We report the temporal evolution of the wettability of highly ordered pyrolytic graphite (HOPG) exposed to environmental conditions. Macroscopic wettability is investigated by static and dynamic contact angles (SCA and DCA) obtaining values comparable to the ones presented in the literature. SCA increases from ∼68° to ∼90° during the first hour of exposure after cleaving, whereas DCA is characterized by longer-scale (24 h) time evolution. We interpret these results in light of Fourier transform infrared spectroscopy, which indicates that the evolution of the HOPG wettability is due to adsorption of molecules from the surrounding atmosphere. This hypothesis is further confirmed by nanoscopic observations obtained by atomic force microscope (AFM)-based force spectroscopy, which monitor the evolution of surface properties with a spatial resolution superior to macroscopic experiments. Moreover, we observe that the results of macro- and nanoscale measurements evolve in similar fashion with time and we propose a quantitative correlation between SCA and AFM measurements. Our results suggest that the cause of the transition in the wettability of HOPG is due to the adsorption of hydrocarbon contaminations and water molecules from the environment. This is corroborated by annealing the HOPG is vacuum conditions at 150°, allowing the desorption of molecules on the surface, and thus re-establishing the initial macro and nano surface properties. Our findings can be used in the interpretation of the wettability of more complicated systems derived from HOPG (i.e., graphene).

The need to resolve the electrical properties of confined structures (CNTs, quantum dots, nanorods, etc) is becoming increasingly important in the field of electronic and optoelectronic devices. Here we propose an approach based on amplitude modulated electrostatic force microscopy to obtain measurements at small tip-sample distances, where highly nonlinear forces are present. We discuss how this improves the lateral resolution of the technique and allows probing of the electrical and surface properties. The complete force field at different tip biases is employed to derive the local work function difference. Then, by appropriately biasing the tip-sample system, short-range forces are reconstructed. The short-range component is then separated from the generic tip-sample force in order to recover the pure electrostatic contribution. This data can be employed to derive the tip-sample capacitance curve and the sample dielectric constant. After presenting a theoretical model that justifies the need for probing the electrical properties of the sample in the vicinity of the surface, the methodology is presented in detail and verified experimentally.

In electrostatic force microscopy (EFM), a conductive atomic force microscopy (AFM) tip is electrically biased against a grounded sample and electrostatic forces are investigated. This methodology has been broadly used in the scientific community to characterize dielectric properties of samples at the nanoscale. Two are the main operating conditions associated with this technique. The oscillation amplitude is usually kept to very small values to allow a linearized approach to the force reconstruction and the tip-sample distance is maintained elevated. However, this latter condition negatively affects the lateral resolution of the technique. Thus, electrostatic interaction should be probed in the vicinity of the sample. Theoretically, in this region the force can be linearized using oscillation amplitudes in the order of Å. This might cause the trapping of the tip on the surface (snap-in). Furthermore, at small distances, short-range forces (i.e. Van der Waals’) might reach values comparable to electrostatic forces.Here we present a framework that combines EFM and dynamic amplitude modulation AFM to achieve decoupled reconstruction of forces. It permits reconstructing the real shape of the electrostatic force and the capacitance of the tip-sample system even in the vicinity of the surface. This is done using a technique proposed in literature by Sader and Katan to reconstruct the force without the linearization approximation. The steps needed to decouple short-range and electrostatic forces are explained in detail. This data can be employed to derive the electrical properties of thin films with enhanced lateral resolution with respect to the commonly used EFM techniques.