Electronic Properties of Metallic Nanoclusters on Semiconductor Surfaces: Implications for Nanoelectronic Device Applications

We review current research on the electronic properties of nanoscale metallic islands and clusters deposited on semiconductor substrates. Reported results for a number of nanoscale metal-semiconductor systems are summarized in terms of their fabrication and characterization. In addition to the issues faced in large-area metal-semiconductor systems, nano-systems present unique challenges in both the realization of well-controlled interfaces at the nanoscale and the ability to adequately characterize their electrical properties. Imaging by scanning tunneling microscopy as well as electrical characterization by current-voltage spectroscopy enable the study of the electrical properties of nanoclusters/semiconductor systems at the nanoscale. As an example of the low-resistance interfaces that can be realized, low-resistance nanocontacts consisting of metal nanoclusters deposited on specially designed ohmic contact structures are described. To illustrate a possible path to employing metal/semiconductor nanostructures in nanoelectronic applications, we also describe the fabrication and performance of uniform 2-D arrays of such metallic clusters on semiconductor substrates. Using self-assembly techniques involving conjugated organic tether molecules, arrays of nanoclusters have been formed in both unpatterned and patterned regions on semiconductor surfaces. Imaging and electrical characterization via scanning tunneling microscopy/spectroscopy indicate that high quality local ordering has been achieved within the arrays and that the clusters are electronically coupled to the semiconductor substrate via the low-resistance metal/semiconductor interface.     

The shape of the total energy distribution from W(110) in sub-threshold photoemission

Measurements of the final state energy distribution of electrons photoemitted from W(110) at energies less than the vacuum level are presented. A 127° velocity selector analyzer was used to energy resolve the photoemitted current. A significant improvement in both energy resolution and signal-to-noise ratio over previous studies resulted. The energy distributions obtained from W(110) are compared the theoretical predictions based on a recent model of photofield emission. The sensitivity of this theoretical model to various parameters of interest are investigated. The reasonable agreement between theory and experiment indicates that the final states probed in these measurements are free electron-like and not strongly representative of the final bulk density of states of the emitting material.     

Electronic states and structural stability of supported Au clusters

The quantized energy levels of electrons in supported nanometer-size Au clusters have been resolved at room temperature using field emission techniques. By studying the time dependence of the electron emission current from an individual supported cluster, information about the structural stability of the cluster can also be obtained. Studies show abrupt jumps between different emission rates that are revisited as time progresses. This phenomenon can be attributed to a rearrangement of the cluster structure and/or orientation on the substrate and provides new evidence of multiple ‘isomeric’ structures for small clusters of metallic atoms.     

Imaging nanometer-size metallic clusters with the atomic force microscope

The atomic force microscope has been used in the attractive (non-contact) force mode to produce images of individual nanometer-size clusters pre-formed in the gas phase and deposited on a wide variety of atomically-flat substrates. Using this technique, it is now possible to reliably image pre-formed clusters in their as-deposited positions. Studies of nanometer-size Au clusters supported on highly oriented pyrolitic graphite clearly show how the clusters are distributed across the scanned region. Cluster coverages inferred from atomic force studies are compared to those obtained from TEM studies of amorphous carbon grids simultaneously exposed to the same cluster beam.     

Scanning probe microscopy study of exfoliated oxidized graphene sheets

Exfoliated oxidized graphene (OG) sheets, suspended in an aqueous solution, were deposited on freshly cleaved HOPG and studied by ambient AFM and UHV STM. The AFM images revealed oxidized graphene sheets with a lateral dimension of 5–10 μm. The oxidized graphene sheets exhibited different thicknesses and were found to conformally coat the HOPG substrate. Wrinkles and folds induced by the deposition process were clearly observed. Phase imaging and lateral force microscopy showed distinct contrast between the oxidized graphene and the underlying HOPG substrate. The UHV STM studies of oxidized graphene revealed atomic scale periodicity showing a (0.273 ± 0.008) nm × (0.406 ± 0.013) nm unit cell over distances spanning few nanometers. This periodicity is identified with oxygen atoms bound to the oxidized graphene sheet. I(V) data were taken from oxidized graphene sheets and compared to similar data obtained from bulk HOPG. The dI/dV data from oxidized graphene reveals a reduction in the local density of states for bias voltages in the range of ±0.1 V.     

Detection of Bacillus subtilis spores using peptide-functionalized cantilever arrays

We move beyond antibody-antigen binding systems and demonstrate that short peptide ligands can be used to efficiently capture Bacillus subtilis (a simulant of Bacillus anthracis) spores in liquids. On an eight-cantilever array chip, four cantilevers were coated with binding peptide (NHFLPKV-GGGC) and the other four were coated with control peptide (LFNKHVP-GGGC) for reagentless detection of whole B. subtilis spores in liquids. The peptide-ligand-functionalized microcantilever chip was mounted onto a fluid cell filled with a B. subtilis spore suspension for approximately 40 min; a 40 nm net differential deflection was observed. Fifth-mode resonant frequency measurements were also performed before and after dipping microcantilever arrays into a static B. subtilis solution showing a substantial decrease in frequency for binding-peptide-coated microcantilevers as compared to that for control peptide cantilevers. Further confirmation was obtained by subsequent examination of the microcantilever arrays under a dark-field microscope. Applications of this technology will serve as a platform for the detection of pathogenic organisms including biowarfare agents.