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.

For systemic delivery of small interfering RNA (siRNA) to solid tumors, the carrier must circulate avoiding premature degradation, extravasate and penetrate tumors, enter target cells, traffic to the intracellular destination, and release siRNA for gene silencing. However, existing siRNA carriers, which typically exhibit positive charges, fall short of these requirements by a large margin; thus, systemic delivery of siRNA to tumors remains a significant challenge. To overcome the limitations of existing approaches, we have developed a carrier of siRNA, called “Nanosac”, a noncationic soft polyphenol nanocapsule. A siRNA-loaded Nanosac is produced by sequential coating of mesoporous silica nanoparticles (MSNs) with siRNA and polydopamine, followed by removal of the sacrificial MSN core. The Nanosac recruits serum albumin, co-opts caveolae-mediated endocytosis to enter tumor cells, and efficiently silences target genes. The softness of Nanosac improves extravasation and penetration into tumors compared to its hard counterpart. As a carrier of siRNA targeting PD-L1, Nanosac induces a significant attenuation of CT26 tumor growth by immune checkpoint blockade. These results support the utility of Nanosac in the systemic delivery of siRNA for solid tumor therapy.

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.

It is well known that sub-surface nano-objects can be detected by Atomic Force Microscopy (AFM) with either sub-surface stress or electric fields, by using dynamic AFM methods such as Contact Resonance AFM (CR-AFM) or 2nd-harmonic Kelvin Probe Force Microscopy (KPFM), respectively. However, little is understood regarding the relative differences between the two methods. We present a head-to-head comparison between the sub-surface imaging capabilities of these two methods through experiments and computational models based on finite element analysis (FEA). High resolution subsurface images are obtained using both techniques, from the same area of a polymer composite film containing single-walled carbon nanotube networks embedded in a polyimide matrix. The results are used to interpret quantitatively the observables from CR-AFM and KPFM, with a particular focus on the depth sensitivity and lateral resolution. The depth of the buried carbon nanotube bundles estimated by combining experiments and FEA is found to be in good agreement between the two methods.

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.