Synthesis of Polymer Dielectric Layers for Organic Thin Film Transistors via Surface-Initiated Ring-Opening Metathesis Polymerization

The use of surface-initiated ring-opening metathesis polymerization (SI-ROMP) for producing polymer dielectric layers is reported. Surface tethering of the catalyst to Au or Si/SiO_2 surfaces is accomplished via self-assembled monolayers of thiols or silanes containing reactive olefins. Subsequent SI-ROMP of norbornene can be conducted under mild conditions. Pentacene semiconducting layers and gold drain/source electrodes are deposited over these polymer dielectric films. The resulting field effect transistors display promising device characteristics, demonstrating for the first time that SI-ROMP can be used in the construction of organic thin-film electronic devices

Simultaneous imaging of dopants and free charge carriers by STEM-EELS

Doping inhomogeneities in solids are not uncommon, but their microscopic observation and understanding are limited due to the lack of bulk-sensitive experimental techniques with high-enough spatial and spectral resolution. Here, we demonstrate nanoscale imaging of both dopants and free charge carriers in La-doped BaSnO3 (BLSO) using high-resolution electron energy-loss spectroscopy (EELS). By analyzing both high- and low-energy excitations in EELS, we reveal chemical and electronic inhomogeneities within a single BLSO nanocrystal. The inhomogeneous doping leads to distinctive localized infrared surface plasmons, including a novel plasmon mode that is highly confined between high- and low-doping regions. We further quantify the carrier density, effective mass, and dopant activation percentage from EELS data and transport measurements on the bulk single crystals of BLSO. These results represent a unique way of studying heterogeneities in solids, understanding structure-property relationships at the nanoscale, and opening the way to leveraging nanoscale doping texture in the design of nanophotonic devices

Metallic Contact Formation for Molecular Electronics:Interactions between Vapor-Deposited Metals and Self-Assembled Monolayers of Conjugated Mono- and Dithiols

We present grazing-incidence Fourier transform infrared and AFM data of Au, Al, and Ti vapor-deposited onto self-assembled monolayers (SAMs) of conjugated mono- and dithiols. SAMs of 4,4'''-dimercapto-p-quaterphenyl, 4,4''-dimercapto-p-terphenyl, and 4,4'-dimercapto-p-biphenyl have reactive thiols at the SAM/vacuum interface that interact with vapor-deposited Au or Al atoms, preventing metal penetration. Conjugated monothiols lack such metal blocking groups, and metals (Au, Al) can penetrate into their SAMs. Vapor deposition of Ti onto conjugated mono- and dithiol SAMs and onto hexadecanethiol SAMs destroys the monolayers

Crustal structure of the Arabian Plate: New constraints from the analysis of teleseismic receiver functions

An edited version of this paper was published by Elsevier Science. Copyright 2005, Elsevier Science. See also: http://dx.doi.org/10.1016/j.epsl.2004.12.020; http://atlas.geo.cornell.edu/SaudiArabia/publications/Al-Damegh%202005.htmReceiver functions for numerous teleseismic earthquakes recorded at 23 broadband and mid-band stations in Saudi Arabia and Jordan were analyzed to map crustal thickness within and around the Arabian plate. We used spectral division as well as time domain deconvolution to compute the individual receiver functions and receiver function stacks. The receiver functions were then stacked using the slant stacking approach to estimate Moho depths and Vp/Vs for each station. The errors in the slant stacking were estimated using a bootstrap re-sampling technique. We also employed a grid search waveform modeling technique to estimate the crustal velocity structure for seven stations. A jackknife re-sampling approach was used to estimate errors in the grid search results for three stations. In addition to our results, we have also included published receiver function results from two temporary networks in the Arabian shield and Oman as well as three permanent GSN stations in the region. The average crustal thickness of the late Proterozoic Arabian shield is 39 km. The crust thins to about 23 km along the Red Sea coast and to about 25 km along the margin of the Gulf of Aqaba. In the northern part of the Arabian platform, the crust varies from 33 to 37 km thick. However, the crust is thicker (41?53 km) in the southeastern part of the platform. There is a dramatic change in crustal thickness between the topographic escarpment of the Arabian shield and the shorelines of the Red Sea. We compared our results in the Arabian shield to nine other Proterozoic and Archean shields that include reasonably well determined Moho depths, mostly based on receiver functions. The average crustal thickness for all shields is 39 km, while the average for Proterozoic shields is 40 km, and the average for Archean shields is 38 km. We found the crustal thickness of Proterozoic shields to vary between 33 and 44 km, while Archean shields vary between 32 and 47 km. Overall, we do not observe a significant difference between Proterozoic and Archean crustal thickness. We observed a dramatic change in crustal thickness along the Red Sea margin that occurs over a very short distance. We projected our results over a cross-section extending from the Red Sea ridge to the shield escarpment and contrasted it with a typical Atlantic margin. The transition from oceanic to continental crust of the Red Sea margin occurs over a distance of about 250 km, while the transition along a typical portion of the western Atlantic margin occurs at a distance of about 450 km. This important new observation highlights the abruptness of the breakup of Arabia. We argue that a preexisting zone of weakness coupled with anomalously hot upper mantle could have initiated and expedited the breakup

NATO Advanced Research Workshop on Advanced Materials and Technologies for Micro/Nano-Devices, Sensors and Actuators

The main goal of this book is to review recent progress and current status of MEMS/NEMS technologies and devices. Several important areas are discussed: history of research in the field, device physics, examples of sucessful applications, sensors, materials and processing aspects. The authors who have contributed to the book represent a diverse group of leading scientists from academic, industrial and governmental labs worldwide who bring a broad array of backgrounds such as device physics, technologists, electrical and mechanical engineering, surface chemistry and materials science). The contributions to this book are accessible to both expert scientists and engineers who need to keep up with leading edge research, and newcomers to the field who wish to learn more about the exciting basic and applied research issues relevant to micromechanical devices and technologies

Interfacial Bonding and Morphological Control of Electropolymerized Polythiophene Films on ZnO

Integrating polymers with inorganic nanostructures is difficult due to wetting and surface energy considerations. In this paper, we developed an electropolymerization method to grow conformal polymers on high aspect ratio nanostructures. Our method is shown to improve the polymer filling rate inside the nanostructures and can be used in the development of efficient hybrid solar cells. As an example, we have studied the hybrid system of electropolymerized polythiophene (e-PT) on ZnO planar and nanorod substrates using surface characterization methods. Although unsubstituted polythiophene is not the ideal polymer material for high efficiency solar cells, it is an excellent choice for studying basic bonding and morphology in hybrid structures. We find that e-PT is covalently bound to the polar ZnO planar substrate via a Zn–S bond, adopting an upright geometry. By contrast, no strong covalent bonding was observed between e-PT and ZnO nanorods that consist of nonpolar ZnO surfaces predominantly. We manipulated the polymer morphology along the ZnO nanorods by tuning the polarity of the solvent used in electropolymerization. Our electropolymerization approach to integrate the organic and inorganic phases aims at understanding the chemistry at the interface, and the electronic and morphological properties of the system. This work should be generally applicable to other conjugated polymers and nanostructures, and it contributes to an understanding of organic–inorganic interfaces and structures that may be advantageous to a range of electronic/photonic applications

Versatile Fluorescence Resonance Energy Transfer-Based Mesoporous Silica Nanoparticles for Real-Time Monitoring of Drug Release

We describe the development of a versatile fluorescence resonance energy transfer (FRET)-based real-time monitoring system, consisting of (a) coumarin-labeled-cysteine tethered mesoporous silica nanoparticles (MSNs) as the drug carrier, (b) a fluorescein isothiocyanate-β-cyclodextrin (FITC-β-CD) as redox-responsive molecular valve blocking the pores, and (c) a FRET donor–acceptor pair of coumarin and FITC integrated within the pore-unlocking event, thereby allowing for monitoring the release of drugs from the pores in real-time. Under nonreducing conditions, when the disulfide bond is intact, the close proximity between coumarin and FITC on the surface of MSNs results in FRET from coumarin to FITC. However, in the presence of the redox stimuli like glutathione (GSH), the disulfide bond is cleaved which leads to the removal of molecular valve (FITC-β-CD), thus triggering drug release and eliminating FRET. By engineering such a FRET-active donor–acceptor structure within the redox-responsive molecular valve, we can monitor the release of the drugs entrapped within the pores of the MSN nanocarrier, following the change in the FRET signal. We have demonstrated that, any exogenous or endogenous change in the GSH concentration will result in a change in the extent of drug release as well as a concurrent change in the FRET signal, allowing us to extend the applications of our FRET-based MSNs for monitoring the release of any type of drug molecule in real-time

Two-Dimensional Copper Iodide-Based Inorganic–Organic Hybrid Semiconductors: Synthesis, Structures, and Optical and Transport Properties

A group of copper iodide-based hybrid semiconductors with the general formula of 2D-CuI(L)0.5 (L = organic ligands) are synthesized and structurally characterized. All compounds are two-dimensional (2D) networks made of one-dimensional (1D) copper iodide staircase chains that are interconnected by bidentate nitrogen-containing ligands. Results from optical absorption and emission experiments and density functional theory (DFT) calculations reveal that their photoluminescence (PL) can be systematically tuned by adjusting the lowest unoccupied molecular orbital (LUMO) energies of the organic ligands. Charge carrier transport measurements were carried out for the first time on single crystals of selected 2D-CuI(L)0.5 structures, and the results show that they possess p-type conductivity with a Hall mobility of ~1 cm2 V-1 s-1 for 2D-CuI(pm)0.5 and 0.13 cm2 V-1 s-1 for 2D-CuI(pz)0.5, respectively. These values are comparable to or higher than the mobilities of typical highly luminescent organic semiconductors. This work suggests that robust, high-dimensional copper iodide hybrid semiconductors are promising candidates to be considered as a new type of emissive layer for light-emitting diode (LED) devices