High resolution subsurface imaging using resonance-enhanced detection in 2nd-harmonic KPFM.

Second harmonic Kelvin probe force microscopy is a robust mechanism for subsurface imaging at the nanoscale. Here we exploit resonance-enhanced detection as a way to boost the subsurface contrast with higher force sensitivity using lower bias voltages, in comparison to the traditional off-resonance case. In this mode, the second harmonic signal of the electrostatic force is acquired at one of the eigenmode frequencies of the microcantilever. As a result, high resolution subsurface images are obtained in a variety of nanocomposites. To further understand the subsurface imaging detection upon electrostatic forces, we use a finite element model that approximates the geometry of the probe and sample. This allows the investigation of the contrast mechanism, the depth sensitivity and lateral resolution depending on tip-sample properties.

Nanoscale Mapping of Dielectric Properties of Nanomaterials from Kilohertz to Megahertz Using Ultrasmall Cantilevers.

Electrostatic force microscopy (EFM) is often used for nanoscale dielectric spectroscopy, the measurement of local dielectric properties of materials as a function of frequency. However, the frequency range of atomic force microscopy (AFM)-based dielectric spectroscopy has been limited to a few kilohertz by the resonance frequency and noise of soft microcantilevers used for this purpose. Here, we boost the frequency range of local dielectric spectroscopy by 3 orders of magnitude from a few kilohertz to a few megahertz by developing a technique that exploits the high resonance frequency and low thermal noise of ultrasmall cantilevers (USCs). We map the frequency response of the real and imaginary components of the capacitance gradient (∂C(ω)/∂z) by using second-harmonic EFM and a theoretical model, which relates cantilever dynamics to the complex dielectric constant. We demonstrate the method by mapping the nanoscale dielectric spectrum of polymer-based materials for organic electronic devices. Beyond offering a powerful extension to AFM-based dielectric spectroscopy, the approach also allows the identification of electrostatic excitation frequencies which affords high dielectric contrast on nanomaterials.

Sub-surface imaging of carbon nanotube-polymer composites using dynamic AFM methods.

High-resolution sub-surface imaging of carbon nanotube (CNT) networks within polymer nanocomposites is demonstrated through electrical characterization techniques based on dynamic atomic force microscopy (AFM). We compare three techniques implemented in the single-pass configuration: DC-biased amplitude modulated AFM (AM-AFM), electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM) in terms of the physics of sub-surface image formation and experimental robustness. The methods were applied to study the dispersion of sub-surface networks of single-walled nanotubes (SWNTs) in a polyimide (PI) matrix. We conclude that among these methods, the KPFM channel, which measures the capacitance gradient (∂C/∂d) at the second harmonic of electrical excitation, is the best channel to obtain high-contrast images of the CNT network embedded in the polymer matrix, without the influence of surface conditions. Additionally, we propose an analysis of the ∂C/∂d images as a tool to characterize the dispersion and connectivity of the CNTs. Through the analysis we demonstrate that these AFM-based sub-surface methods probe sufficiently deep within the SWNT composites, to resolve clustered networks that likely play a role in conductivity percolation. This opens up the possibility of dynamic AFM-based characterization of sub-surface dispersion and connectivity in nanostructured composites, two critical parameters for nanocomposite applications in sensors and energy storage devices.