Spectroscopic Characterization of III-V Semiconductor Nanomaterials

III-V semiconductor materials form a broad basis for optoelectronic applications, including the broad basis of the telecom industry as well as smaller markets for high-mobility transistors. In a somewhat analogous manner as the traditional silicon logic industry has so heavily depended upon process manufacturing development, optoelectronics often relies instead on materials innovations. This thesis focuses particularly on III-V semiconductor nanomaterials, detailed characterization of which is invaluable for translating the exhibited behavior into useful applications. Specifically, the original research described in these thesis chapters is an investigation of semiconductors at a fundamental materials level, because the nanostructures in which they appear crystallize in quite atypical forms for the given semiconductors. Rather than restricting the experimental approaches to any one particular technique, many different types of optical spectroscopies are developed and applied where relevant to elucidate the connection between the crystalline structure and exhibited properties. 2 In the first chapters, for example, a wurtzite crystalline form of the prototypical zincblende III-V binary semiconductor, GaAs, is explored through polarization-dependent Raman spectroscopy and temperature-dependent photoluminescence, as well as second-harmonic generation (SHG). The altered symmetry properties of the wurtzite crystalline structure are particularly evident in the Raman and SHG polarization dependences, all within a bulk material realm. A rather different but deeply elegant aspect of crystalline symmetry in GaAs is explored in a separate study on zincblende GaAs samples quantum-confined in one direction, i.e. quantum well structures, whose quantization direction corresponds to the (110) direction. The (110) orientation modifies the low-temperature electron spin relaxation mechanisms available compared to the usual (001) samples, leading to altered spin coherence times explored through a novel spectroscopic technique first formulated for the rather different purpose of dispersion engineering for slow-light schemes. The frequency-resolved technique combined with the unusual (110) quantum wells in a furthermore atypical waveguide experimental geometry has revealed fascinating behavior of electron spin splitting which points to the possibility of optically orienting electron spins with linearly polarized light—an experimental result supporting a theoretical description of the phenomenon itself only a few years old. Lastly, to explore a space of further-restricted dimensionality, the final chapters describe InP semiconductor nanowires with dimensions small enough to be considered truly one-dimensional. Like the bulk GaAs of the first few chapters, the InP nanowires here crystallize in a wurtzite structure. In the InP nanowire case, though, the 3 experimental techniques explored for characterization are temperature-dependent time-integrated photoluminescence at the single-wire level (including …