Synthesis of ZSM‐5 Films and Monoliths with Bimodal Micro/Mesoscopic Structures

A route to synthesize ZSM‐5 crystals with a bimodal micro/mesoscopic pore system has been developed in this study; the successful incorporation of the mesopores within the ZSM‐5 structure was performed using tetrapropylammonium hydroxide (TPAOH)‐impregnated mesoporous materials containing carbon nanotubes in the pores, which were encapsulated in the ZSM‐5 crystals during a solid rearrangement process within the framework. Such mesoporous ZSM‐5 zeolites can be readily obtained as powders, thin films, or monoliths.     

High-performance MIM capacitor using ALD high-k HfO/sub 2/-Al/sub 2/O/sub 3/ laminate dielectrics

For the first time, we successfully fabricated and demonstrated high performance metal-insulator-metal (MIM) capacitors with HfO/sub 2/-Al/sub 2/O/sub 3/ laminate dielectric using atomic layer deposition (ALD) technique. Our data indicates that the laminate MIM capacitor can provide high capacitance density of 12.8 fF//spl mu/m/sup 2/ from 10 kHz up to 20 GHz, very low leakage current of 3.2 /spl times/ 10/sup -8/ A/cm/sup 2/ at 3.3 V, small linear voltage coefficient of capacitance of 240 ppm/V together with quadratic one of 1830 ppm/V/sup 2/, temperature coefficient of capacitance of 182 ppm//spl deg/C, and high breakdown field of /spl sim/6 MV/cm as well as promising reliability. As a result, the HfO/sub 2/-Al/sub 2/O/sub 3/ laminate is a very promising candidate for next generation MIM capacitor for radio frequency and mixed signal integrated circuit applications.     

Inside Front Cover: The Elastic Properties and Plastic Behavior of Two‐Dimensional Polymer Structures Fabricated by Laser Interference Lithography (Adv. Funct. Mater. 10/2006)

The probing of the micromechanical properties within a two‐dimensional polymer structure with sixfold symmetry fabricated via interference lithography reveals a nonuniform spatial distribution in the elastic modulus “imprinted” with an interference pattern in work reported by Tsukruk, Thomas, and co‐workers on p. 1324. The image prepared by M. Lemieux and T. Gorishnyy shows how the interference pattern is formed by three laser beams and is transferred to the solid polymer structure. The elastic and plastic properties within a two‐dimensional polymer (SU8) structure with sixfold symmetry fabricated via interference lithography are presented. There is a nonuniform spatial distribution in the elastic modulus, with a higher elastic modulus obtained for nodes (brightest regions in the laser interference pattern) and a lower elastic modulus for beams (darkest regions in the laser interference pattern) of the photopatterned films. We suggest that such a nonuniformity and unusual plastic behavior are related to the variable material properties “imprinted” by the interference pattern.     

High-resolution photonics-based interference suppression filter with wide passband

A new topology for a photonic signal processor, which overcomes the basic recursive frequency response problem that limits the passband range, is presented. The structure is based on a new multiple-wavelength offset-cavity structure that is cascaded with a series of unbalanced delay line structures. This not only can synthesize a very narrow notch response with good shape factor but also permits a multifold extension of the free spectral range (FSR) and passband width. Results on the interference mitigation filter demonstrate a stopband of 1% of center frequency and a fourfold increase in the FSR and passband width, while also having a very small shape factor, in excellent agreement with predictions.     

Phosphorus‐containing polyaryloxydiphenylsilanes with high flame retardance arising from a phosphorus–silicon synergistic effect

Polyaryloxydiphenylsilanes were prepared from phosphorus‐containing diols and diphenydichlorolsilane through solution polymerization. With a stoichiometric imbalance in feed monomers, the resulting polymers exhibited moderate melting points and good processing properties. The polymers prepared showed initial decomposition temperatures above 340 °C, excellent thermal stability, high char yields at 850 °C and very high limited oxygen index values of 56–59. The polymers' char yields and their (P + Si) contents showed linear relationships. © 2003 Society of Chemical Industry     

Enhanced Photoelectrochemistry in CdS/Au Nanoparticle Bilayers

Three different configurations of Au‐nanoparticle/CdS‐nanoparticle arrays are organized on Au/quartz electrodes for enhanced photocurrent generation. In one configuration, Au‐nanoparticles are covalently linked to the electrode and the CdS‐nanoparticles are covalently linked to the bare Au‐nanoparticle assembly. The resulting photocurrent, φ = 7.5 %, is ca. 9‐fold higher than the photocurrent originating from a CdS‐nanoparticle layer that lacks the Au‐nanoparticles, φ = 0.8 %. The enhanced photocurrent in the Au/CdS nanoparticle array is attributed to effective charge separation of the electron–hole pair by the injection of conduction‐band electrons from the CdS‐ to the Au‐nanoparticles. Two other configurations involving electrostatically stabilized bipyridinium‐crosslinked Au/CdS or CdS/Au nanoparticle arrays were assembled on the Au/quartz crystal. The photocurrent quantum yields in the two systems are φ = 10 % and φ = 5 %, respectively. The photocurrents in control systems that include electrostatically bridged Au/CdS or CdS/Au nanoparticles by oligocationic units that lack electron‐acceptor units are substantially lower than the values observed in the analogous bipyridinium‐bridged systems. The enhanced photocurrents in the bipyridinium‐crosslinked systems is attributed to the stepwise electron transfer of conduction‐band electrons to the Au‐nanoparticles by the bipyridinium relay bridge, a process that stabilizes the electron–hole pair against recombination and leads to effective charge separation.     

Development of a Continuous Segmented Flow Tubular Reactor and the “Scale‐out” Concept – In Search of Perfect Powders

The synthesis of powders with controlled shape and narrow particle size distributions is still a major challenge for many industries. A continuous Segmented Flow Tubular Reactor (SFTR) has been developed to overcome homogeneity and scale‐up problems encountered when using batch reactors. Supersaturation is created by mixing the co‐reactants in a micromixer inducing precipitation; the suspension is then segmented into identical micro‐volumes by a non‐miscible fluid and sent through a tube. These micro‐volumes are more homogeneous when compared to large batch reactors leading to narrower size distributions, better particle morphology, polymorph selectivity and stoichiometry. All these features have been demonstrated on single tube SFTR for different chemical systems. To increase productivity for commercial application the SFTR is being “scaled‐out” by multiplying the number of tubes running in parallel instead of scaling‐up by increasing their size. The versatility of the multi‐tube unit will allow changes in type of precipitate with a minimum of new investment as new chemistry can be researched, developed and optimised in a single tube SFTR and then transferred to the multi‐tube unit for powder production.     

Panchromatic Chromophore Mixtures in an AlPO4‐5 Molecular Sieve: Spatial Separation Effects and Energy Transfer Cascades

Dye‐loaded AlPO₄‐5 single crystals were prepared by microwave‐assisted hydrothermal synthesis from a batch, containing a mixture of three chromophores (Coumarin 40, Rhodamine BE50, and Oxazine 1) differing in their absorption range, molecular dimensions, and solubilities. Confocal fluorescence images reveal a spatial separation effect of the dye molecules, where the slimmer, more‐soluble dye molecule (Coumarin 40) is uniformly distributed in the body of the single crystal, and the bulky and/or less‐soluble ones (Rhodamine BE50, Oxazine 1) are situated in distinct domains. Visible spectra show good panchromatic absorption of visible light. Fluorescence lifetime measurements indicate the presence of an energy transfer cascade of the entirely fixed dye molecules from Coumarin 40 to Oxazine 1. The transfer mechanism is predominantly radiative.     

Influence of quantum capture and tunneling mechanisms on the dark current of bound-to-continuum quantum-well infrared photodetectors

We present a theoretical model for the dark current of bound-to-continuum quantum-well infrared photodetectors (QWIPs), by considering the field-induced mixing effect, tunneling rate and phonon scattering rate between bound and continuum states. Using this model, we can see clearly how these mechanisms significantly influence the Fermi levels of bound and continuum electrons, and thus, the dark current. Nonlinear temperature dependence of the dark current at low temperature is predicted and discussed in detail. The simulated dark currents exhibit good agreement with the experimental results, without use of parameter fitting techniques.