This is the report of a DOE-sponsored workshop organized to discuss the status of our understanding of charge-transfer processes on the nanoscale and to identify research and other needs for progress in nanoscience and nanotechnology. The current status of basic electron-transfer research, both theoretical and experimental, is addressed, with emphasis on the distance-dependent measurements, and we have attempted to integrate terminology and notation of solution electron-transfer kinetics with that of conductance analysis. The interface between molecules or nanoparticles and bulk metals is examined, and new research tools that advance description and understanding of the interface are presented. The present state-of-the-art in molecular electronics efforts is summarized along with future research needs. Finally, novel strategies that exploit nanoscale architectures are presented for enhancing the efficiences of energy conversion based on photochemistry, catalysis, and electrocatalysis principles.
Ultrasmooth octadecyltrichlorosilane (OTS) monolayers (2.6 ( 0.2 nm thick, RMS roughness ∼1.0 Å) can be obtained reproducibly by exposing clean native SiO2 surfaces to a dry solution of OTS in Isopar-G. A clean room is not required. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), contact angle data, and ellipsometry show that film formation occurs through a "patch expansion" process and terminates once a single monolayer is formed, after about 2 days. These monolayers are suitable as substrates for high-resolution electron beam and AFM or STM lithography. Further observations highlight the importance of controlling water content during deposition of siloxane self-assembled monolayers. OTS covers the surface much faster when there is a little water in the OTS solution; contact angle and ellipsometry data indicate formation of a hydrophobic, 2.6 nm thick film after about 2 h. However, these OTS films have a totally different growth mechanism than films grown from dry solutions and are not really monolayers. The OTS forms platelike islands that then adsorb onto the surface; the resulting overlayers have RMS roughness of more than 3 Å. Continued exposure to the OTS solution results in continued island deposition and increased roughness.
Molecular electronics is commonly conceived as reproducing diode or transistor action at the molecular level. The quantum-dot cellular automata (QCA) approach offers an attractive alternative in which binary information is encoded in the configuration of charge among redox-active molecular sites. The Coulomb interaction between neighboring molecules provides device-device coupling. No current flow between molecules is required. We present an ab initio analysis of a simple molecular system which acts as a molecular QCA cell. The intrinsic bistability of the charge configuration results in dipole or quadrupole fields which couple strongly to the state of neighboring molecules. We show how logic gates can be implemented. We examine the role of the relaxation of nuclear coordinates in the molecular charge reconfiguration.
The ability to efficiently utilize solar thermal energy to enable liquid-to-vapor phase transition has great technological implications for a wide variety of applications, such as water treatment and chemical fractionation. Here, we demonstrate that functionalizing graphene using hydrophilic groups can greatly enhance the solar thermal steam generation efficiency. Our results show that specially functionalized graphene can improve the overall solar-to-vapor efficiency from 38% to 48% at one sun conditions compared to chemically reduced graphene oxide. Our experiments show that such an improvement is a surface effect mainly attributed to the more hydrophilic feature of functionalized graphene, which influences the water meniscus profile at the vapor-liquid interface due to capillary effect. This will lead to thinner water films close to the three-phase contact line, where the water surface temperature is higher since the resistance of thinner water film is smaller, leading to more efficient evaporation. This strategy of functionalizing graphene to make it more hydrophilic can be potentially integrated with the existing macroscopic heat isolation strategies to further improve the overall solar-to-vapor conversion efficiency.
We investigate poly͑methylmethacrylate͒ ͑PMMA͒ development processing with cold developers ͑4-10°C͒ for its effect on resolution, resist residue, and pattern quality of sub-10 nm electron beam lithography ͑EBL͒. We find that low-temperature development results in higher EBL resolution and improved feature quality. PMMA trenches of 4-8 nm are obtained reproducibly at 30 kV using cold development. Fabrication of single-particle-width Au nanoparticle lines was performed by lift-off. We discuss key factors for formation of PMMA trenches at the sub-10 nm scale.
Two resorcinarene surfactants with sulfur-functionalized headgroups have been evaluated for their ability to stabilize dispersions of midnanometer (16−87 nm)-sized gold particles in organic solvents. Citrate-stabilized colloidal gold nanoparticles were extracted from aqueous solutions into toluene or chloroform by tetrabenzylthiol resorcinarene 1 or tetraarylthiol resorcinarene 2. The nanoparticle dispersions were subjected to various conditions and monitored for changes in plasmon absorption intensity. The stability of the dispersions was dependent on the chemisorptive properties of the surfactant headgroup, with tetrabenzylthiol 1 being the more effective dispersant. Nanoparticles encapsulated by 1 were also highly robust, demonstrated good resistance to alkanethiol-induced flocculation, and could be redispersed after repeated precipitations in polar solvents. Surface-enhanced Raman scattering analysis and X-ray photoelectron spectroscopic studies confirmed significant differences in the chemisorptive properties of tetrathiols 1 and 2, indicating that surface passivation is an important factor in the dispersibility of colloidal gold nanoparticles in nonpolar solvents.
Reports of low quality pharmaceuticals have been on the rise in the last decade with the greatest prevalence of substandard medicines in developing countries, where lapses in manufacturing quality control or breaches in the supply chain allow substandard medicines to reach the marketplace. Here, we describe inexpensive test cards for fast field screening of pharmaceutical dosage forms containing beta lactam antibiotics or combinations of the four first-line antituberculosis (TB) drugs. The devices detect the active pharmaceutical ingredients (APIs) ampicillin, amoxicillin, rifampicin, isoniazid, ethambutol, and pyrazinamide, and also screen for substitute pharmaceuticals such as acetaminophen and chloroquine that may be found in counterfeit pharmaceuticals. The tests can detect binders and fillers like chalk, talc, and starch not revealed by traditional chromatographic methods. These paper devices contain twelve lanes, separated by hydrophobic barriers, with different reagents deposited in the lanes. The user rubs some of the solid pharmaceutical across the lanes and dips the edge of the paper into water. As water climbs up the lanes by capillary action, it triggers a library of different chemical tests and a timer to indicate when the tests are completed. The reactions in each lane generate colors to form a “color bar code” which can be analyzed visually by comparison to standard outcomes. While quantification of the APIs is poor compared to conventional analytical methods, the sensitivity and selectivity for the analytes is high enough to pick out suspicious formulations containing no API or a substitute API, as well as formulations containing APIs that have been “cut” with inactive ingredients.
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