High Shear Thin Film Synthesis of Partially Oxidized Gallium and Indium Composite 2D Sheets.

Reducing resistance in silicon-based devices is important as they get miniaturized further. 2D materials offer an opportunity to increase conductivity whilst reducing size. A scalable, environmentally benign method is developed for preparing partially oxidized gallium/indium sheets down to 10 nm thick from a eutectic melt of the two metals. Exfoliation of the planar/corrugated oxide skin of the melt is achieved using the vortex fluidic device with a variation in composition across the sheets determined using Auger spectroscopy. From an application perspective, the oxidized gallium indium sheets reduce the contact resistance between metals such as platinum and silicon (Si) as a semiconductor. Current-voltage measurements between a platinum atomic force microscopy tip and a Si-H substrate show that the current switches from being a rectifier to a highly conducting ohmic contact. These characteristics offer new opportunities for controlling Si surface properties at the nanoscale and enable the integration of new materials with Si platforms.

Continuous flow fabrication of green graphene oxide in aqueous hydrogen peroxide.

Highly processible graphene oxide (GO) has a diversity of applications as a material readily dispersed in aqueous media. However, methods for preparing such free-standing GO use hazardous and toxic reagents and generate significant waste streams. This is an impediment for uptake of GO in any application, for developing sustainable technologies and industries, and overcoming this remains a major challenge. We have developed a robust scalable continuous flow method for fabricating GO directly from graphite in 30% aqueous hydrogen peroxide which dramatically minimises the generation of waste. The process features the continuous flow thin film microfluidic vortex fluidic device (VFD), operating at specific conditions while irradiated sequentially by UV LED than a NIR pulsed laser. The resulting 'green' graphene oxide (gGO) has unique properties, possessing highly oxidized edges with large intact sp2 domains which gives rise to exceptional electrical and optical properties, including purple to deep blue emission of narrow full width at half maximum (<35 nm). Colloidally stable gGO exhibits cytotoxicity owing to the oxidised surface groups while solid-state films of gGO are biocompatible. The continuous flow method of generating gGO also provides unprecedented control of the level of oxidation and its location in the exfoliated graphene sheets by harnessing the high shear topological fluid flows in the liquid, and varying the wavelength, power and pulse frequency of the light source.

Electro-polymerization rates of diazonium salts are dependent on the crystal orientation of the surface.

Electro-polymerization of diazonium salts is widely used for modifying surfaces with thin organic films. Initially this method was primarily applied to carbon, then to metals, and more recently to semiconducting Si. Unlike on other surfaces, electrochemical reduction of diazonium salts on Si, which is one of the most industrially dominant material, is not well understood. Here, we report the electrochemical reduction of diazonium salts on a range of silicon electrodes of different crystal orientations (111, 211, 311, 411, and 100). We show that the kinetics of surface reaction and the reduction potential is Si crystal-facet dependent and is more favorable in the hierarchical order (111) > (211) > (311) > (411) > (100), a finding that offers control over the surface chemistry of diazonium salts on Si. The dependence of the surface reaction kinetics on the crystal orientation was found to be directly related to differences in the potential of zero charge (PZC) of each crystal orientation, which in turn controls the adsorption of the diazonium cations prior to reduction. Another consequence of the effect of PZC on the adsorption of diazonium cations, is that molecules terminated by distal diazonium moieties form a compact film in less time and requires less reduction potentials compared to that formed from diazonium molecules terminated by only one diazo moiety. In addition, at higher concentrations of diazonium cations, the mechanism of electrochemical polymerization on the surface becomes PZC-controlled adsorption-dominated inner-sphere electron transfer while at lower concentrations, diffusion-based outer-sphere electron transfer dominates. These findings help understanding the electro-polymerization reaction of diazonium salts on Si en route towards an integrated molecular and Si electronics technology.

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.

High shear in situ exfoliation of 2D gallium oxide sheets from centrifugally derived thin films of liquid gallium.

A diversity of two-dimensional nanomaterials has recently emerged with recent attention turning to the post-transition metal elements, in particular material derived from liquid metals and eutectic melts below 330 °C where processing is more flexible and in the temperature regime suitable for industry. This has been explored for liquid gallium using an angled vortex fluidic device (VFD) to fabricate ultrathin gallium oxide (Ga2O3) sheets under continuous flow conditions. We have established the nanosheets to form highly insulating material and have electrocatalytic activity for hydrogen evolution, with a Tafel slope of 39 mV dec-1 revealing promoting effects of the surface oxidation (passivation layer).

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.