Grafting of Organophosphonic Acid Monolayers on Hydrogen-Terminated Silicon Surface and Secondary Functionalization in Supercritical Carbon Dioxide Media.

The monolayer grafting on the oxide-free Si surface is challenging due to vulnerability of the surface against oxide formation in an ambient atmosphere. Most of the conventional studies focused on organic solvent-based chemistry and solvent and substrate interfaces, and residual solvents after the monolayer grafting play a key role in producing the highly stable monolayers. CO in its supercritical state (SCCO) provides an elegant engineering solution for the problem faced as it can be used as inert processing environment and as carrier fluid for monolayer grafting taking up the role of organic solvents.

Universal Single-Step Approach to the Immobilization of Cyclodextrins in a Supercritical Medium for Capturing Drug, Dye, and Metal Nanoclusters.

By utilizing nanoreactor-like structures, the immobilization of macromolecules such as calixarenes and cyclodextrins (CD) with bucket-like structures provides new possibilities for engineered surface-molecule systems. The practical use of any molecular system depends on the availability of a universal procedure for immobilizing molecules with torus-like structures on various surfaces while maintaining identical operating parameters. There are currently several steps, including toxic solvent-based approaches using modified β-CD to covalently attach to surfaces with multistep reactions.

Surface Nanostructure Formation and Atomic-Scale Templates for Nanodevices.

The holy grail in nanoelectronics is the construction of nanodevices with high density, low cost, and high performance per device and per integrated circuit. One approach is the fabrication of surface nanostructures and atomic-scale templates via the autonomous assembly of atoms and/or molecules on well-defined surfaces. To steer the atomic or molecular growth processes and create a wide range of surface nanostructures with desired properties, a comprehensive understanding of the mechanisms that control the surface self-assembly processes is required.

Highly Stable Bonding of Thiol Monolayers to Hydrogen-Terminated Si via Supercritical Carbon Dioxide: Toward a Super Hydrophobic and Bioresistant Surface.

Oxide-free silicon chemistry has been widely studied using wet-chemistry methods, but for emerging applications such as molecular electronics on silicon, nanowire-based sensors, and biochips, these methods may not be suitable as they can give rise to defects due to surface contamination, residual solvents, which in turn can affect the grafted monolayer devices for practical applications. Therefore, there is a need for a cleaner, reproducible, scalable, and environmentally benign monolayer grafting process. In this work, monolayers of alkylthiols were deposited on oxide-free semiconductor surfaces using supercritical carbon dioxide (SCCO2) as a carrier fluid owing to its favorable physical properties.

Application of Organophosphonic Acids by One-Step Supercritical CO2 on 1D and 2D Semiconductors: Toward Enhanced Electrical and Sensing Performances.

Formation of dense monolayers with proven atmospheric stability using simple fabrication conditions remains a major challenge for potential applications such as (bio)sensors, solar cells, surfaces for growth of biological cells, and molecular, organic, and plastic electronics. Here, we demonstrate a single-step modification of organophosphonic acids (OPA) on 1D and 2D structures using supercritical carbon dioxide (SCCO2) as a processing medium, with high stability and significantly shorter processing times than those obtained by the conventional physisorption-chemisorption method (2.5 h vs 48-60 h).

Electronically transparent graphene barriers against unwanted doping of silicon.

Diffusion barriers prevent materials from intermixing (e.g., undesired doping) in electronic devices.

Supramolecular structure of self-assembled monolayers of ferrocenyl terminated n-alkanethiolates on gold surfaces.

It is important to understand the structure of redox-active self-assembled monolayers (SAMs) down to the atomic scale, since these SAMS are widely used as model systems in studies of mechanisms of charge transport or to realize electronic functionality in molecular electronic devices. We studied the supramolecular structure of SAMs of n-alkanethiolates with ferrocenyl (Fc) end groups (S(CH2)nFc, n = 3 or 4) on Au(111) by scanning tunneling microscopy (STM). In this system, the tilt angle of the Fc units with respect to the surface normal (α) depends on the value of n because the Au-S-C bond angle is fixed.

One-step synthesis of zero-dimensional hollow nanoporous gold nanoparticles with enhanced methanol electrooxidation performance.

Nanoporous gold with networks of interconnected ligaments and highly porous structure holds stimulating technological implications in fuel cell catalysis. Current syntheses of nanoporous gold mainly revolve around de-alloying approaches that are generally limited by stringent and harsh multistep protocols. Here we develop a one-step solution phase synthesis of zero-dimensional hollow nanoporous gold nanoparticles with tunable particle size (150-1,000 nm) and ligament thickness (21-54 nm).

Stable Organic Monolayers on Oxide-Free Silicon/Germanium in a Supercritical Medium: A New Route to Molecular Electronics.

Oxide-free Si and Ge surfaces have been passivated and modified with organic molecules by forming covalent bonds between the surfaces and reactive end groups of linear alkanes and aromatic species using single-step deposition in supercritical carbon dioxide (SCCO2). The process is suitable for large-scale manufacturing due to short processing times, simplicity, and high resistance to oxidation. It also allows the formation of monolayers with varying reactive terminal groups, thus enabling formation of nanostructures engineered at the molecular level.

Effect of molecule-substrate interaction on thin-film structures and molecular orientation of pentacene on silver and gold.

Evaporated pentacene thin films with thicknesses from several nm to 150 nm on gold and silver substrates have been studied by ultraviolet photoelectron spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS), scanning tunneling microscopy (STM), and atomic force microscopy (AFM). It was found that pentacene thin-film structures, particularly their molecular orientations, are strongly influenced by the metal substrates. UPS measurements revealed a distinct change in the valence band structures of pentacene on Au compared to those on Ag, which is attributed to the different packing between adjacent molecules.

Switching in organic devices caused by nanoscale Schottky barrier patches.

We have identified a possible electronic origin of metal filaments, invoked to explain the switching behavior of organic devices. Interfaces of two representative organics polyparaphenylene (PPP) and poly(2-methoxy-5-2-ethyl-hexyloxy-1,4-phenylenevinylene) with Ag are investigated using ballistic emission microscopy. Nanometer scale spatial nonuniformity of carrier injection is observed in ballistic electron emission microscopy images of both interfaces.