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A study of donor electron spins and spin--dependent electronic transitions involving phosphorous ($^{31}$P) atoms in proximity of the (111) oriented crystalline silicon (c-Si) to silicon dioxide (SiO$_{2}$) interface is presented for [$^{31}$P] = 10$^{15}$ $\mathrm{cm}^{-3}$ and [$^{31}$P] = 10$^{16}$ $\mathrm{cm}^{-3}$ at about liquid $^4$He temperatures ($T = 5$ $\mathrm{K} - 15$ $\mathrm{K}$). Using pulsed electrically detected magnetic resonance (pEDMR), spin--dependent transitions between the \Phos donor state and two distinguishable interface states are observed, namely (i) \Pb centers which can be identified by their characteristic anisotropy and (ii) a more isotropic center which is attributed to E$^\prime$ defects of the \sio bulk close to the interface. Correlation measurements of the dynamics of spin--dependent recombination confirm that previously proposed transitions between \Phos and the interface defects take place. The influence of these electronic near--interface transitions on the \Phos donor spin coherence time $T_2$ as well as the donor spin--lattice relaxation time $T_1$ is then investigated by comparison of spin Hahn--echo decay measurements obtained from conventional bulk sensitive pulsed electron paramagnetic resonance and surface sensitive pEDMR, as well as surface sensitive electrically detected inversion recovery experiments. The measurements reveal that both $T_2$ and $T_1$ of \Phos donor electrons spins in proximity of energetically lower interface states at $T\leq 13$ K are reduced by several orders of magnitude.

Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high temperatures and oxidizing environments. Thruster chambers were developed using chemical-vapor-deposited (CVD) Re coated with CVD Ir on the inside surface which is exposed to hot combustion gases. Ir serves as an oxidation barrier protecting the Re which maintains structural integrity at high temperatures. In order to predict and extend the performance limits of these Ir-coated Re thrusters, the diffusion kinetics of CVD materials at temperature are studied. Thruster end ring sections were examined using electron microprobe analysis both before and after exposure to high temperature vacuum environments. The resulting elemental maps for Re, Ir, and Mo in the near-surface region allow identification of diffusion mechanisms operating at these temperatures. Line scans for Ir and Re were fit using a diffusion model to extract relevant diffusion constants. The fastest diffusion process is seen to be grain boundary diffusion with Re diffusing down grain boundaries in the Ir overlayer. The measured dependence of the diffusion rate on temperature will allow prediction of operating lifetimes for these thrusters.

Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.