Subsurface imaging of carbon nanotube networks in polymers with DC-biased multifrequency dynamic atomic force microscopy.

The characterization of dispersion and connectivity of carbon nanotube (CNT) networks inside polymers is of great interest in polymer nanocomposites in new material systems, organic photovoltaics, and in electrodes for batteries and supercapacitors. We focus on a technique using amplitude modulation atomic force microscopy (AM-AFM) in the attractive regime of operation, using both single and dual mode excitation, which upon the application of a DC tip bias voltage allows, via the phase channel, the in situ, nanoscale, subsurface imaging of CNT networks dispersed in a polymer matrix at depths of 10-100 nm. We present an in-depth study of the origins of phase contrast in this technique and demonstrate that an electrical energy dissipation mechanism in the Coulomb attractive regime is key to the formation of the phase contrast which maps the spatial variations in the local capacitance and resistance due to the CNT network. We also note that dual frequency excitation can, under some conditions, improve the contrast for such samples. These methods open up the possibility for DC-biased amplitude modulation AFM to be used for mapping the variations in local capacitance and resistance in nanocomposites with conducting networks.

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.

Strain energy and lateral friction force distributions of carbon nanotubes manipulated into shapes by atomic force microscopy.

The interplay between local mechanical strain energy and lateral frictional forces determines the shape of carbon nanotubes on substrates. In turn, because of its nanometer-size diameter, the shape of a carbon nanotube strongly influences its local electronic, chemical, and mechanical properties. Few, if any, methods exist for resolving the strain energy and static frictional forces along the length of a deformed nanotube supported on a substrate. We present a method using nonlinear elastic rod theory in which we compute the flexural strain energy and static frictional forces along the length of single walled carbon nanotubes (SWCNTs) manipulated into various shapes on a clean SiO(2) substrate. Using only high resolution atomic force microscopy images of curved single walled nanotubes, we estimate flexural strain energy distributions on the order of attojoules per nanometer and the static frictional forces between a SWCNT and SiO(2) surface to be a minimum of 230 pN nm(-1).

Compositional contrast of biological materials in liquids using the momentary excitation of higher eigenmodes in dynamic atomic force microscopy.

Atomic Force microscope (AFM) cantilevers commonly used for imaging soft biological samples in liquids experience a momentary excitation of the higher eigenmodes at each tap. This transient response is very sensitive to the local sample elasticity under gentle imaging conditions because the higher eigenmode time period is comparable to the tip-sample contact time. By mapping the momentary excitation response, we demonstrate a new scanning probe spectroscopy capable of resolving with high sensitivity the variations in the elasticity of soft biological materials in liquids.