A new extended x-ray-absorption fine structure spectroscopy study of local bonding identifies for the first time significant concentrations of Ge-Ge bonds in amorphous Ge2Sb2Te5. The study provides a new understanding of the local molecular structure of this phase-change material. Application of bond constraint theory indicates that the amorphous phase is an ideal network structure in which the average number of constraints per atom equals the network dimensionality. Analysis within this framework imparts new and significant insights concerning the nature of the reversible optically driven amorphous-crystalline phase transition of Ge2Sb2Te5.

Phase selective synthesis of type II silicon clathrates from thermal decomposition of NaSi has previously been limited to small quantities due to the simultaneous formation of competing phases. In this work we show that the local sodium vapor pressure during the NaSi precursor decomposition is a critical parameter for controlling phase selection. We demonstrate synthesis techniques that allow us to tune the local Na vapor pressure, yielding type I or II clathrate products that are ≥90 wt.% phase pure. The "cold plate" reactor design discussed in this work maintains low Na vapor pressure during thermal decomposition of NaSi, thus yielding large scale, phase selective synthesis of type II silicon clathrates. The low Na vapor pressure maintained in this reactor is also shown to efficiently produce low Na (x ~1; Na x Si 136 ) Si clathrate through Na sublimation. To further reduce sodium occupancy (x < 1), we demonstrate etching of Na x Si 136 in HF/HNO 3 solutions, which rapidly yields a clathrate product with reduced x. 29 Si NMR and electron spin resonance (ESR) characterization validate the low Na occupancy of Si clathrate synthesized.The acid etch also selectively dissolves the type I silicon clathrate impurity phase, thereby enabling the synthesis of large quantities of phase pure type II silicon clathrate with low Na content.

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Doping a perylene diimide organic semiconductor with a one-electron reduced perylene diimide containing a covalently bound counterion provides a well-characterized system for understanding doping in organic semiconductors. We obtain insight into the doping process by electron paramagnetic resonance (EPR) measurements of the dopant solutions, the dopant plus host solutions from which thin films are spin-coated, and the resulting solid films. After correction for some trace impurities in the solutions, the spin density incorporated into the solid films is linearly proportional to the added dopant density. Nevertheless, the film conductivity increases superlinearly with dopant concentration. Although neither pure dopant nor host aggregate in solution, they aggregate when combined. This is presumably a result of the delocalization of the dopant electron over a number of host molecules. Angle-dependent EPR measurements on thin films suggest that the g-tensor symmetry axis is close to the π-π stacking axis, consistent with relatively delocalized electrons in this crystal direction. Nevertheless, most electrons are not entirely free, but still bound in the vicinity of the dopant cation by Coulomb attraction. At low concentration, dopants appear to segregate primarily to crystallite grain boundaries, while at higher concentration they are incorporated into the bulk of the crystallites. About half of the spins are paired in the solid at room temperature, and more at lower temperature.

A systematic study of tin-catalyzed vapor−liquid−solid (VLS) growth of silicon nanowires by plasma-enhanced chemical vapor deposition at temperatures ranging from 300 to 400 °C is presented. Wire structure, morphology, and growth rate are characterized as a function of process variables. The nanowires are observed to have a crystalline core with a polycrystalline shell due to simultaneous VLS axial growth and vapor−solid radial growth. Axial and radial growth rates are controllable through hydrogen dilution of the plasma which affects the concentration of silane radicals in the plasma. In addition, wire length is observed to saturate with increasing growth time. Post growth chemical analysis suggests this is due to etching and disappearance of tin seeds in the hydrogen plasma which occur in parallel with wire growth. This opens up the possibility of a unique in situ approach to fabricating metal-free nanowire arrays for device applications.