III-nitrides are a promising material system with unique material properties, which allows them to be utilized in a variety of semiconductor devices. III-nitrides grown by NH3-MOMBE are typically grown with high carbon levels (> 1021 cm-3) as a result of the incomplete surface pyrolysis of the metal-organic sources. Recent research has involved the compensating nature of carbon in III-nitrides to produce semi-insulating films, which can provide low-leakage buffer layers in transistor devices. The aim of this work is to investigate the possibility of forming a 2DEG, which utilizes the highly carbon-doped GaN layers grown by NH3-MOMBE to produce low-leakage buffer layers in the fabrication of HEMTs. These low leakage GaN buffers would provide increased HEMT performance, with better pinch-off, higher breakdown voltages and increased power densities. Additionally, methods of controlling and/or reducing the incorporation of carbon will be undertaken in an attempt to broaden the range of possible device applications for NH3-MOMBE. To realize these transistor devices, optimization and improved understanding of the growth conditions for both GaN and AlGaN will be explored with the ultimate goal of determining the feasibility of III-nitride transistors grown by NH3-MOMBE.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / Hexagonal boron nitride (hBN) is a wide bandgap III-V semiconductor that has seen new interest due to the development of other III-V LED devices and the advent of graphene and other 2-D materials. For device applications, high quality, low defect density materials are needed. Several applications for hBN crystals are being investigated, including as a neutron detector and interference-less infrared-absorbing material. Isotopically enriched crystals were utilized for enhanced propagation of phonon modes. These applications exploit the unique physical, electronic and nanophotonics applications for bulk hBN crystals. In this study, bulk hBN crystals were grown by the flux method using a molten Ni-Cr solvent at high temperatures (1500°C) and atmospheric pressures. The effects of growth parameters, source materials, and gas environment on the crystals size, morphology and purity were established and controlled, and the reliability of the process was greatly improved. Single-crystal domains exceeding 1mm in width and 200μm in thickness were produced and transferred to handle substrates for analysis. Grain size dependence with respect to dwell temperature, cooling rate and cooling temperature were analyzed and modeled using response surface morphology. Most significantly, crystal grain width was predicted to increase linearly with dwell temperature, with single-crystal domains exceeding 2mm in at 1700°C. Isotopically enriched ¹⁰B and ¹¹B hBN crystal were produced using a Ni-Cr-B flux method, and their properties investigated. ¹⁰B concentration was evaluated using SIMS and correlated to the shift in the Raman peak of the E[subscript 2g] mode. Crystals with enrichment of 99% ¹⁰B and >99% ¹¹B were achieved, with corresponding Raman shift peaks at 1392.0 cm⁻¹ and 1356.6 cm⁻¹, respectively. Peak FWHM also decreased as isotopic enrichment approached 100%, with widths as low as 3.5 cm⁻¹ achieved, compared to 8.0 cm⁻¹ for natural abundance samples. Defect selective etching was performed using a molten NaOH-KOH etchant at 425°C-525°C, to quantify the quality of the crystals. Three etch pit shapes were identified and etch pit width was investigated as a function of temperature. Etch pit density and etch pit activation energy was estimated at 5×10⁷ cm⁻² and 60 kJ/mol, respectively. Screw and mixed-type dislocations were identified using diffraction-contrast TEM imaging.

Le contexte de cette thèse se situe dans les nombreuses applications de sources UV tels que la stérilisation et la purification. Comparés aux sources conventionnelles, les dispositifs à base de semiconducteur présentent la fiabilité, l'efficacité élevée, et les effets minimaux sur l'environnement. Sur l'aspect des matériaux, III-Nitrures (BAlGaInN) sont les candidats prometteurs car ils sont stables chimiquement et physiquement, et ils présentent les bandes interdites couvrant le spectre visible à l'UV profond. Sur l'aspect des structures, le laser à cavité vertical émettant par la surface (VCSEL) est l'une des configurations les plus attrayantes, et il offre des avantages tels que le seuil bas, le haut rendement, la possibilité d'intégration des réseaux 2D et les tests au niveau de la plaquette. Néanmoins, il n'existe aucun VCSEL fonctionnant en dessous de 300 nm. Des défis importants concernent l'efficacité de MQWs et la réflectivité de réflecteur de Bragg distribué (DBR), qui sont limitées par la qualité des matériaux, les propriétés optiques des MQWs, le contraste faible d'indice de réfraction pour les couches dans les DBRs à des longueurs d'onde courtes, etc. L'objectif de cette thèse est de répondre aux défis relevés auparavant en étudiant la croissance de BAlGaN par épitaxie en phase vapeur aux organométalliques (MOVPE), en développant les MQWs d'AlGaN avec l'augmentation des émissions par la surface, et en explorant les DBRs en BAlN/AlGaN, en vue du développement de VCSEL à pompage optique fonctionnant dans DUV / The context of this thesis falls in the wide applications of UV light sources such as sterilization and purification. Compared to the conventional UV sources (excimer lasers, Nd: YAG lasers or mercury lamps), the semiconductor devices have advantages in reliability, compactness, high efficiency and minimum environmental effects. On the material aspect, III-nitrides (BAlGaInN) are promising candidates since they are chemically and physically stable with direct bandgaps covering from visible to DUV spectrum. On the structure aspect, vertical-cavity surface-emitting laser (VCSEL) is one of the most attractive configurations considering its low threshold, high efficiency, and the possibility for the integration of 2D arrays and the wafer-level tests. It constitutes a multiple-quantum-well (MQW) active region sandwiched by a top and a bottom distributed Bragg reflector (DBR). However, no VCSELs can operate below 300 nm until now. The major challenges lie in the two main blocks: the emission efficiency of MQWs and the reflectivity of DBRs, which are limited by the quality of the substrates and epitaxial layers, optical-polarization properties of the MQW emission, small refractive index contrast of the layers used for DBRs at short wavelengths, etc. The objective of this thesis is to address this need by studying metal-organic vapor-phase epitaxy (MOVPE) growth of BAlGaN materials, developing AlGaN MQWs with enhanced surface emission and exploring BAlN/AlGaN DBRs, for the future development of optically-pumped VCSELs operating below 300 nm

III-nitride semiconductors suffer significant efficiency limitations; ‘efficiency’ being an umbrella term that covers an extensive list of challenges that must be overcome if they are to fulfil their vast potential. To this end, it is imperative to understand the underlying phenomena behind such limitations. In this dissertation, I combine powerful optical and structural characterization techniques to investigate the effect of different defects on the carrier dynamics in III-nitride materials for light emitting devices. The results presented herein will enhance the current understanding of the carrier mechanisms in such devices, which will lead to device efficiency improvements. In the first part of this dissertation, the effects of some important types of crystal defects present in III-nitride structures are investigated. Here, two types of defects are studied in two different III-nitride-based light emitting structures. The first defects of interest are V-pit defects in InGaN/GaN multiple quantum well (MQW) blue LEDs, where their contribution to the high-efficiency of such LEDs is discussed. In addition, the effect of these defects on the efficiency droop phenomenon in these LEDs is elucidated. Secondly, the optical effects of grain boundary defects in AlN-rich AlGaN/AlGaN MQWs is studied. In this study, it is shown that grain boundary defects may result in abnormal carrier localization behavior in these deep ultraviolet (UV) structures. While both defects are treated individually, it is evident from these studies that threading dislocation (TD) defects are an underlying contributor to the more undesirable outcomes of the said defects. In the second part, the dissertation reports on the carrier dynamics of III-nitride LED structures grown on emerging substrates—as possible efficiency enhancing techniques—aimed at mitigating the effects of TD defects. Thus, the carrier dynamics of GaN/AlGaN UV MQWs grown, for the first time, on (2̅01) – oriented β-Ga2O3 is studied. It is shown to be a candidate substrate for highly efficient vertical UV devices. Finally, results from the carrier dynamics investigation of an AlGaN/AlGaN MQW LED structure homoepitaxially grown on AlN substrate are discussed, where it is shown that its high-efficiency is sustained at high temperatures through the thermal redistribution of carriers to highly efficient recombination sites.

<p>Infrared intersubband absorption of III-nitride materials has been studied rigorously due to its broad potential applications into optoelectronic devices. III-nitrides have advantages of large conduction band offset, large longitudinal-optical phonon energy, and fast intersubband relaxation time. These special characteristics make nitrides promising materials for intersubband devices in the near-infrared range. However, the existence of challenges from these materials delays the progress towards the realization of high performance nitride intersubband devices. In this document, we discuss the challenges of III-nitrides and our efforts towards high intersubband transitions strength of different nitrides, in particular non-polar m-plane AlGaN/GaN, non-polar m-plane near strain-balanced (In)AlGaN/InGaN, and polar lattice-matched InAlN/GaN. Samples are characterized by multiple methods including atomic force microscopy, high-resolution x-ray diffraction, high-resolution (scanning) transmission electron microscopy, and Fourier transform infrared spectroscopy.</p> <p>Polar c-plane AlGaN/GaN exhibits good agreement between experimental and predicted results for the intersubband transition energy. However, the lattice strain between layers caused by the lattice mismatch between materials leads to a large number of defects, affecting the vertical transport and resulting in low-quality devices. Lattice-matched InAlN/GaN was suggested as an alternative to eliminate this lattice strain, thus providing a better quality material for devices. We discuss the challenges of growing homogeneous InAlN alloys that persist after exploring a wide range of growth conditions. Additionally, the non-polar mplane AlGaN/GaN is also being investigated. Low Al-composition m-plane AlGaN/GaN experimental intersubband absorption shows good agreement with the theoretical results. As the Al composition exceeds 60%, however, the m-plane AlGaN alloy becomes kinetically unstable during plasma-assisted molecular beam epitaxy growth, resulting in unique nanostructures that affect the intersubband transition energy and linewidth. For the first time, we reported the ISBA energy of near strain-balanced non-polar m-plane (In)AlGaN/InGaN heterostructures in the mid-infrared range with narrow linewidths comparable to tdth-half-max published in the literature for non-polar m-plane AlGaN/GaN superlattices. Additionally, we propose polar near lattice-matched Sc0.15Al0.85N/GaN as an alternative to c-plane lattice-matched InAlN/GaN. </p>

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In this research the growth of InN epilayers by high-pressure chemical vapor deposition (HPCVD) and structural, optical properties of HPCVD grown InN layers has been studied. We demonstrated that the HPCVD approach suppresses the thermal decomposition of InN, and therefore extends the processing parameters towards the higher growth temperatures (up to 1100K for reactor pressures of 15 bar, molar ammonia and TMI ratios around 800, and a carrier gas flow of 12 slm). Structural and surface morphology studies of InN thin layers have been performed by X-ray diffraction, low energy electron diffraction (LEED), auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS) and atomic force microscopy (AFM). Raman spectroscopy, infrared reflection, transmission, photoluminescence spectroscopy studies have been carried out to investigate the structural and optical properties of InN films grown on sapphire and GaN/sapphire templates. InN layers grown on a GaN (0002) epilayer exhibit single-phase InN (0002) X-ray diffraction peaks with a full width at half maximum (FWHM) around 200 arcsec. Auger electron spectroscopy confirmed the cleanliness of the surface, and low energy electron diffraction yielded a 1×1 hexagonal pattern indicating a well-ordered surface. The plasmon excitations are shifted to lower energies in HREEL spectra due to the higher carrier concentration at the surface than in the bulk, suggesting a surface electron accumulation. The surface roughness of samples grown on GaN templates is found to be smoother (roughness of 9 nm) compared to the samples grown on sapphire. We found that the deposition sometimes led to the growth of 3 dimensional hexagonal InN pyramids. Results obtained from Raman and IR reflectance measurements are used to estimate the free carrier concentrations, which were found in the range from mid 10^18 cm-3 to low 10^20 cm-3. The optical absorption edge energy calculated from the transmission spectra is 1.2 eV for samples of lower electron concentration. The Raman analysis revealed a high-quality crystalline layer with a FWHM for the E2(high) peak around 6.9 cm^-1. The results presented in our study suggest that the optimum molar ratio might be below 800, which is due to the efficient cracking of the ammonia precursor at the high reactor pressure and high growth temperature.

The objective of the proposed research is to establish the technology for material growth by molecular beam epitaxy (MBE) and fabrication of indium gallium nitride/gallium nitride (InxGa1-xN/GaN) heterojunction solar cells. InxGa1-xN solar cell have the potential to span 90% of the solar spectrum, however there has been no success with high indium (In) incorporation and only limited success with low In incorporation InxGa1-xN. Therefore, this present work focuses on 15 - 30% In incorporation leading to a bandgap value of 2.3 - 2.8 eV. This work will exploit the revision of the indium nitride (InN) bandgap value of 0.68 eV, which expands the range of the optical emission of nitride-based devices from ultraviolet to near infrared regions, by developing transparent InxGa1-xN solar cells outside the visible spectrum. Photovoltaic devices with a bandgap greater than 2.0 eV are attractive because over half the available power in the solar spectrum is above the photon energy of 2.0 eV. The ability of InxGa1-xN materials to optimally span the solar spectrum offers a tantalizing solution for high-efficiency photovoltaics. Using the metal modulated epitaxy (MME) technique in a new, ultra-clean refurbished MBE system, an innovative growth regime is established where In and Ga phase separation is diminished by increasing the growth rate for InxGa1-xN. The MME technique modulates the metal shutters with a fixed duty cycle while maintaining a constant nitrogen flux and proves effective for improving crystal quality and p-type doping. We demonstrate the ability to repeatedly grow high hole concentration Mg-doped GaN films using the MME technique. The highest hole concentration obtained is equal to 4.26 e19 cm-3, resistivity of 0.5 Ω-cm, and mobility of 0.28 cm2/V-s. We have achieved hole concentrations significantly higher than recorded in the literature, proving that our growth parameters and the MME technique is feasible, repeatable, and beneficial. The high hole concentration p-GaN is used as the emitter in our InxGa1-xN solar cell devices.

8-band k.p theory was applied to bulk GaN and InN. The optical transitionintensity was computed and results show &gt; 80-90% degree of polarization inthe direction of compression. Polarization switching is observed when strainwas reversed from compressive to tensile. 6 band k.p theory was used tostudy InGaN quantum dot/GaN elliptical pyramid structures. The opticaltransition intensity was calculated for different elongations of the pyramid.Elongation of the pyramid gives rise to a small polarization in the directionof the pyramid elongation. The optical transition intensity was calculatedfor elongated quantum dots and was strongly in uencing the polarization inthe direction of the quantum dot elongation, with a degree of polarization of &gt;90%.

Semiconductor based micro- and nano-structures grown in a systematic and controlled way using selective area growth are emerging as a promising route toward devices for integrated optical circuitry in optoelectronics and photonics field. This dissertation focuses on the experimental investigation of the nonlinear optical effects in selectively grown gallium nitride micro-pyramids that act as optical cavities, zinc oxide submicron rods and indium gallium nitride multiple quantum well core shell submicron tubes on the apex of GaN micro pyramids that act as optical antennae. Localized spatial excitation of these low dimensional semiconductor structures was optimized for nonlinear optical light (NLO) generation due to second harmonic generation (SHG) and multi-photon luminescence (MPL). The evolution of both processes are mapped along the symmetric axis of the individual structures for multiple fundamental input frequencies of light. Effects such as cavity formation of generated light, electron-hole plasma generation and coherent emission are observed. The efficiency and tunability of the frequency conversion that can be achieved in the individual structures of various geometries are estimated. By controlling the local excitation cross-section within the structures along with modulation of optical excitation intensity, the nonlinear optical process generated in these structures can be manipulated to generate coherent light in the UV-Blue region via SHG process or green emission via MPL process. The results show that these unique structures hold the potential to convert red input pulsed light into blue output pulsed light which is highly directional.