abstract: III-nitride alloys are wide band gap semiconductors with a broad range of applications in optoelectronic devices such as light emitting diodes and laser diodes. Indium gallium nitride light emitting diodes have been successfully produced over the past decade. But the progress of green emission light emitting devices has been limited by the incorporation of indium in the alloy, mainly due to phase separation. This difficulty could be addressed by studying the growth and thermodynamics of these alloys. Knowledge of thermodynamic phase stabilities and of pressure - temperature - composition phase diagrams is important for an understanding of the boundary conditions of a variety of growth techniques. In this dissertation a study of the phase separation of indium gallium nitride is conducted using a regular solution model of the ternary alloy system. Graphs of Gibbs free energy of mixing were produced for a range of temperatures. Binodal and spinodal decomposition curves show the stable and unstable regions of the alloy in equilibrium. The growth of gallium nitride and indium gallium nitride was attempted by the reaction of molten gallium - indium alloy with ammonia at atmospheric pressure. Characterization by X-ray diffraction, photoluminescence, and secondary electron microscopy show that the samples produced by this method contain only gallium nitride in the hexagonal phase. The instability of indium nitride at the temperatures required for activation of ammonia accounts for these results. The photoluminescence spectra show a correlation between the intensity of a broad green emission, related to native defects, and indium composition used in the molten alloy. A different growth method was used to grow two columnar-structured gallium nitride films using ammonium chloride and gallium as reactants and nitrogen and ammonia as carrier gasses. Investigation by X-ray diffraction and spatially-resolved cathodoluminescence shows the film grown at higher temperature to be primarily hexagonal with small quantities of cubic crystallites, while the one grown at lower temperature to be pure hexagonal. This was also confirmed by low temperature photoluminescence measurements. The results presented here show that cubic and hexagonal crystallites can coexist, with the cubic phase having a much sharper and stronger luminescence. Controlled growth of the cubic phase GaN crystallites can be of use for high efficiency light detecting and emitting devices. The ammonolysis of a precursor was used to grow InGaN powders with different indium composition. High purity hexagonal GaN and InN were obtained. XRD spectra showed complete phase separation for samples with x < 30%, with ~ 9% indium incorporation in the 30% sample. The presence of InGaN in this sample was confirmed by PL measurements, where luminescence from both GaN and InGaN band edge are observed. The growth of higher indium compositions samples proved to be difficult, with only the presence of InN in the sample. Nonetheless, by controlling parameters like temperature and time may lead to successful growth of this III-nitride alloy by this method. / Dissertation/Thesis / Ph.D. Physics 2011

Materials have always had a large impact on society over the different ages. Piezoelectric materials are the often ‘invisible’ materials which find widespread use, unknown to the general public by large. Mobile electronics, automotive systems, medical and industrial systems are few of the key areas where ‘piezoelectricity’ is indispensable. The parking sensor of our car uses the effect and even the echo to image an unborn baby in a womb requires the exploitation of the piezoelectric effect. The work presented in this thesis investigates the piezoelectric effect in semiconductors, namely in III V, III N and II VI materials to have a better understanding and design potential applications in light emitting diodes (LEDs) and other electronic devices. The current work focuses on the non-linear behaviour in the strain of the piezo effect, which is manifested by the generation of electric field under crystal deformation. Previous works have already confirmed the reports of the existence of non-linear piezoelectric effects in zincblende III V semiconductors. Here, the same semiempirical approach using Density Functional Theory has been utilized to investigate the strain dependent elastic and dielectric properties of wurtzite III N materials. While we report the strong non-linear strain induced piezoelectric behaviour with second order coefficients, all spontaneous polarization terms are substantially smaller than the previously proposed values. We show that, unlike existing models, our calculated piezoelectric coefficients and nonlinear model provide a close match to the internal piezoelectric fields of quantum well and superlattice structures. Also, pressure dependence of the piezoelectric field in InGaN based LEDs predicts a significant improvement of the spontaneous emission rate can be achieved as a result of a reduction of the internal field. The LED devices using the proposed structures including a metamorphic layer under the active region of the device are expected to increase their light output power by up to 10%. We also explored the impact of the non-linear piezo effect in nanowires and present a further theoretical computational study of single photon sources optimization in InGaN based wurtzite single quantum dots. We observed the light emission can be made by those single photon sources covering the entire visible spectrum through suitable change in the alloy composition.

III-nitride direct bandgap semiconductors have attracted significant research interest due to their outstanding potential for modern optoelectronic and electronic applications. However, the high cost of III-nitride devices, along with low performance due to dislocation defects, remains an obstacle to their further improvement. In this dissertation, I present a significant enhancement of III-nitride devices based on emerging materials. A promising substrate, (-201)-oriented β-Ga2O3 with unique properties that combine high transparency and conductivity, is used for the first time in the development of high-quality vertical III-nitride devices, which can be cost-effective for large-scale production. In addition, hybridizing GaN with emerging materials, mainly perovskite, is shown to extend the functionality of III-nitride applications. As a part of this investigation, high-performance and high-responsivity fast perovskite/GaN-based UV-visible broadband photodetectors were developed. State-of-the-art GaN epilayers grown on (-201)-oriented β-Ga2O3 using AlN and GaN buffer layers are discussed, and their high optical quality without using growth enhancement techniques is demonstrated. In particular, a low lattice mismatch (⁓4.7%) between GaN and the substrate results in a low density of dislocations ~4.8Å~107 cm−2. To demonstrates the effect of (-201)-oriented β-Ga2O3 substrate on the quality of III-nitride alloys, high-quality ternary alloy InxGa1−xN film is studied, followed by the growth of high quality InxGa1−xN/GaN single and multiple quantum wells (QWs). The optical characterization and carrier dynamics by photoluminescence (PL) and time-resolved PL measurements were subsequently performed. Lastly, to investigate the performance of a vertical emitting device based on InGaN/GaN multiple QWs grown on (-201)-oriented β-Ga2O3 substrate, high-efficiency vertical-injection emitting device is developed and extensively investigated. The conductive nature of the substrate developed as a part of this study yields better current and heat characteristics, while its transparency ensures high light extraction. The straightforward and direct growth process employed does not require a high-cost complex fabrication process. Finally, a broadband photodetector composed of the emerging CH3NH3PbI3 perovskite with the p-GaN, is developed. The findings reported in this dissertation demonstrate the superior performance of CH3NH3PbI3/GaN photodetectors produced by simple and cost-effective solution processed spray-coating method. In particular, it is demonstrated that perovskite/GaN device can work as a self-powered photodetector.

Group-III-nitrides have been intensively investigated for optoelectronics and power electronics and are uniquely suitable for energy-related applications, such as solar hydrogen generation and nanogenerators. Compared to planar group-III-nitrides, their nanostructures offer a high surface-to-volume ratio, increased light absorption cross-section, and improved carrier transportation behavior. This thesis focuses on molecular-beam-epitaxy-grown group-III-nitrides, specifically nanowires and membranes, and applications in renewable energy harvesting and conversion. A Mo2C-decorated (In,Ga)N nanowire-based photocathode was demonstrated for nitrogen fixation. The conventional Haber-Bosch method demands high reaction pressure and temperature while releasing a considerable amount of greenhouse gas. The proposed photoelectrocatalytic method can utilize solar energy to generate ammonia without carbon emissions. The proposed photocathodes can achieve maximum faradaic efficiency of 12 %, ammonia yield of 8.9 µg/h/cm2, and excellent stability for over 12 hrs. Moreover, group-III-nitrides were fabricated into a freestanding membrane through a novel method combining electrochemical porosification and controlled spalling. The novel method is reproducible and scalable, which can significantly reduce the consumption of sacrificial substrates compared to existing nitride membrane exfoliation techniques, thus promising a scalable platform. The as-fabricated GaN membranes were demonstrated for photoelectrocatalytic methylene blue degradation. Through laboratory tests and rooftop field tests, we proved the feasibility of our wafer-scale GaN membranes in achieving a dye degradation efficiency of 92%, a total organic carbon removal rate of 50.2%, and extraordinary stability for ~ 50 hours under solar illumination. The membrane can also degrade ~87% of MB under visible-light illumination. Furthermore, the (Al,Ga)N membranes were fabricated into flexible transparent piezoelectric devices. The devices can sense compression pressure and bending strain while giving a comparable compression sensitivity to other thin film piezotronics devices of ~ 2.41 mV/kPa and 42.36 pA/kPa, a maximum bending gauge factor of ~ 1271, and an output power density of ~ 5.38 nW/cm2. The sensors can withstand over 35000 cycles of operation and can be utilized for sensing and harvesting mechanical energies from human motions and environmental signals. This research utilized nanowires and membrane-based group-III-nitrides for different photoelectrocatalytic reactions and piezotronics devices, from material preparation and characterizations, and demonstrated practical devices for clean energy-related applications.

After the invention of the high-efficiency blue light-emitting diode (LED) at the end of the twentieth century, a new generation of light-emitting devices based on III-nitrides emerged, showcasing the capabilities of this semiconductor family. Despite the current limitations in the fabrication of III-nitrides, their optical and electronic properties still place them as some of the most promising semiconductors to continue the development of optoelectronic devices. To take full advantage of the versatility offered by these materials, the fabrication of novel III-nitride-based devices demands rigorous control of all of its stages. From the initial deposition of the materials, which involves controlling the composition and size of often complex heterostructures, up to the microfabrication processing used to create a final device, any deficiency occurring will negatively impact the performance of the device. Most of the time, these deficiencies reflect in microscopic defects, hindering their detection and identification of their origin. Without such knowledge, the deficiencies cannot be fixed, stalling the improvement of the device fabrication process and, consequently, its performance. This dissertation presents a variety of methodological approaches to characterize, from a microstructural point of view, different properties of novel III-nitride-based heterostructures and devices. The characterizations include studying the structure, interface, composition, and crystalline defects of different heterostructures and evaluating the microfabrication quality of microscopic LEDs. The results of the different characterizations contributed to developing novel LED and photocatalytic devices, for example, a single-quantum-well InGaN-based red LED with a high color purity, a monolithic phosphor-free white LED, microscopic green LEDs with a size smaller than 5×5 μm$^2$, and metal oxide/GaN-based photocatalysts with improved resilience to photocorrosion. The analyses and results presented in this dissertation strongly relied on the analytical capabilities offered by transmission electron microscopy, which proved to be a convenient and versatile tool for the characterization of many aspects related to the fabrication of III-nitride-based optoelectronic devices.

Les dispositifs intersousbandes à base de nitrures d’éléments III ont des propriétés très intéressantes pour l’optoélectronique et la photonique dans l’infrarouge. Les hétérostructures formées par l’AlN et le GaN ont une discontinuité de potentiel en bande de conduction de 1.75 eV et permettent donc de couvrir les deux extrémités du spectre électromagnétique infrarouge. Ces matériaux sont en outre caractérisés par des temps de relaxation ISB extrêmement courts et sont par conséquent des candidats potentiels pour le développement de composants optoélectroniques ultrarapides aux longueurs d’onde des télécommunications. D’autre part, grâce à l’énergie du phonon LO élevée dans ces matériaux, ces hétérostructures ouvrent la voie vers la réalisation de lasers à cascade quantique THz fonctionnant à la température ambiante. Dans ce contexte, je présente dans une première partie de ma thèse une étude théorique et expérimentale du transport électronique dans des hétérostructures GaN/Al(Ga)N simples comme les diodes tunnel résonnantes (DTRs) et plus complexes comme les multi-puits quantiques. La modélisation du transport quantique dans les DTRs AlGaN/GaN m’a permis de mettre en évidence la dépendance de résonance quantique du signe de la tension appliquée et de la composition des barrières. Du point de vue expérimental, je montre que le comportement électrique instable dans ces dispositifs est dû aux défauts dans le matériau. Dans les structures à multi-puits, je présente la première évidence expérimentale d’un transport tunnel résonnant reproductible. Dans une deuxième partie, je propose et développe plusieurs principes originaux de détecteurs à cascade quantique (QCD)s GaN/AlGaN entre 1 et 2 μm fonctionnant à la température ambiante. Je montre en utilisant des techniques de mesure de spectroscopie femtoseconde qu’ils sont intrinsèquement ultrarapides (picoseconde). Je développe aussi des micro-QCDs qui présentent une bande passante au-delà des 40 GHz. La conception des QCDs à plus grandes longueurs d’onde est discutée. Dans la dernière partie de ce manuscrit, je présente une étude spectroscopique dans le THz de superréseaux à base de GaN. Je montre que l’utilisation de puits quantiques à marche de potentiel permet d’accorder l’absorption ISB dans le THz. Je présente ensuite la première démonstration de l’électroluminescence intersousbande de 2 à 9 THz. / Intersubband devices based on III-nitrides have interesting properties for optoelectronics and photonics applications in the infrared. The heterostructures of these materials have a large conduction band offset of 1.75 eV and therefore allow covering the whole infrared electromagnetic spectral range. Furthermore, these materials are characterized by extremely short ISB relaxation times and are, consequently, potential candidates for the development of ultrafast optoelectronic devices at the fiber optics telecommunication wavelengths for fiber optics or for free space communication. On the other hand, thanks to the large LO phonon energy in these materials, these heterostructures offer the possibility of fabricating compact THz lasers operating at room temperature. In this context, I firstly present in this manuscript a theoretical and an experimental study of the electronic transport in simple AlGaN/GaN heterostructures namely resonant tunneling diodes and more complex structures such as multi-quantum wells based on III-nitrides. The modeling of the transport in RTDs shows the dependency of the current resonances on the sign of the applied voltage as well as the height of the double barrier. I also demonstrate that the experimentally observed electrical instabilities in these devices are due to the defects in the material. In the multiple quantum well structures, I give the first evidence of reproducible resonant tunneling transport. In chapter 3, I propose and develop several principles of quantum cascade detectors in the near infrared between 1 and 2 μm operating at room temperature. I demonstrate, using time-resolved bias-lead monitoring technique, that they are intrinsically very fast (picosecond). I also develop micro - QCD devices that have a -3 dB cut-off frequency beyond 40 GHz. The design of QCDs operating at longer wavelengths is discussed. In the last part of the manuscript, I present a spectroscopic study of GaN superlattices with ISB transitions in the far-infrared. I show that the utilization of step quantum wells allows to tune the ISB absorption frequency to the THz. I finally present the first demonstration of the intersubband electroluminescence from 2 to 9 THz in these structures.

abstract: The work contained in this dissertation is focused on the optical properties of direct band gap semiconductors which crystallize in a wurtzite structure: more specifically, the III-nitrides and ZnO. By using cathodoluminescence spectroscopy, many of their properties have been investigated, including band gaps, defect energy levels, carrier lifetimes, strain states, exciton binding energies, and effects of electron irradiation on luminescence. Part of this work is focused on p-type Mg-doped GaN and InGaN. These materials are extremely important for the fabrication of visible light emitting diodes and diode lasers and their complex nature is currently not entirely understood. The luminescence of Mg-doped GaN films has been correlated with electrical and structural measurements in order to understand the behavior of hydrogen in the material. Deeply-bound excitons emitting near 3.37 and 3.42 eV are observed in films with a significant hydrogen concentration during cathodoluminescence at liquid helium temperatures. These radiative transitions are unstable during electron irradiation. Our observations suggest a hydrogen-related nature, as opposed to a previous assignment of stacking fault luminescence. The intensity of the 3.37 eV transition can be correlated with the electrical activation of the Mg acceptors. Next, the acceptor energy level of Mg in InGaN is shown to decrease significantly with an increase in the indium composition. This also corresponds to a decrease in the resistivity of these films. In addition, the hole concentration in multiple quantum well light emitting diode structures is much more uniform in the active region when Mg-doped InGaN (instead of Mg-doped GaN) is used. These results will help improve the efficiency of light emitting diodes, especially in the green/yellow color range. Also, the improved hole transport may prove to be important for the development of photovoltaic devices. Cathodoluminescence studies have also been performed on nanoindented ZnO crystals. Bulk, single crystal ZnO was indented using a sub-micron spherical diamond tip on various surface orientations. The resistance to deformation (the "hardness") of each surface orientation was measured, with the c-plane being the most resistive. This is due to the orientation of the easy glide planes, the c-planes, being positioned perpendicularly to the applied load. The a-plane oriented crystal is the least resistive to deformation. Cathodoluminescence imaging allows for the correlation of the luminescence with the regions located near the indentation. Sub-nanometer shifts in the band edge emission have been assigned to residual strain the crystals. The a- and m-plane oriented crystals show two-fold symmetry with regions of compressive and tensile strain located parallel and perpendicular to the ±c-directions, respectively. The c-plane oriented crystal shows six-fold symmetry with regions of tensile strain extending along the six equivalent a-directions. / Dissertation/Thesis / Ph.D. Physics 2013

Group III-nitride materials have attracted great attention for applications in high efficiency electronic and optoelectronics devices such as high electron mobility transistors, light emitting diodes, and laser diodes. On the other hand, group VI transition metal dichalcogenides (TMDs) in the form of MX2 has recently emerged as a novel atomic layered material system with excellent thermoelectric, electronic and optoelectronic properties. Also, the recent investigations reveal that the dissimilar heterojunctions formed by TMDs and III-nitrides provide the route for novel devices in the area of optoelectronic, electronics, and water splitting applications. In addition, integration of III-nitrides and TMDs will enable high density integrated optoelectronic circuits and the development of hybrid integration technologies. In this work, we have demonstrated kinetically controlled growth processes in plasma assisted molecular beam epitaxy (PAMBE) for the III-nitrides and their engineered heterostructures. Techniques such as Ga irradiation and nitrogen plasma exposure has been utilized to implement bulk GaN, InGaN and their heterostructures in PAMBE. For the growth of III-nitride based heterostructures, the in-situ surface stoichiometry monitoring (i-SSM) technique was developed and used for implementing stepped and compositionally graded InGaN-based multiple quantum wells (MQWs). Their optical and microstrain analysis in conjunction with theoretical studies confirmed improvement in the radiative recombination rate of the graded-MQWs as compared to that of stepped-MQWs, owing to the reduced strain in graded-MQWs. Our achievement also includes the realization of the p-type MoS2 by engineering pristine MoS2 layers in PAMBE. Mainly, Ga and nitrogen plasma irradiation on the pristine MoS2 in PAMBE has resulted in the realization of the p-type MoS2. Also, GaN epitaxial thin layers were deposited on MoS2/c-sapphire, WSe2/c-sapphire substrates by PAMBE to study the band discontinuity at GaN/TMDs heterointerface. The determination of band offset parameters for both GaN/MoS2 and GaN/WSe2 heterostructures revealed realization of type-II band alignment. Also, heterojunctions such as AlGaN/MoS2 is implemented to achieve type-I heterojunction. This work may open up a new avenue towards photonic quantum devices based on the integration of III-nitrides with 2D TMDs.

No description available.

Doctor of Philosophy / Department of Physics / Jingyu Lin / III-nitride nanostructures and devices were synthesized by metal organic chemical vapor deposition (MOCVD) for their applications in various photonic, optoelectronic, and energy devices such as deep ultraviolet (DUV) photodetectors, solar cells, visible emitters, thermometric (TE) power generators, etc. Structural and optical properties in thicker AlN epilayers were found to be better than those in thinner AlN epilayers. Full-width at half maxima (FWHM) of x-ray diffraction (XRD) rocking curves as small as 63 and 437 arcsec were measured at (002) and (102) reflections, respectively in a thick AlN epilayer (4 m). The dark current of the fabricated AlN detectors decreases drastically as AlN epilayer thickness increases. DUV photoluminescence (PL) spectroscopy and x-ray diffraction (XRD) measurements were employed to study the effect of biaxial stress in AlN epilayers grown on different substrates. Stress-induced band gap shift of 45 meV/GPa was obtained in AlN epilayers. The potential of InGaN alloys as TE materials for thermopower generation has been investigated. It was found that as In content increases, thermal conductivity decreases and power factor increases, which leads to an increase in the TE figure of merit (ZT). The value of ZT was found to be 0.08 at 300 K and reached 0.23 at 450 K for In0.36Ga0.64N alloy, which is comparable to that of SiGe based alloys. Single phase InxGa1−xN alloys inside the theoretically predicted miscibility gap region (x = 0.4 to 0.7) were successfully synthesized. A single peak of XRD -2 scans of the (002) plane in InGaN alloys confirms that there is no phase separation. Electrical properties and surface morphologies were found to be reasonably good. It was found that growth rate should be high enough (>400 nm/hr) to achieve high quality and single phase InxGa1−xN alloys in this miscibility gap region. Mg-doped InxGa1-xN alloys were synthesized and characterized by Hall-effect and PL measurements for their application as visible emitters. P-type conductivity was measured up to x = 0.35 with accepter activation energy as low as 43 meV, which is about 4 times lower than that of Mg-doped p-type GaN. Resistivity as low as 0.4 -cm with a free hole concentration as high as 5x1018 cm-3 was measured in Mg-doped In0.22Ga0.78N. PL intensity decreased ~3 orders in magnitude when x increased from 0 to 0.22 in Mg-doped InxGa1-xN alloys.