Albert Verdaguer

The environment of graphene probed by electrostatic force microscopy

We employ electrostatic force microscopy to study the electrostatic environment of graphene sheets prepared with the micromechanical exfoliation technique. We detect the electric dipole of residues left from the adhesive tape during graphene preparation, as well as the dipole of water molecules adsorbed on top of graphene. Water molecules form a dipole layer that can generate an electric field as large as ∼109Vm−1. We expect that water molecules can significantly modify the electrical properties of graphene devices.

Charging and discharging of graphene in ambient conditions studied with scanning probe microscopy

By means of scanning probe microscopy we are able to inject charges in isolated graphene sheets deposited on SiO2/Si wafers and characterize the discharge induced by water in controlled ambient conditions. Contact potential differences between the graphene surface and the probe tip, measured by Kelvin probe microscopy, show a linear relationship with the tip bias during charge injection. The discharge depends on relative humidity and decays exponentially with time constants of the order of tens of minutes. We propose that graphene discharges through the water film adsorbed on the SiO2 surface.

How localized are energy dissipation processes in nanoscale interactions

We describe fundamental energy dissipation in dynamic nanoscale processes in terms of the localization of the interactions. In this respect, the areal density of the energy dissipated per cycle and the effective area of interaction in which each process occurs are calculated for four elementary dissipative processes. It is the ratio between these two, which we term M, that provides information about how localized the interactions are. While our results are general, we use concepts from dynamic atomic force microscopy to describe the physical phenomenon. We show that neither the phase lag, nor the magnitude of the energy dissipated alone provide information about how dissipative processes are localized. Instead, M has to be considered.

Thin water films grown at ambient conditions on BaF2(111) studied by scanning polarization force microscopy

The interaction of water with freshly cleaved BaF(2)(111) surfaces has been studied using scanning force microscopy operated in different modes at room temperature and under controlled humidity. The Kelvin probe microscopy (KPM) mode has been used to study the evolution of the surface potential differences (SPDs). In the 20%-50% relative humidity (RH) range, adsorbed water forms two-dimensional solidlike bilayers (islands). The SPD between water islands and the bare substrate surface exhibits a sign crossover from negative ( approximately -30 mV) at low RHs to positive ( approximately +50 mV) at higher RHs, evidencing a cooperative and irreversible flipping of the preferential orientation of water dipoles, from pointing toward the surface evolving into the opposite direction. The KPM results suggest that the classical hexagonal (I(h)) bilayer configuration is not the most favorable structure.

Subharmonic excitation in amplitude modulation atomic force microscopy in the presence of adsorbed water layers

In ambient conditions, nanometric water layers form on hydrophilicsurfaces covering them and significantly changing their properties and characteristics. Here we report the excitation of subharmonics in amplitude modulation atomic force microscopy induced by intermittent water contacts. Our simulations show that there are several regimes of operation depending on whether there is perturbation of water layers. Single period orbitals, where subharmonics are never induced, follow only when the tip is either in permanent contact with the water layers or in pure noncontact where the water layers are never perturbed. When the water layers are perturbed subharmonic excitation increases with decreasing oscillation amplitude. We derive an analytical expression which establishes whether water perturbations compromise harmonic motion and show that the predictions are in agreement with numerical simulations. Empirical validation of our interpretation is provided by the observation of a range of values for apparent height of water layers when subharmonic excitation is predicted.

Two-dimensional wetting: The role of atomic steps on the nucleation of thin water films on BaF2(111) at ambient conditions

The interaction of water with freshly cleaved BaF(2)(111) surfaces at ambient conditions (room temperature and under controlled humidity) has been studied using scanning force microscopy in different operation modes. The images strongly suggest a high surface diffusion of water molecules on the surface indicated by the accumulation of water at step edges forming two-dimensional bilayered structures. Steps running along the 110 crystallographic directions show a high degree of hydrophilicity, as evidenced by small step-film contact angles, while steps running along other directions exhibiting a higher degree of kinks surprisingly behave in a quite opposite way. Our results prove that morphological defects such as steps can be crucial in improving two-dimensional monolayer wetting and stabilization of multilayer grown on surfaces that show good lattice mismatch with hexagonal ice.

Influence of the macroscopic shape of the tip on the contrast in scanning polarization force microscopy images

We demonstrate that a quantitative analysis of the contrast obtained in electrostatic force microscopy images that probe the dielectric response of the sample (scanning polarization force microscopy (SPFM)) requires numerical simulations that take into account both the macroscopic shape of the tip and the nanoscopic tip apex. To simulate the SPFM contrast, we have used the generalized image charge method (GICM), which is able to accurately deal with distances between a few nanometers and several microns, thus involving more than three orders of magnitude. Our numerical simulations show that the macroscopic shape of the tip accounts for most of the SPFM contrast. Moreover, we find a quasi-linear relation between the working tip-sample distance and the contrast for tip radii between 50 and 200 nm. Our calculations are compared with experimental measurements of the contrast between a thermally grown silicon oxide sample and a few-layer graphene film transferred onto it.

Investigation of nanoscale interactions by means of subharmonic excitation

Multifrequency atomic force microscopy holds promise as a method to provide qualitative and quantitative information about samples with high spatial resolution. Here, we provide experimental evidence of the excitation of subharmonics in ambient conditions in the regions where capillary interactions are predicted to be the mechanism of excitation. We also experimentally decouple a second mechanism for subharmonic excitation that is highly independent of environmental conditions such as relative humidity. This implies that material properties could be mapped. Subharmonic excitation could lead to experimental determination of surface water affinity in the nanoscale whenever water interactions are the mechanism of excitation.

Energy dissipation in the presence of sub-harmonic excitation in dynamic atomic force microscopy

Amplitude modulation atomic force microscopy allows quantifying energy dissipation in the nanoscale with great accuracy with the use of analytical expressions that account for the fundamental frequency and higher harmonics. Here, we focus on the effects of sub-harmonic excitation on energy dissipation and its quantification. While there might be several mechanisms inducing sub-harmonics, a general analytical expression to quantify energy dissipation whenever sub-harmonics are excited is provided. The expression is a generalization of previous findings. We validate the expression via numerical integration by considering capillary forces and provide experimental evidence of sub-harmonic excitation for a range of operational parameters.

Strong water-mediated friction asymmetry and surface dynamics of zwitterionic solids at ambient conditions: L-alanine as a case study

Water molecules strongly interact with freshly cleaved (011) surfaces of L-alanine single crystals at low relative humidity (below 10%) promoting diffusion of L-alanine molecules. Species mobility is enhanced above ~40% leading to the formation of two-dimensional islands with long-range order through Ostwald ripening. Scanning force microscopy experiments reveal that both, islands and terraces, are identical in nature (composition and crystallographic structure) but a relevant friction asymmetry appearing upon water-surface interaction evidences that orientation dependent properties exist between them at the molecular level. We interpret this observation as due to water incorporation in the topmost surface crystal structure. Eventually, for high humidity values, surface dissolution and roughening occur.