Effect of Electric Fields on Silicon-Based Monolayers.

Electric fields can induce bond breaking and bond forming, catalyze chemical reactions on surfaces, and change the structure of self-assembled monolayers on electrode surfaces. Here, we study the effect of electric fields supplied either by an electrochemical potential or by conducting atomic force microscopy (C-AFM) on Si-based monolayers. We report that typical monolayers on silicon undergo partial desorption followed by the oxidation of the underneath silicon at +1.5 V vs Ag/AgCl. The monolayer loses 28% of its surface coverage and 55% of its electron transfer rate constant (ket) when +1.5 V electrochemical potential is applied on the Si surface for 10 min. Similarly, a bias voltage of +5 V applied by C-AFM induces complete desorption of the monolayer at specific sites accompanied by an average oxide growth of 2.6 nm when the duration of the bias applied is 8 min. Current-voltage plots progressively change from rectifying, typical of metal-semiconductor junctions, to insulating as the oxide grows. These results define the stability of Si-based organic monolayers toward electric fields and have implication in the design of silicon-based monolayers, molecular electronics devices, and on the interpretation of charge-transfer kinetics across them.

On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?

Owing to its simplicity, selectivity, high yield, and the absence of byproducts, the "click" azide-alkyne reaction is widely used in many areas. The reaction is usually catalyzed by copper(I), which selectively produces the 1,4-disubstituted 1,2,3-triazole regioisomer. Ruthenium-based catalysts were later developed to selectively produce the opposite regioselectivity─the 1,5-disubstituted 1,2,3-triazole isomer. Ruthenium-based catalysis, however, remains only tested for click reactions in solution, and the suitability of ruthenium catalysts for surface-based click reactions remains unknown. Also unknown are the electrical properties of the 1,4- and 1,5-regioisomers, and to measure them, both isomers need to be assembled on the electrode surface. Here, we test whether ruthenium catalysts can be used to catalyze surface azide-alkyne reactions to produce 1,5-disubstituted 1,2,3-triazole, and compare their electrochemical properties, in terms of surface coverages and electron transfer kinetics, to those of the compound formed by copper catalysis, 1,4-disubstituted 1,2,3-triazole isomer. Results show that ruthenium(II) complexes catalyze the click reaction on surfaces yielding the 1,5-disubstituted isomer, but the rate of the reaction is remarkably slower than that of the copper-catalyzed reaction, and this is related to the size of the catalyst involved as an intermediate in the reaction. The electron transfer rate constant (ket) for the ruthenium-catalyzed reaction is 30% of that measured for the copper-catalyzed 1,4-isomer. The lower conductivity of the 1,5-isomer is confirmed by performing nonequilibrium Green's function computations on relevant model systems. These findings demonstrate the feasibility of ruthenium-based catalysis of surface click reactions and point toward an electrical method for detecting the isomers of click reactions.

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.

Controlling piezoresistance in single molecules through the isomerisation of bullvalenes.

Nanoscale electro-mechanical systems (NEMS) displaying piezoresistance offer unique measurement opportunities at the sub-cellular level, in detectors and sensors, and in emerging generations of integrated electronic devices. Here, we show a single-molecule NEMS piezoresistor that operates utilising constitutional and conformational isomerisation of individual diaryl-bullvalene molecules and can be switched at 850 Hz. Observations are made using scanning tunnelling microscopy break junction (STMBJ) techniques to characterise piezoresistance, combined with blinking (current-time) experiments that follow single-molecule reactions in real time. A kinetic Monte Carlo methodology (KMC) is developed to simulate isomerisation on the experimental timescale, parameterised using density-functional theory (DFT) combined with non-equilibrium Green's function (NEGF) calculations. Results indicate that piezoresistance is controlled by both constitutional and conformational isomerisation, occurring at rates that are either fast (equilibrium) or slow (non-equilibrium) compared to the experimental timescale. Two different types of STMBJ traces are observed, one typical of traditional experiments that are interpreted in terms of intramolecular isomerisation occurring on stable tipped-shaped metal-contact junctions, and another attributed to arise from junction‒interface restructuring induced by bullvalene isomerisation.

Electrochemical grafting of organic films on silica.

Traditionally, self-assembled monolayers formed on silicon require the removal of the insulating and chemically inert silica layer that naturally forms on the surface of crystalline silicon. The removal of silica is thought to be necessary in order to expose the conducting Si-H surface, which is reactive towards molecules. Here we report the unexpected result of electrochemical formation of thin organic films on silica-terminated silicon with silica thickness up to 20 nm. The process is facilitated by the electrochemical generation of aryl radicals that react with silanol groups at the distal end of silica.