-loop techniques within 1%. Quantitative validation of DH-KPFM may lead to a wider adoption of open-loop KPFM techniques by the scanning probe community.
      548Scopus© Citations 13
  • Publication
    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.
      720Scopus© Citations 62
  • Publication
    Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy
    Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid-liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does notrequire a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid-liquid interface.
      554Scopus© Citations 36
  • Publication
    Photoreduction of SERS-active metallic nanostructures on chemically-patterned ferroelectric crystals
    Photodeposition of metallic nanostructures onto ferroelectric surfaces is typically based on patterning local surface reactivity via electric field poling. Here, we demonstrate metal deposition onto substrates which have been chemically patterned via proton exchange (i.e., without polarization reversal). The chemical patterning provides the ability to tailor the electrostatic fields near the surface of lithium niobate crystals and these engineered fields are used to fabricate metallic nanostructures. The effect of the proton exchange process on the piezoelectric and electrostatic properties of the surface is characterized using voltage modulated atomic force microscopy techniques, which combined with modeling of the electric fields at the surface of the crystal, reveal that the deposition occurs preferentially along the boundary between ferroelectric and proton exchanged regions. The metallic nanostructures have been further functionalized with a target probe molecule, 4-aminothiophenol, from which surface enhanced Raman scattering (SERS) signal is detected, demonstrating the suitability of chemically patterned ferroelectrics as SERS-active templates.
      691Scopus© Citations 60
  • Publication
    Photoreduction of metal nanostructures on periodically proton exchanged MgO-doped lithium niobate crystals
    Local reactivity on periodically proton exchanged lithium niobate (PPE:LN) surfaces is a promising route for the fabrication of regularly spaced nanostructures. Here, using MgO-doped PPE:LN templates, we investigate the influence of the doping on the nanostructure formation as a function of the proton exchange (PE) depth. The deposition is found to occur preferentially along the boundary between MgO-doped LN and the PE region when the PE depth is at least 1.73 μm, however, for shallower depths, deposition occurs across the entire PE region. The results are found to be consistent with an increased photoconductivity of the MgO-doped LN.
      515Scopus© Citations 12
  • Publication
    Surface Chemistry Controls Anomalous Ferroelectric Behavior in Lithium Niobate
    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 probe force microscopy and chemical imaging by time-of-flight mass-spectrometry and demonstrate pronounced chemical differences between the domains. 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.
      313Scopus© Citations 20