Terminal Deuterium Atoms Protect Silicon from Oxidation.

In recent years, the hybrid silicon-molecular electronics technology has been gaining significant attention for applications in sensors, photovoltaics, power generation, and molecular electronics devices. However, Si-H surfaces, which are the platforms on which these devices are formed, are prone to oxidation, compromising the mechanical and electronic stability of the devices. Here, we show that when hydrogen is replaced by deuterium, the Si-D surface becomes significantly more resistant to oxidation when either positive or negative voltages are applied to the Si surface. Si-D surfaces are more resistant to oxidation, and their current-voltage characteristics are more stable than those measured on Si-H surfaces. At positive voltages, the Si-D stability appears to be related to the flat band potential of Si-D being more positive compared to Si-H surfaces, making Si-D surfaces less attractive to oxidizing OH- ions. The limited oxidation of Si-D surfaces at negative potentials is interpreted by the frequencies of the Si-D bending modes being coupled to that of the bulk Si surface phonon modes, which would make the duration of the Si-D excited vibrational state significantly less than that of Si-H. The strong surface isotope effect has implications in the design of silicon-based sensing, molecular electronics, and power-generation devices and the interpretation of charge transfer across them.

Common Background Signals in Voltammograms of Crystalline Silicon Electrodes are Reversible Silica-Silicon Redox Chemistry at Highly Conductive Surface Sites.

The electrochemical reduction of bulk silica, due to its high electrical resistance, is of limited viability, namely, requiring temperatures in excess of 850 °C. By means of electrochemical and electrical measurements in atomic force microscopy, we demonstrate that at a buried interface, where silica has grown on highly conductive Si(110) crystal facets, the silica-silicon conversion becomes reversible at room temperature and accessible within a narrow potential window. We conclude that parasitic signals commonly observed in voltammograms of silicon electrodes originate from silica-silicon redox chemistry. While these findings do not remove the requirement of high temperature toward bulk silica electrochemical reduction, they redefine for silicon the potential window free from parasitic signals and, as such, significantly restrict the conditions where electroanalytical methods can be applied to the study of silicon surface reactivity.

Covalent Linkages of Molecules and Proteins to Si-H Surfaces Formed by Disulfide Reduction.

Thiols and disulfide contacts have been, for decades, key for connecting organic molecules to surfaces and nanoclusters as they form self-assembled monolayers (SAMs) on metals such as gold (Au) under mild conditions. In contrast, they have not been similarly deployed on Si owing to the harsh conditions required for monolayer formation. Here, we show that SAMs can be simply formed by dipping Si-H surfaces into dilute solutions of organic molecules or proteins comprising disulfide bonds. We demonstrate that S-S bonds can be spontaneously reduced on Si-H, forming covalent Si-S bonds in the presence of traces of water, and that this grafting can be catalyzed by electrochemical potential. Cyclic disulfide can be spontaneously reduced to form complete monolayers in 1 h, and the reduction can be catalyzed electrochemically to form full surface coverages within 15 min. In contrast, the kinetics of SAM formation of the cyclic disulfide molecule on Au was found to be three-fold slower than that on Si. It is also demonstrated that dilute thiol solutions can form monolayers on Si-H following oxidation to disulfides under ambient conditions; the supply of too much oxygen, however, inhibits SAM formation. The electron transfer kinetics of the Si-S-enabled SAMs on Si-H is comparable to that on Au, suggesting that Si-S contacts are electrically transmissive. We further demonstrate the prospect of this spontaneous disulfide reduction by forming a monolayer of protein azurin on a Si-H surface within 1 h. The direct reduction of disulfides on Si electrodes presents new capabilities for a range of fields, including molecular electronics, for which highly conducting SAM-electrode contacts are necessary and for emerging fields such as biomolecular electronics as disulfide linkages could be exploited to wire proteins between Si electrodes, within the context of the current Si-based technologies.

Reduced graphene oxide-silicon interface involving direct Si-O bonding as a conductive and mechanical stable ohmic contact.

Metal-semiconductor junctions are essential contacts for semiconductor devices, but high contact junction resistance is a limiting operational factor. Here, we establish an ohmic contact of low resistance of <4 × 10-6 Ω cm2 between platinum and n-type Si (111)-H surfaces. This involved Si-O covalent bonding a monolayer of graphene oxide (GO) to the Si surface followed by electrochemical reduction to form reduced graphene oxide (rGO). Current-voltage plots demonstrate that the GO/rGO transformation is associated with a change from a rectifying to an ohmic contact. The process is a viable method for constructing semiconductor-rGO interfaces and demonstrates that GO/rGO monolayers can be used as active components in tuning the contact resistance of metal-semiconductor junctions.

Spontaneous S-Si bonding of alkanethiols to Si(111)-H: towards Si-molecule-Si circuits.

We report the synthesis of covalently linked self-assembled monolayers (SAMs) on silicon surfaces, using mild conditions, in a way that is compatible with silicon-electronics fabrication technologies. In molecular electronics, SAMs of functional molecules tethered to gold via sulfur linkages dominate, but these devices are not robust in design and not amenable to scalable manufacture. Whereas covalent bonding to silicon has long been recognized as an attractive alternative, only formation processes involving high temperature and/or pressure, strong chemicals, or irradiation are known. To make molecular devices on silicon under mild conditions with properties reminiscent of Au-S ones, we exploit the susceptibility of thiols to oxidation by dissolved O2, initiating free-radical polymerization mechanisms without causing oxidative damage to the surface. Without thiols present, dissolved O2 would normally oxidize the silicon and hence reaction conditions such as these have been strenuously avoided in the past. The surface coverage on Si(111)-H is measured to be very high, 75% of a full monolayer, with density-functional theory calculations used to profile spontaneous reaction mechanisms. The impact of the Si-S chemistry in single-molecule electronics is demonstrated using STM-junction approaches by forming Si-hexanedithiol-Si junctions. Si-S contacts result in single-molecule wires that are mechanically stable, with an average lifetime at room temperature of 2.7 s, which is five folds higher than that reported for conventional molecular junctions formed between gold electrodes. The enhanced "ON" lifetime of this single-molecule circuit enables previously inaccessible electrical measurements on single molecules.

Chemically and Mechanically Controlled Single-Molecule Switches Using Spiropyrans.

Developing molecular circuits that can function as the active components in electrical devices is an ongoing challenge in molecular electronics. It demands mechanical stability of the single-molecule circuit while simultaneously being responsive to external stimuli mimicking the operation of conventional electronic components. Here, we report single-molecule circuits based on spiropyran derivatives that respond electrically to chemical and mechanical stimuli. The merocyanine that results from the protonation/ring-opening of the spiropyran form showed single-molecule diode characteristics, with an average current rectification ratio of 5 at ±1 V, favoring the orientation where the positively charged end of the molecule is attached to the negative terminal of the circuit. Mechanical pulling of a single spiropyran molecule drives a switch to a more conducting merocyanine state. The mechanical switching is enabled by the strong Au-C covalent bonding between the molecule and the electrodes, which allows the tensile force delivered by the STM piezo to break the molecule at its spiropyran C-O bond.

Metal-Single-Molecule-Semiconductor Junctions Formed by a Radical Reaction Bridging Gold and Silicon Electrodes.

Here we report molecular films terminated with diazonium salts moieties at both ends which enables single-molecule contacts between gold and silicon electrodes at open circuit via a radical reaction. We show that the kinetics of film grafting is crystal-facet dependent, being more favorable on ⟨111⟩ than on ⟨100⟩, a finding that adds control over surface chemistry during the device fabrication. The impact of this spontaneous chemistry in single-molecule electronics is demonstrated using STM-break junction approaches by forming metal-single-molecule-semiconductor junctions between silicon and gold source and drain, electrodes. Au-C and Si-C molecule-electrode contacts result in single-molecule wires that are mechanically stable, with an average lifetime at room temperature of 1.1 s, which is 30-400% higher than that reported for conventional molecular junctions formed between gold electrodes using thiol and amine contact groups. The high stability enabled measuring current-voltage properties during the lifetime of the molecular junction. We show that current rectification, which is intrinsic to metal-semiconductor junctions, can be controlled when a single-molecule bridges the gap in the junction. The system changes from being a current rectifier in the absence of a molecular bridge to an ohmic contact when a single molecule is covalently bonded to both silicon and gold electrodes. This study paves the way for the merging of the fields of single-molecule and silicon electronics.