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

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

New Electrode–Molecule Contacts for Functional Molecular Electronics

This thesis developed new protocols to enable connecting molecules, materials, and proteins to electrodes via covalent bonding, towards applications in molecular electronics. The developed methods overcame some of the challenges in the field such as connecting one contact group to various electrodes. This enabled studying fundamental electrochemical and electronics correlations, that were largely debated in literature. In addition to molecules, this work enabled connecting two-dimensional material such as graphene oxide (GOx), and proteins to semiconductors

Electrochemical Detection of Dinitrobenzene on Silicon Electrodes: Toward Explosives Sensors

Detection of explosives is vital for protection and criminal investigations, and developing novel explosives’ sensors stands at the forefront of the analytical and forensic chemistry endeavors. Due to the presence of terminal nitro groups that can be electrochemically reduced, nitroaromatic compounds (NACs) have been an analytical target for explosives’ electrochemical sensors. Various electrode materials have been used to detect NACs in solution, including glassy carbon electrodes (GCE), platinum (Pt), and gold (Au) electrodes, by tracking the reversible oxidation/reduction properties of the NACs on these electrodes. Here, we show that the reduction of dinitrobenzene (DNB) on oxide-free silicon (Si–H) electrodes is irreversible with two reduction peaks that disappear within the successive voltammetric scanning. AFM imaging showed the formation of a polymeric film whose thickness scales up with the DNB concentration. This suggest that Si–H surfaces can serve as DNB sensors and possibly other explosive substances. Cyclic voltammetry (CV) measurements showed that the limit of detection (LoD) on Si–H is one order of magnitude lower than that obtained on GCE. In addition, EIS measurements showed that the LoD of DNB on Si–H is two orders of magnitude lower than the CV method. The fact that a Si–H surface can be used to track the presence of DNB makes it a suitable surface to be implemented as a sensing platform. To translate this concept into a sensor, however, it would require engineering and fabrication prospect to be compatible with the current semiconductor technologies

Spontaneous Grafting of OH-Terminated Molecules on Si−H Surfaces via Si–O–C Covalent Bonding

The surface functionalization of oxide-free hydrogen-terminated silicon (Si−H) enables predictably tuning its electronic properties, by incorporating tailored functionality for applications such as photovoltaics, biosensing and molecular electronics devices. Most of the available chemical functionalization approaches require an external radical initiator, such as UV light, heat or chemical reagents. Here, we report forming organic monolayers on Si–H surfaces using molecules comprising terminal alcohol (–OH) groups. Self-assembled monolayer (SAM) formation is spontaneous, requires no external stimuli–and yields Si–O–C covalently bound monolayers. The SAMs were characterized by X-ray photoelectron spectroscopy (XPS) to determine the chemical bonding, by X-ray reflectometry (XRR) to determine the monolayers thicknesses on the surface and by atomic force microscopy (AFM) to probe surface topography and surface roughness. The redox activity and the electrochemical properties of the SAMs were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The availability and the ease of incorporating OH groups in organic molecules, makes this spontaneous grafting as a reliable method to attach molecules to Si surfaces in applications ranging from sensing to molecular electronics where incorporating radical initiator setups is not accessible

Stochastic Electrochemical Measurement of a Biofouling Layer on Gold

Adsorption of a biofouling layer on the surface of biosensors decreases the electrochemical activity and hence shortens the service life of biosensors, particularly implantable and wearable biosensors. Real-time quantification of the loss of activity is important for in situ assessment of performance while presenting an opportunity to compensate for the loss of activity and recalibrate the sensor to extend the service life. Here, we introduce an electrochemical noise measurement technique as a tool for the quantification of the formation of a biofouling layer on the surface of gold. The technique uniquely affords thermodynamic and kinetic information without applying an external bias (potential and/or current), hence allowing the system to be appraised in its innate state. The technique relies on the analysis of non-faradaic current and potential fluctuations that are intrinsically generated by the interaction of charged species at the electrode surface, i.e., gold. An analytical model is extended to explain the significance of parameters drawn from statistical analysis of the noise signal. This concept is then examined in buffered media in the presence of albumin, a common protein in the blood and a known source of a fouling layer in biological systems. Results indicate that the statistical analysis of the noise signal can quantify the loss of electrochemical activity, which is also corroborated by impedance spectroscopy as a complementary technique

Condensin Smc2-Smc4 Dimers Are Flexible and Dynamic

Structural maintenance of chromosomes (SMC) protein complexes, including cohesin and condensin, play key roles in the regulation of higher-order chromosome organization. Even though SMC proteins are thought to mechanistically determine the function of the complexes, their native conformations and dynamics have remained unclear. Here, we probe the topology of Smc2-Smc4 dimers of the S. cerevisiae condensin complex with high-speed atomic force microscopy (AFM) in liquid. We show that the Smc2-Smc4 coiled coils are highly flexible polymers with a persistence length of only ~4 nm. Moreover, we demonstrate that the SMC dimers can adopt various architectures that interconvert dynamically over time, and we find that the SMC head domains engage not only with each other, but also with the hinge domain situated at the other end of the ~45-nm-long coiled coil. Our findings reveal structural properties that provide insights into the molecular mechanics of condensin complexes.BN/Cees Dekker La