Publications

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Thermionic energy conversion in a miniature format shows potential as a viable, high efficiency, micro to macro-scale power source. A microminiature thermionic converter (MTC) with inter-electrode spacings on the order of microns has been prototyped and evaluated at Sandia. The remaining enabling technology is the development of low work function materials and processes that can be integrated into these converters to increase power production at modest temperatures (800 - 1300 K). The electrode materials are not well understood and the electrode thermionic properties are highly sensitive to manufacturing processes. Advanced theoretical, modeling, and fabrication capabilities are required to achieve optimum performance for MTC diodes. This report describes the modeling and fabrication efforts performed to develop micro dispenser cathodes for use in the MTC.

Density functional theory is used to predict workfunctions, {psi}. For relaxed clean W(1 0 0), the local density approximation (LDA) agrees with experiment better than the newer generalized gradient approximation, probably due to the surface electron self-energy. The large Ba metallic radius indicates it covers W(1 0 0) at about 0.5 monolayer (ML). However, Ba{sup 2+}, O{sup 2-}, and metallic W all have similar radii. Thus 1 ML of BaO (one BaO unit for each two W atoms) produces minimum strain, indicating commensurate interfaces. BaO (1 ML) and Ba (1/2 ML) have the same {psi} to within 0.02 V, so at these coverages reduction or oxidation is not important. Due to greater chemical activity of ScO vs. highly ionic BaO, when mixing the latter with this suboxide of scandia, the overlayer always has BaO as the top layer and ScO as the second layer. The BaO/ScO bilayer has a rocksalt structure, suggesting high stability. In the series BaO/ScO/, BaO/YO/, and BaO/LaO/W(1 0 0), the latter has a remarkably low {psi} of 1.3 V (LDA), but 2 ML of rocksalt BaO also has {psi} at 1.3 V. We suggest BaO (1 ML) does not exist and that it is worthwhile to attempt the direct synthesis and study of BaO (2 ML) and BaO/LaO.

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Under UHV conditions at 300 K, the applied electric field and/or resulting current from an STM tip creates nanoscale voids at the interface between an epitaxial, 7.0 {angstrom} thick Al{sub 2}O{sub 3} film and a Ni{sub 3}Al(111) substrate. This phenomenon is independent of tip polarity. Constant current (1 nA) images obtained at +0.1 V bias and +2.0 bias voltage (sample positive) reveal that voids are within the metal at the interface and, when small, are capped by the oxide film. Void size increases with time of exposure. The rate of void growth increases with applied bias/field and tunneling current, and increases significantly for field strengths >5 MV/cm, well below the dielectric breakdown threshold of 12 {+-} 1 MV/cm. Slower rates of void growth are, however, observed at lower applied field strengths. Continued growth of voids, to {approximately}30 {angstrom} deep and {approximately}500 {angstrom} wide, leads to the eventual failure of the oxide overlayer. Density Functional Theory calculations suggest a reduction-oxidation (REDOX) mechanism: interracial metal atoms are oxidized via transport into the oxide, while oxide surface Al cations are reduced to admetal species which rapidly diffuse away. This is found to be exothermic in model calculations, regardless of the details of the oxide film structure; thus, the barriers to void formation are kinetic rather than thermodynamic. We discuss our results in terms of mechanisms for the localized pitting corrosion of aluminum, as our results suggest nanovoid formation requires just electric field and current, which are ubiquitous in environmental conditions.

First principles density-functional slab calculations are used to study 5 {angstrom} (two O-layer) Al{sub 2}O{sub 3} films on Ru(0001) and Al(111). Using larger unit cells than in a recent study, it is found that the lowest energy stable film has an even mix of tetrahedral (t) and octahedral (o) site Al ions, and thus most closely resembles the {kappa}-phase of bulk alumina. Here, alternating zig-zag rows of t and o occur within the surface plane, resulting in a greater average lateral separation of the Al-ions than with pure t or o. A second structure with an even mix of t and o has also been found, consisting of alternating stripes. These patterns mix easily, can exist in three equivalent directions on basal substrates, and can also be displaced laterally, suggesting a mechanism for a loss of long-range order in the Al-sublattice. While the latter would cause the film to appear amorphous in diffraction experiments, local coordination and film density are little affected. On a film supported by rigid Ru(0001), overlayers of Cu, Pd, and Pt bind similarly as on bulk truncated {alpha}-Al{sub 2}O{sub 3}(0001). However, when the film is supported by soft Al(111), the adhesion of Cu, Pd, and Pt metal overlayers is significantly increased: Oxide-surface Al atoms rise so only they contact the overlayer, while substrate Al metal atoms migrate into the oxide film. Thus the binding energy of metal overlayers is strongly substrate dependent, and these numbers for the above Pd-overlayer systems bracket a recent experimentally derived value for a film on NiAl(110).

Atoms and molecules adsorbed on metals affect each other even over considerable distances. In a tour-de-force of density-functional methods, the authors establish the nature and strength of such indirect interactions, and explain for what adsorbate systems they can critically affect important materials properties. These perceptions are verified in kinetic Monte Carlo simulations of epitaxial growth, and help rationalize a cascade of recent experimental reports on anomalously low diffusion prefactors. The authors focus their study on two metal systems: Al/Al(111) and Cu/Cu(111).