The electron ionization rate in multilayered semiconductor structures

We present theoretical results of the electron impact ionization rate in GaAs/AlGaAs multiquantum well structures as a function of applied electric field for various geometries, i.e., well and barrier widths. In addition, we present preliminary measurements of the current-voltage characteristics of MBE grown devices which demonstrate very low leakage current as well as sharp breakdwon behavior. It is found that the net ionization rate, determined by averaging over the constitutent GaAs and AlGaAs layers, approaches the weighted average of the constituent bulk rates at high electric field strengths; the potential discontinuity is relatively unimportant. The electron ionization rate within the well regions alone is still higher than that in bulk GaAs, but is insufficiently enhanced to compensate for the much lower rate in the AlGaAs layers. As the field is lowered to 250.0 kV/cm, the average ionization rate in the multiquantum well structure becomes larger than in the bulk.     

New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Conformation and luminescence of isolated molecular semiconductor molecules

In this article, we describe, for the first time, direct comparisons of the detailed structures of two small molecule organic semiconductors, oligo(phenylenvinylene) (OPV) molecules with chains of five and six phenyl rings (5R-OC(8)H(17) and 6R-OC(8)H(17)), respectively, and their luminescence properties on a single molecule level. Our data originate from a combination of two powerful diagnostic tools in physical chemistry: ion mobility and single molecule fluorescence spectroscopy. These techniques enable us to precisely determine the shapes of isolated molecules in the gas phase and to correlate these structures to the emission from single molecules supported on bare glass substrates. The principal structural uncertainty in OPVs is the (possible) presence and location of cis-vinylene linkages (cis-defects) in the oligomer. The results show that the structures observed in the gas phase are strongly correlated to the categories of molecules observed in the single molecule polarization anisotropy measurements with nearly identical distributions for the two OPV molecules studied. Each category is also characterized by the luminescence efficiency of the molecules in each class, providing a direct correlation between the luminescence efficiency and the shape of the molecule. This combination of techniques provides a level of information far beyond that obtained via any other analytical technique.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.