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Robert A Wolkow

Publications and source records attributed to Robert A Wolkow.

6 recordsLinked to original sources

Linear nanostructure formation of aldehydes by self-directed growth on hydrogen-terminated silicon(100).

The self-directed growth of organic molecules on silicon surfaces allows for the rapid, parallel production of hybrid organic-silicon nanostructures. In this work, the formation of benzaldehyde- and acetaldehyde-derived nanostructures on hydrogen-terminated H-Si(100)-2x1 surface is studied by scanning tunneling microscopy in ultrahigh vacuum and by quantum mechanical methods. The reaction is a radical-mediated process that binds the aldehydes, through a strong Si-O covalent bond, to the surface. The aldehyde nanostructures are generally composed of double lines of molecules. Two mechanisms that lead to double line growth are elucidated.

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Detailed studies of molecular conductance using atomic resolution scanning tunneling microscopy.

Atomically resolved scanning tunneling microscopy and spectroscopy (STM/STS) have been used to carefully examine the relationship between molecular conductivity and the adsorption state of various organic molecules on silicon surfaces. We show that the particular configuration of styrene and cyclopentene molecules on silicon affects the conductivity of the molecules. Detailed correlation of STM images with point specific current-voltage spectroscopy reveal that observed negative peaks are due to random configuration changes driven by inelastically scattered electrons and not due to tuned alignment of molecule and electrode levels. These random processes, which include molecular rearrangement, desorption, and/or decomposition occur with increasing frequency at larger voltage and current settings.

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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.

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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.

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Protection-deprotection chemistry to control styrene self-directed line growth on hydrogen-terminated Si(100).

TEMPO, 2,2,6,6-tetramethylpiperidinyloxy, was used in a series of protection-deprotection chemical reactions in order to gain single molecule-level control over the extent of styrene line growth on hydrogen-terminated Si(100). The mechanism involves the reaction of TEMPO with the dangling bond at the end of individual styrene lines. The TEMPO cap protects the dangling bond from further reaction with styrene resulting in the termination of line growth. TEMPO is then selectively removed from desired lines, deprotecting the dangling bond, using the scanning tunneling microscope. Further exposure of the surface to styrene ensures that only the deprotected areas continue to grow while the protected lines do not. All lines can then be capped with TEMPO, and this allows for the generation of stable styrene lines of varying lengths.

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Dispersion interactions enable the self-directed growth of linear alkane nanostructures covalently bound to silicon.

Current interest in methods for controllably adding organic molecules to silicon surfaces relates to proposed hybrid silicon-organic devices. It was recently shown that a "self-directed" growth process, requiring only limited scanned probe intervention, has the potential to permit rapid, parallel production of ordered molecular nanostructures on silicon with predefined absolute position, structure, composition, and extent of growth. The hybrid organic-silicon structures formed are bound by strong covalent interactions. In this work, we use scanning tunneling microscopy and density functional theory techniques to show that molecule-surface dispersion interactions enable the growth process and play a crucial role in the final configurations of the nanostructures.

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