Schottky Diode Leakage Current Fluctuations: Electrostatically Induced Flexoelectricity in Silicon.

Nearly four decades have passed since IBM scientists pioneered atomic force microscopy (AFM) by merging the principles of a scanning tunneling microscope with the features of a stylus profilometer. Today, electrical AFM modes are an indispensable asset within the semiconductor and nanotechnology industries, enabling the characterization and manipulation of electrical properties at the nanoscale. However, electrical AFM measurements suffer from reproducibility issues caused, for example, by surface contaminations, Joule heating, and hard-to-minimize tip drift and tilt. Using as experimental system nanoscale Schottky diodes assembled on oxide-free silicon crystals of precisely defined surface chemistry, it is revealed that voltage-dependent adhesion forces lead to significant rotation of the AFM platinum tip. The electrostatics-driven tip rotation causes a strain gradient on the silicon surface, which induces a flexoelectric reverse bias term. This directional flexoelectric internal-bias term adds to the external (instrumental) bias, causing both an increased diode leakage as well as a shift of the diode knee voltage to larger forward biases. These findings will aid the design and characterization of silicon-based devices, especially those that are deliberately operated under large strain or shear, such as in emerging energy harvesting technologies including Schottky-based triboelectric nanogenerators (TENGs).

Insulator-on-Conductor Fouling Amplifies Aqueous Electrolysis Rates.

The chemical industry is a major consumer of fossil fuels. Several chemical reactions of practical value proceed with the gain or loss of electrons, opening a path to integrate renewable electricity into chemical manufacturing. However, most organic molecules have low aqueous solubility, causing green and cheap electricity-driven reactions to suffer from intrinsically low reaction rates in industry's solvent of choice: water. Here, we show that a strategic, partial electrode fouling with hydrophobic insulators (oils and plastics) offsets kinetic limitations caused by poor reactant solubility, opening a new path for the direct integration of renewable electricity into the production of commodity chemicals. Through electrochemiluminescence microscopy, we reveal for the oxidation of organic reactants up to 6-fold reaction rate increase at the "fouled" oil-electrolyte-electrode interface relative to clean electrolyte-electrode areas. Analogously, electrodes partially masked (fouled) with plastic patterns, deposited either photolithographically (photoresists) or manually (inexpensive household glues and sealants), outperform clean electrodes. The effect is not limited to reactants of limited water solubility, and, for example, net gold electrodeposition rates are up to 22% larger at fouled than clean electrodes. In a system involving a surface-active reactant, rate augmentation is driven by the synergy between insulator-confined reactant enrichment and insulator-induced current crowding, whereas only the latter and possibly localized decrease in iR drop near the insulator are relevant in a system composed of non-surface-active species. Our counterintuitive electrode design enhances electrolysis rates despite the diminished area of intimate electrolyte-electrode contact and introduces a new path for upscaling aqueous electrochemical processes.

Hydroxylation of the indium tin oxide electrode promoted by surface bubbles.

Adherent bubbles at electrodes are generally treated as reaction penalties. Herein, in situ hydroxylation of indium tin oxide surfaces can be easily achieved by applying a constant potential of +1.0 V in the presence of bubbles. Its successful hydroxylation is further demonstrated by preparing a ferrocene-terminated film, which is confirmed by cyclic voltammetry and X-ray photoelectron spectroscopy.

Triboelectric Spectroscopy for In Situ Chemical Analysis of Liquids.

Chemical analysis of ions and small organic molecules in liquid samples is crucial for applications in chemistry, biology, environmental sciences, and health monitoring. Mainstream electrochemical and chromatographic techniques often suffer from complex and lengthy sample preparation and testing procedures and require either bulky or expensive instrumentation. Here, we combine triboelectrification and charge transfer on the surface of electrical insulators to demonstrate the concept of triboelectric spectroscopy (TES) for chemical analysis. As a drop of the liquid sample slides along an insulating reclined plane, the local triboelectrification of the surface is recorded, and the charge pattern along the sample trajectory is used to build a fingerprinting of the charge transfer spectroscopy. Chemical information extracted from the charge transfer pattern enables a new nondestructive and ultrafast (<1 s) tool for chemical analysis. TES profiles are unique, and through an automated identification, it is possible to match against standard and hence detect over 30 types of common salts, acids, bases and organic molecules. The qualitative and quantitative accuracies of the TES methodology is close to 93%, and the detection limit is as low as ppb levels. Instruments for TES chemical analysis are portable and can be further miniaturized, opening a path to in situ and rapid chemical detection relying on inexpensive, portable low-tech instrumentation.

Galinstan Liquid Metal Electrical Contacts for Monolayer-Modified Silicon Surfaces.

Galinstan is the brand name for a low-melting gallium-based alloy, which is a promising nontoxic alternative to mercury, the only elemental metal found in the liquid state at room temperature. Liquid alloys such as Galinstan have found applications as electromechanical actuators, sensors, and soft contacts for molecular electronics. In this work, we validate the scope of Galinstan top contacts to probe the electrical characteristics of Schottky junctions made on Si(111) and Si(211) crystals modified with Si-C-bound organic monolayers. We show that the surface-to-volume ratio of the Galinstan drop used as a macroscopic contact defines the junction stability. Further, we explore chemical strategies to increase Galinstan surface tension to obtain control over the junction area, hence improving the repeatability and reproducibility of current-voltage (I-V) measurements. We explore Galinstan top contacts as a means to monitor changes in rectification ratios caused by surface reactions and use these data, most notably the static junction leakage, toward making qualitative predictions on the DC outputs recorded when these semiconductor systems are incorporated in Schottky-based triboelectric nanogenerators. We found that the introduction of iron particles leads to poor data repeatability for capacitance-voltage (C-V) measurements but has only a small negative impact in a dynamic current measurement (I-V).

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.

Separating Convective from Diffusive Mass Transport Mechanisms in Ionic Liquids by Redox Pro-fluorescence Microscopy.

The study of electrochemical reactivity requires analytical techniques capable of probing the diffusion of reactants and products to and from electrified interfaces. Information on diffusion coefficients is often obtained indirectly by modeling current transients and cyclic voltammetry data, but such measurements lack spatial resolution and are accurate only if mass transport by convection is negligible. Detecting and accounting for adventitious convection in viscous and wet solvents, such as ionic liquids, is technically challenging. We have developed a direct, spatiotemporally resolved optical tracking of diffusion fronts which can detect and resolve convective disturbances to linear diffusion. By tracking the movement of an electrode-generated fluorophore, we demonstrate that parasitic gas evolving reactions lead to 10-fold overestimates of macroscopic diffusion coefficients. A hypothesis is put forward linking large barriers to inner-sphere redox reactions, such as hydrogen gas evolution, to the formation of cation-rich overscreening and crowding double layer structures in imidazolium-based ionic liquids.

Luciferase-free Luciferin Electrochemiluminescence.

Luciferin is one of Nature's most widespread luminophores, and enzymes that catalyze luciferin luminescence are the basis of successful commercial "glow" assays for gene expression and metabolic ATP formation. Herein we report an electrochemical method to promote firefly's luciferin luminescence in the absence of its natural biocatalyst-luciferase. We have gained experimental and computational insights on the mechanism of the enzyme-free luciferin electrochemiluminescence, demonstrated its spectral tuning from green to red by means of electrolyte engineering, proven that the colour change does not require, as still debated, a keto/enol isomerization of the light emitter, and gained evidence of the electrostatic-assisted stabilization of the charge-transfer excited state by double layer electric fields. Luciferin's electrochemiluminescence, as well as the in situ generation of fluorescent oxyluciferin, are applied towards an optical measurement of diffusion coefficients.

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.

Non-Ideal Cyclic Voltammetry of Redox Monolayers on Silicon Electrodes: Peak Splitting is Caused by Heterogeneous Photocurrents and Not by Molecular Disorder.

Over the last three decades, research on redox-active monolayers has consolidated their importance as advanced functional material. For widespread monolayer systems, such as alkanethiols on gold, non-ideal multiple peaks in cyclic voltammetry are generally taken as indication of heterogeneous intermolecular interactions─namely, disorder in the monolayer. Our findings show that, contrary to metals, peak multiplicity of silicon photoelectrodes is not diagnostic of heterogeneous intermolecular microenvironments but is more likely caused by photocurrent being heterogeneous across the monolayer. This work is an important step toward understanding the cause of electrochemical non-idealities in semiconductor electrodes so that these can be prevented and the redox behavior of molecular monolayers, as photocatalytic systems, can be optimized.

Experimental Evidence of Long-Lived Electric Fields of Ionic Liquid Bilayers.

Herein we demonstrate that ionic liquids can form long-lived double layers, generating electric fields detectable by straightforward open circuit potential (OCP) measurements. In imidazolium-based ionic liquids an external negative voltage pulse leads to an exceedingly stable near-surface dipolar layer, whose field manifests as long-lived (∼1-100 h) discrete plateaus in OCP versus time traces. These plateaus occur within an ionic liquid-specific and sharp potential window, defining a simple experimental method to probe the onset of interfacial ordering phenomena, such as overscreening and crowding. Molecular dynamics modeling reveals that the OCP arises from the alignment of the individual ion dipoles to the external electric field pulse, with the magnitude of the resulting OCP correlating with the product of the projected dipole moment of the cation and the ratio between the cation diffusion coefficient and its volume. Our findings also reveal that a stable overscreened structure is more likely to form if the interface is first forced through crowding, possibly accounting for the scattered literature data on relaxation kinetics of near-surface structures in ionic liquids.

Impermeable Graphene Oxide Protects Silicon from Oxidation.

The presence of a natural silicon oxide (SiOx) layer over the surface of silicon (Si) has been a roadblock for hybrid semiconductor and organic electronics technology. The presence of an insulating oxide layer is a limiting operational factor, which blocks charge transfer and therefore electrical signals for a range of applications. Etching the SiOx layer by fluoride solutions leaves a reactive Si-H surface that is only stable for few hours before it starts reoxidizing under ambient conditions. Controlled passivation of silicon is also of key importance for improving Si photovoltaic efficiency. Here, we show that a thin layer of graphene oxide (GOx) prevents Si surfaces from oxidation under ambient conditions for more than 30 days. In addition, we show that the protective GOx layer can be modified with molecules enabling a functional surface that allows for further chemical conjugation or connections with upper electrodes, while preserving the underneath Si in a nonoxidized form. The GOx layer can be switched electrochemically to reduced graphene oxide, allowing the development of a dynamic material for molecular electronics technologies. These findings demonstrate that 2D materials are alternatives to organic self-assembled monolayers that are typically used to protect and tune the properties of Si and open a realm of possibilities that combine Si and 2D materials technologies.

Electrostatics and Electrochemistry: Mechanism and Scope of Charge-Transfer Reactions on the Surface of Tribocharged Insulators.

The phenomenon of surface electrification upon contact is a long-standing scientific puzzle, with for instance written accounts of charged samples of amber attracting feathers dating back to the 600 B.C. Electrostatic hazards associated with electrical insulators subject to mechanical friction are well documented, and the design of commercial products, such as copiers and laser printers, is based on the static charging of electrical insulators. Nonetheless, the physical-chemical origin of this phenomenon remains debated. This Perspective outlines recent advances in our understanding of the mechanism behind contact electrification, as well as the emerging research area of electrochemistry on insulators. Research is beginning to demonstrate how to exploit static charges present on insulating surfaces, with the goal of driving redox reactivity. These studies have helped to clarify the triboelectrification mechanism and have defined new platforms for electrochemiluminescence, metal nucleation, and mask-free lithography. This Perspective will help researchers working within electrochemistry, physics, green energy, sensing, and materials to gain an understanding of the implications of contact electrification to their respective fields. Special attention is given to the chemical, electronic, and mechanical factors influencing triboelectrochemical reactions, concluding with the perceived challenges facing further development of this field.

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.

The corona of a surface bubble promotes electrochemical reactions.

The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode's surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.

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.

Irreproducibility in the triboelectric charging of insulators: evidence of a non-monotonic charge versus contact time relationship.

Here, we investigate the development and relaxation of static charges on the surface of plastic materials that are first brought in contact, and then macroscopically separated. Experimentalists dealing with the static electrification of insulators are aware of difficulties predictably attaining, and precisely reproducing, a given charging magnitude. Here we have observed for the first time that in homo-systems (e.g. PTFE rubbed against PTFE) charge densities reach the maximum value after a material-specific contact time. Attempts to charge a sample beyond its peak value leads to a progressive drop in charge. We propose this drop to result both from the electrostatically driven segregation of polymer ionic fragments, as well as from the discharge of unstable fragments by dielectric breakdown when a sufficiently high surface charge density is reached. We therefore highlight the general existence of two branches in the charging versus charging time curve: the assumption of a monotonous charging slope holds only left or right of the charging maxima and to achieve a specific charge density, care has to be taken to remain within one branch. Differences between materials in the tribocharging peak time are shown to reflect difference in material transfer rates and water adsorption, rather than differences in electronic factors such as the relative stability of cationic and anionic fragments.

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.