The combination of monocrystalline silicon's well-defined structure and the ability to prepare hydrogen-terminated surfaces (Si-H) easily and reproducibly has made this material a very attractive substrate for immobilizing functional molecules. The functionalization of Si-H using the covalent attachment of organic monolayers has received intense attention due to the numerous potential applications of controlled and robust organic/Si interfaces. Researchers have investigated these materials in diverse fields such as molecular electronics, chemistry, and bioanalytical chemistry. Applications include the preparation of surface insulators, the incorporation of chemical or biochemical functionality at interfaces for use in photovoltaic conversion, and the development of new chemical and biological sensing devices. Unlike those of gold, silicon's electronic properties are tunable, and researchers can directly integrate silicon-based devices within electronic circuitry. Moreover, the technological processes used for the micro- and nanopatterning of silicon are numerous and mature enough for producing highly miniaturized functional electronic components. In this Account, we describe a powerful approach that integrates redox-active molecules, such as ferrocene, onto silicon toward electrically addressable systems devoted to information storage or transfer. Ferrocene exhibits attractive electrochemical characteristics: fast electron-transfer rate, low oxidation potential, and two stable redox states (neutral ferrocene and oxidized ferrocenium). Accordingly, ferrocene-modified silicon surfaces could be used as charge storage components with the bound ferrocene center as the memory element. Upon application of a positive potential to silicon, ferrocene is oxidized to its corresponding ferrocenium form. This redox change is equivalent to the change of a bit of information from the "0" to "1" state. To erase the stored charge and return the device to its initial state, a low potential must be applied to reduce the whole generated ferrocenium. In this type of application, the electron is transferred from the ferrocene headgroups to the underlying conducting silicon surface by a tunneling process across the monolayer. To produce a stable and reproducible electrical response, this process must be efficient, fast, and reversible. The stability, charge density, and capacitance performances of high-quality ferrocene-terminated monolayers could compete with those of the existing semiconductor-based memory devices, such as dynamic random access memories, DRAMs. Moreover, we provide experimental evidence that a series of immobilized ferrocene centers can efficiently communicate via a lateral electron hopping process. Using these modified interfaces, we demonstrate that the thin redox-active monolayer can behave as a purely conducting material, highlighting an unprecedented very fast electron communication between immobilized redox groups. Perhaps more importantly, the surface coverage of ferrocene allows us to precisely control the rat...

This review provides a comprehensive survey of the derivatization of hydrogen-terminated, oxide-free silicon surfaces with electroactive assemblies (from molecules to polymers) attached through strong interactions (covalent, electrostatic, and chimisorption). Provided that surface modification procedures are thoroughly optimized, such an approach has appeared as a promising strategy toward high-quality functional interfaces exhibiting excellent chemical and electrochemical stabilities. The attachment of electroactive molecules exhibiting either two stable redox states (e.g., ferrocene and quinones) or more than two stable redox states (e.g., metalloporphyrins, polyoxometalates, and C60) is more particularly discussed. Attention is also paid to the immobilization of electrochemically polymerizable centers. Globally, these functional interfaces have been demonstrated to show great promise for the molecular charge storage and information processing or the elaboration of the electrochemically switchable devices. Besides, there are also some relevant examples dealing with their activity for other fields of interest, such as sensing and electrochemical catalysis.

Self-assembled ferrocene monolayers covalently bound to monocrystalline Si(111) surfaces have been prepared from the attachment of an amine-substituted ferrocene derivative to a pre-assembled acid-terminated alkyl monolayer using carbodiimide coupling. This derivatization strategy yielded nanometer-scale clean, densely packed monolayers, with the ferrocene units being more than 20 A from the semiconductor surface. The amount of immobilized electroactive units could be varied in the range 2 x 10(-11) to approximately 3.5 x 10(-10) mol cm(-2) by diluting the ferrocene-terminated chains by inert n-decyl chains. The highest coverage obtained for the single-component monolayer corresponded to 0.25-0.27 bound ferrocene per surface silicon atom. The electrochemical characteristics of the mixed n-decyl/ferrocene-terminated monolayers were found to not depend significantly on the surface coverage of ferrocene units. The reversible one-electron wave of the ferrocene/ferrocenium couple was observed at E degrees ' = 0.50 +/- 0.01 V vs SCE, and the rate constant of electron transfer kapp was about 50 s(-1).

International audienceNi electrodeposited on n-type Si from aqueous solutions in the form of isolated or coalescent nanoparticles (NPs) protects the underlying and partially exposed Si from photocorrosion-induced electrical passivation. Such photoanodes, fabricated without the need for additional protecting layers, a buried junction, and high vacuum techniques, show a high photovoltage of similar to 500 mV for the oxygen evolution reaction (OER), state-of-the-art photocurrents, and faradaic efficiencies > 90% under AM 1.5G illumination conditions at pH 14. Remarkably, these photoelectrodes are stable and can be operated at the light limited catalytic current from 10 h to more than 40 h in 1 M NaOH. These findings demonstrate that robust and efficient Si-based photoanodes can be produced easily, which opens new opportunities for the implementation of low-cost Si-based monolithic photoelectrochemical cells for efficient solar fuel production

The redox activity of a ferrocenyl monolayer grafted on an n-type Si111 substrate was investigated by scanning electrochemical microscopy (SECM) in conditions where the substrate plays the role of an insulator. This approach permits the differentiation between the different possible electron-transfer and mass-transport pathways occurring at the interface. As an exciting result, the thin ferrocenyl monolayer behaves like a purely conducting material, highlighting very fast electron communication between immobilized ferrocenyl headgroups in a 2D-like charge-transport mechanism.

In spite of the notorious instability of Si in alkaline solutions, Si partially covered with hemispherical Ni particles show striking performances for sunlight-assisted water oxidation.

Apart from being key structures of modern microelectronics, metal-insulator-semiconductor (MIS) junctions are highly promising electrodes for artificial leaves, i.e. photoelectrochemical cells that can convert sunlight into energy-rich fuels. Here, we demonstrate that homogeneous Si/SiO x /Ni MIS junctions, employed as photoanodes, can be functionalized with a redox-active species and simultaneously converted into high-photovoltage inhomogeneous MIS junctions by electrochemical dissolution. We also report on the considerable enhancement of performance towards urea oxidation, induced by this process. Finally, we demonstrate that both phenomena can be employed synergistically to design highly-efficient Si-based photoanodes. These findings open doors for the manufacturing of artificial leaves that can generate H 2 under solar illumination using contaminated water.

International audienceThe electrocatalytic redn. of CO2 to CO in hydroorg. medium has been investigated at illuminated (λ \textgreater 600 nm; 20 mW cm-2) hydrogen-terminated silicon nanowires (SiNWs-H) photocathodes using three Mn-based carbonyl bipyridyl complexes as homogeneous mol. catalysts ([Mn(L) (CO)3(CH3CN)](PF6) and [Mn(bpy) (CO)3Br] with L = bpy = 2,2'-bipyridine and dmbpy = 4,4'-dimethyl-2,2'-bipyridine). Systematic comparison of their cyclic voltammetry characteristics with those obtained at flat hydrogen-terminated silicon and traditional glassy carbon electrodes (GCE) enabled us to demonstrate the superior catalytic efficiency of SiNWs-H in terms of cathodic photocurrent densities and overpotentials. For example, the photocurrent densities measured at -1.0 V vs SCE for [Mn(bpy) (CO)3(CH3CN)](PF6) at SiNWs-H exceeded 1.0 mA cm-2 in CO2-satd. CH3CN + 5% vol./vol. H2O, whereas almost zero current was measured at this potential at GCE. Such characteristics have been supported by the energetic diagrams built for the different SiNWs\textbarMn-based catalyst interfaces. The fill factor FF and energy conversion efficiency η calcd. under catalytic conditions were higher for [Mn(bpy or dmbpy) (CO)3(CH3CN)](PF6) (FF = 0.35 and 0.34; η = 3.0 and 2.0%, resp.). Further preparative-scale electrolysis at SiNWs-H photocathode with Mn-based complex catalysts in electrolytic soln. evidenced the quant. conversion of CO2 to CO with a higher stability of the [Mn(dmbpy) (CO)3(CH3CN)](PF6) complex. Finally, in order to develop technol. viable electrocatalytic devices, the elaboration of SiNWs-H photoelectrodes modified with a Mn-based complex has been successfully achieved from an electropolymerizable catalyst, and it was shown that the electrocatalytic activity of the complex was retained after immobilization