Surface Chemistry at the Nanometer Scale

This thesis describes research towards understanding surface chemical and physical processes, as well as their effects on the underlying substrate properties, at the nanometer and atomic scales. We demonstrate a method to tune the density of etch pits on Si(111) during the chlorination process so as to change the surface reactivity. Subsequent grafting of an azide group to replace chlorine demonstrates an example of non-oxidative passivation of silicon surfaces with new functionalities. Depending upon the solvent used in the azidation process, it is shown to yield different azidation kinetic rates, different final azide coverages, and different surface-area distributions. Scanning tunneling spectroscopy studies show that both chlorination and azidation processes significantly modify the surface electronic structures, with the former leading to a non-zero density of states at the Fermi level. Our studies on a new class of corrugation, i.e., wrinkles, in exfoliated graphene on SiO2 show that a "three-for-six" triangular pattern of atoms is exclusively and consistently observed on wrinkles, suggesting the local curvature of the wrinkle is a perturbation that breaks the six-fold symmetry of the graphene lattice. Lower electrical conductance is also found on the top of wrinkles compared to other regions of graphene. The wrinkles are characterized by the presence of midgap states, which is in agreement with recent theoretical predictions. A general method is also reported for reliably fabricating ultrahigh-density graphene nanoribbon (GNR) arrays. We have clearly observed how the properties of GNRs evolve as a function of number of graphene layers. The band gap (and so the on-off ratio) decreases as the number of layers increases. These results suggest that, in addition to single layer graphene, properties of GNRs of different thicknesses can also be harnessed for engineering GNRs as different building blocks towards FET applications. A novel imaging technique, graphene-templated scanning probe microscopy, has been developed and applied for the study on the condensation process of water and small organic molecules on mica. We found that these molecular adlayers grow epitaxially on the mica substrate in a layer-by-layer fashion. In particular, submonolayers of water form atomically flat, faceted islands of height 0.37 plus or minus 0.02 nm, in agreement with the height of a monolayer of ice. The second adlayers also appear ice-like, and thicker layers appear liquid-like. This general mechanism, however, is not universal. Exclusively three-dimensional droplets of water are observed on chemically modified (hydrophobic) mica surfaces, suggesting a 3D growth mechanism. This thesis also includes my work on the design of a quartz-tuning-fork-based force sensor and related electronics for applications on low-temperature atomic force microscopy. Results show that the force-sensor-global-feedback circuit detector system induced lowest noise floor. The high detection sensitivity of this system demonstrates its ability to be used in frequency-modulated AFM at cryogenic temperatures. Surface topographic imaging of H-terminated Si(111) has been achieved at low temperatures.