Robert A. Wolkow

Field regulation of single-molecule conductivity by a charged surface atom

Electrical transport through molecules has been much studied since it was proposed that individual molecules might behave like basic electronic devices, and intriguing single-molecule electronic effects have been demonstrated. But because transport properties are sensitive to structural variations on the atomic scale, further progress calls for detailed knowledge of how the functional properties of molecules depend on structural features. The characterization of two-terminal structures has become increasingly robust and reproducible, and for some systems detailed structural characterization of molecules on electrodes or insulators is available. Here we present scanning tunnelling microscopy observations and classical electrostatic and quantum mechanical modelling results that show that the electrostatic field emanating from a fixed point charge regulates the conductivity of nearby substrate-bound molecules. We find that the onset of molecular conduction is shifted by changing the charge state of a silicon surface atom, or by varying the spatial relationship between the molecule and that charged centre. Because the shifting results in conductivity changes of substantial magnitude, these effects are easily observed at room temperature.

Tungsten nanotip fabrication by spatially controlled field-assisted reaction with nitrogen

In this report we present a straightforward new technique for fabricating nanotips. This approach is based on spatially controlling the reaction of nitrogen gas with the surface atoms of a tungsten tip in a field ion microscope (FIM). Confining this field-assisted etching reaction to the shank has enabled us to produce single-atom tips with an apex radius far sharper than the nominal 10 nm radius of curvature tips we start with. Tip sharpening is evidenced in several ways. The FIM imaging voltage drops dramatically from, typically, 4.4 to 1.6 kV. Nanotip formation is also evident from the increase in the FIM magnification and the decrease in the apex area, which are monitored throughout the experiment. A subsequent field evaporation allows the nanotip to be sequentially deconstructed to further describe the extraordinary sharp tip that was formed. We also demonstrate the utility of these nanotips for the scanning tunneling microscope.

Linear chains of styrene and methylstyrene molecules and their heterojunctions on silicon: Theory and experiment

We report on the synthesis, scanning tunnel microscope (STM) imaging, and theoretical studies of the structure, electronic structure, and transport properties of linear chains of styrene and methylstyrene molecules and their heterojunctions on hydrogen-terminated dimerized silicon (001) surfaces. The theory presented here accounts for the essential features of the experimental STM data including the nature of the corrugation observed along the molecular chains and the pronounced changes in the contrast between the styrene and methylstyrene parts of the molecular chains that are observed as the applied bias is varied. The observed evolution with applied bias of the STM profiles near the ends of the molecular chains is also explained. Calculations are also presented of electron transport along styrene linear chains adsorbed on the silicon surface at energies in the vicinity of the molecular highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels. For short styrene chains this lateral transport is found to be due primarily to direct electron transmission from molecule to molecule rather than through the silicon substrate, especially in the molecular LUMO band. Differences between the calculated position dependences of the STM current around a junction of styrene and methylstyrene molecular chains under positive and negative tip bias are related to the nature of lateral electron transmission along the molecular chains and to the formation in the LUMO band of an electronic state localized around the heterojunction.

Efficient silicon surface and cluster modeling using quantum capping potentials

A one-electron, silicon quantum capping potential for use in capping the dangling bonds formed by artificially limiting silicon clusters or surfaces is developed. The quantum capping potentials are general and can be used directly in any computational package that can handle effective core potentials. For silicon clusters and silicon surface models, we compared the results of traditional hydrogen atom capping with those obtained from capping with quantum capping potentials. The results clearly show that cluster and surface models capped with quantum capping potentials have ionization potentials, electron affinities, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps that are in very good agreement with those of larger systems. The silicon quantum capping potentials should be applied in cases where one wishes to model processes involving charges or low-energy excitations in silicon clusters and surfaces consisting of more than ca. 150 atoms.

Low-energy electron point projection microscopy of suspended graphene, the ultimate 'microscope slide'

Point projection microscopy (PPM) is used to image suspended graphene by using low-energy electrons (100–205 eV). Because of the low energies used, the graphene is neither damaged nor contaminated by the electron beam for doses of the order of 107 electrons per nm2. The transparency of graphene is measured to be 74%, equivalent to electron transmission through a sheet twice as thick as the covalent radius of sp2-bonded carbon. Also observed is rippling in the structure of the suspended graphene, with a wavelength of approximately 26 nm. The interference of the electron beam due to diffraction off the edge of a graphene knife edge is observed and is used to calculate a virtual source size of 4.7±0.6 A for the electron emitter. It is demonstrated that graphene can serve as both the anode and the substrate in PPM, thereby avoiding distortions due to strong field gradients around nanoscale objects. Graphene can be used to image objects suspended on the sheet using PPM and, in the future, electron holography.

Conduction Pathway of π-Stacked Ethylbenzene Molecular Wires on Si(100)

One of the most important challenges of molecular electronics is to enable systematic fabrication of molecular functional components on well-characterized solid-state substrates in a controlled manner. Recently, experimental techniques were developed to achieve such fabrication where lines of pi-stacked ethylbenzene molecules are induced to self-assemble on an H-terminated Si(100) surface at precise locations and along precise directions. In this work, we theoretically analyze charge transport properties of these ethylbenzene wires using a state-of-the-art first-principles technique where density functional theory (DFT) is used within the nonequilibrium Greens function formalism (NEGF). Our device model consists of ethylbenzene stacks bonded to an H-terminated Si(100) surface and bridging two metal leads. The electron transmission spectrum and its associated scattering states as well as the resistance of the molecular wire are determined by the self-consistent NEGF-DFT formalism. The transmission spectrum has a resonance nature for energies around the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the ethylbenzene wires. However, near the Fermi level of the device, which sits inside the HOMO-LUMO gap, the Si substrate is found to play an important role in providing additional pathways for conduction. It has emerged that, within our model system, the transmission peak nearest to the Fermi level corresponds to transport through the Si substrate and not the pi-stacked molecular line. The low-bias resistance R is found to increase exponentially with the length of the molecular line n, as R approximately e(betan), indicating a tunneling behavior in conduction. We further found that the exponential scaling has two regimes characterized by two different scaling parameters beta: a high value for conduction through the molecular stack in short lines and a lower value for conduction through the substrate in longer lines. Our results suggest that when the conduction of molecular wires bonded to semiconductor substrates is theoretically analyzed, conduction pathways through the substrate need to be taken into account.

Single-electron dynamics of an atomic silicon quantum dot on the H-Si(100)-(2×1) surface.

Here we report the direct observation of single electron charging of a single atomic dangling bond (DB) on the H-Si(100)-2×1 surface. The tip of a scanning tunneling microscope is placed adjacent to the DB to serve as a single-electron sensitive charge detector. Three distinct charge states of the dangling bond--positive, neutral, and negative--are discerned. Charge state probabilities are extracted from the data, and analysis of current traces reveals the characteristic single-electron charging dynamics. Filling rates are found to decay exponentially with increasing tip-DB separation, but are not a function of sample bias, while emptying rates show a very weak dependence on tip position, but a strong dependence on sample bias, consistent with the notion of an atomic quantum dot tunnel coupled to the tip on one side and the bulk silicon on the other.

Theory of nonequilibrium single-electron dynamics in STM imaging of dangling bonds on a hydrogenated silicon surface

During fabrication and scanning-tunneling-microscope (STM) imaging of dangling bonds (DBs) on a hydrogenated silicon surface, we consistently observed halo-like features around isolated DBs for specific imaging conditions. These surround individual or small groups of DBs, have abnormally sharp edges, and cannot be explained by conventional STM theory. Here we investigate the nature of these features by a comprehensive 3-dimensional model of elastic and inelastic charge transfer in the vicinity of a DB. Our essential finding is that non-equilibrium current through the localized electronic state of a DB determines the charging state of the DB. This localized charge distorts the electronic bands of the silicon sample, which in turn affects the STM current in that vicinity causing the halo effect. The influence of various imaging conditions and characteristics of the sample on STM images of DBs is also investigated.

Scanning tunneling spectroscopy reveals a silicon dangling bond charge state transition

We report the study of single dangling bonds (DB) on the hydrogen terminated silicon (100) surface using a low temperature scanning tunneling microscope (LT-STM). By investigating samples prepared with different annealing temperatures, we establish the critical role of subsurface arsenic dopants on the DB electronic properties. We show that when the near surface concentration of dopants is depleted as a result of

Tunnel coupled dangling bond structures on hydrogen terminated silicon surfaces

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