Work function changes of Au were measured by Kelvin probe force microscopy (KPFM) in the nonpolar liquid decane. As a proof of principle for the measurement in liquids, we investigated the work function change of an Au substrate upon hexadecanethiol chemisorption. To relate the measured contact potential difference (CPD) during the chemisorption of alkanethiols to a change of the work function, the influence of physisorbed decane must be taken into account. It is crucial that either the work function of the scanning probe microscope (SPM) tip or the sample surface remains constant throughout the reaction, since both contribute to the CPD. We describe two routes for determining the work function shift of Au coated with a monolayer of alkanethiols: In the first route, the SPM tips were taken as reference surfaces (constant tip work function). For this approach, we used Au(111) surfaces and kept the SPM tip ex situ during the adsorption process. In the second route, structured surfaces with reactive and inert parts were studied by KPFM (constant reference work function). For this route, we prepared nanometer sized Au structures by nanosphere lithography on SiO(x) substrates. Now, the SiO(x) served as the inert reference surface. The shifts in the work function after exposure to the hexadecanethiol (HDT) solution were determined to be ΔΦ(Au+HDT,decane-Au,air) = -1.33 eV ± 0.07 eV (route I) and ΔΦ(Au+HDT,decane-Au,air) = -1.46 eV ± 0.04 eV (route II). Both values are in excellent agreement with the work function shifts determined by ultraviolet photoemission spectroscopy (UPS) reported in literature. The presented procedures of measuring work function changes in decane open new ways to study local reactions at solid-liquid interfaces.

The effect of nanoroughness on contact angles and pinning is investigated experimentally and numerically for low-energy surfaces. Nanoroughness is introduced by chemical vapor deposition of tetraethoxysilane and was quantified by scanning force microscopy. Addition of a root-mean-square roughness of 2 nm on a flat surface can increase the contact angle after fluorination by a semifluorinated silane by up to 30°. On the other hand, nanoroughness can improve or impair the liquid repellency of superhydrophobic surfaces that were made from assembled raspberry particles. Molecular dynamics simulations are performed in order to gain a microscopic understanding on how the length and the surface coating density of semifluorinated silanes influence the hydrophobicity. Solid-liquid surface free energy computations reveal that the wetting behavior strongly depends on the density and alignment of the semifluorinated silane. At coating densities in the range of experimental values, some water molecules can penetrate between the semifluorinated chains, thus increasing the surface energy. Combining the experimental and numerical data exhibits that a roughness-induced increase of the contact angle competes with increased pinning caused by penetration of liquid into nanopores or between neighboring semifluorinated molecules.

The Kelvin equation relates the vapor pressure of a volatile liquid to the curvature of the liquid surface. It describes phenomena such as capillary condensation, capillary adhesion, nucleation, and the adsorption of vapors into porous media. Here we propose an extension of the Kelvin equation, which takes into account changes of the vapor pressure due to electric fields. The presence of electric fields reduces the saturation vapor pressure and leads to field-induced condensation. Field-induced condensation can explain the presence of water bridges in scanning probe nanolithographic methods such as anodic oxidation.

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We investigated the photoinduced changes in the surface potential and conductivity for locally degraded active layers of organic solar cell materials using electrical modes of scanning force microscopy. Samples were degraded under different partial pressures of oxygen and humidity in the presence of light. Degraded and nondegraded areas were investigated by Kelvin Probe Force Microscopy (KPFM) and conductive scanning force microscopy (cSFM). The analysis allowed us to quantify the extent of degradation and compensate the contribution of the probe tip. Two typical blends used for organic solar cell, i.e., P3HT:PCBM and PCPDTBT:PCBM, were investigated. We observed that P3HT:PCBM photodegraded significantly more than PCPDTBT:PCBM for an environment containing oxygen. For short photodegradation times (1 h), we verified that changes in the surface potential and conductivity of P3HT:PCBM films were fully reversible after annealing. For individual layers of P3HT and PCBM, we found that only P3HT degrades. However, the blend material of P3HT and PCBM leads to an accelerated degradation supporting the interpretation that PCBM undergoes a series of oxidations in the blend.