Several rare-earth pnictide suboxides were investigated for their structures, chemistry, and physical properties. The goal of this research was to develop a highly stable material that could combine the thermally insulating properties of a rare-earth oxide framework with the electrically conductive properties of a rare-earth pnictide framework. These materials were synthesized by solid state reactions at high temperatures, producing highly pure products for measurement. All phases were subjected to several different forms of analysis, including X-ray powder and single crystal diffraction, energy dispersive X-ray spectroscopy (EDS), electron microprobe analysis (EPMA), magnetization, and hall resistivity measurements. Sufficiently pure bulk samples were then measured for thermoelectric properties in terms of electrical resistivity, Seebeck coefficient, and thermal conductivity, where applicable. The roles of structure and chemistry for each phase were then discussed with respect to the obtained physical properties and calculated electronic structures. Seven distinct classes of rare-earth pnictide suboxides were investigated in this dissertation: the tetragonal (REIREII)3SbO3 phases (space group C2/m), the CaRE3SbO4 phases (space group I4/m), the Ca2RE8Sb3O10 phases (space group C2/m), the Gd3BiO3 phase and Gd8Bi3O8 phases (space groups C2/m), and the Ca2RE7Sb5O5 phase and Ca2RE7Bi5O5 phases (space groups P4/n). All of these phases share many common structural features, and can be related by different RE4O tetrahedral building block stacking sequences and locations of the pnictide atoms. Structurally speaking, the simplest possible arrangement of the RE-O and RE-Pn frameworks we investigated are found in the CaRE3SbO4 phase. This phase contains the smallest unit cell of all known rare-earth pnictide suboxides with only a two unit RE4O tetrahedral building block and ordered antimony atoms. Extended heat treatments gradually convert this phase into the corresponding Ca2RE8Sb3O10 phase, with a significantly more complicated arrangement of RE4O building blocks. By controlling the loading composition and reaction conditions, the CaRE3SbO4 phase can be prepared as a kinetic product, while the Ca2RE8Sb3O10 phase forms as the thermodynamic product. Likewise, the tetragonal (REIREII)3SbO3 phases can also be prepared through high temperature reactions. This phase contains a unique three RE4O unit (RE8O3) building block in its structure, which creates two rare-earth sites with a large difference in site volume. Thus, this phase can only be prepared when two rare-earth atoms of sufficiently different size are present. Despite similar structures, the physical properties of the studied rare-earth pnictide suboxide phases can display quite different behavior. For the CaRE3SbO4, Ca2RE7Sb5O5, Ca2RE7Bi5O5, and tetragonal (REIREII)3SbO3 phases, the electrical resistivity remains fairly constant throughout the series, which can be traced to their highly ordered structures, as well as the physical and chemical similarities between rare-earths. Conversely, the more structurally disordered Ca2RE8Sb3O10 and Gd8Bi3O8 phases behave as semiconductors despite the fact they are not charge balanced. This anomalous behavior arises from the disorder of Sb and Bi atoms, which are responsible for electrical conduction in the phase. Interestingly, the level of disorder and thus, the magnitude of the electrical resistivity, can be greatly influenced by the rare-earth atom that is present, despite maintaining similar structures and charge carrier concentrations. Smaller rare earth atoms introduce a larger chemical pressure on the disordered antimony/bismuth atoms which lowers the range of Anderson localized states, pushing the system closer to metallic-type conduction. / Thesis / Doctor of Philosophy (PhD)

Heterostructures of materials with dramatically different properties are exciting for a variety of devices. In particular, the epitaxial integration of metals with semiconductors is promising for low-loss tunnel junctions, embedded Ohmic contacts, high-conductivity spreading layers, as well as optical devices based on the surface plasmons at metal/semiconductor interfaces. This thesis investigates the structural, electrical, and optical properties of compound (III-V) semiconductors employing rare-earth monopnictide (RE-V) nanostructures. Tunnel junctions employing RE-V nanoparticles are developed to enhance current optical devices, and the epitaxial incorporation of RE-V films is discussed for embedded electrical and plasmonic devices. Leveraging the favorable band alignments of RE-V materials in GaAs and GaSb semiconductors, nanoparticle-enhanced tunnel junctions are investigated for applications of wide-bandgap tunnel junctions and lightly-doped tunnel junctions in optical devices. Through optimization of the growth space, ErAs nanoparticle-enhanced GaAs tunnel junctions exhibit conductivity similar to the best reports on the material system. Additionally, GaSb-based tunnel junctions are developed with low p-type doping that could reduce optical loss in the cladding of a 4 μm laser by ~75%. These tunnel junctions have several advantages over competing approaches, including improved thermal stability, precise control over nanoparticle location, and incorporation of a manifold of states at the tunnel junction interface. Investigating the integration of RE-V nanostructures into optical devices revealed important details of the RE-V growth, allowing for quantum wells to be grown within 15nm of an ErAs nanoparticle layer with minimal degradation (i.e. 95% of the peak photoluminescence intensity). This investigation into the MBE growth of ErAs provides the foundation for enhancing optical devices with RE-V nanostructures. Additionally, the improved understanding of ErAs growth leads to development of a method to grow full films of RE-V embedded in III-V materials. The growth method overcomes the mismatch in rotational symmetry of RE-V and III-V materials by seeding film growth with epitaxial nanoparticles, and growing the film through a thin III-V spacer. The growth of RE-V films is promising for both embedded electrical devices as well as a potential path towards realization of plasmonic devices with epitaxially integrated metallic films. / text