III-nitride nanowires (NWs) have been recognized as efficient photoelectrochemical (PEC) devices due to their large surface-to-volume ratio, tunable bandgap, and chemical stability. Doping engineering can help to enhance the PEC performance further. Therefore, addressing the effects of Si and Mg doping on the III-nitride NW photoelectrodes is of great interest. In this study, doping levels of NWs were tuned by the dopant effusion cell temperature of the molecular beam epitaxy (MBE) growth. The successful doping of the III-nitride NWs was confirmed using photoluminescence (PL), Raman spectroscopy, and open circuit potential (OCP) measurements. The ionized dopant concentrations of Si-doped InGaN/GaN NWs were systematically quantified by electrochemical impedance studies (EIS). Due to the three dimensional surfaces of NWs, modified Mott-Schottky formulas were induced to improve the accuracy of ionized dopant concentrations. The highest dopant concentration of Si-doped InGaN NWs can reach 2.1x1018 cm-3 at Tsi = 1120 oC. Accordingly, the estimated band edge potentials of the tested NWs straddled the redox potential of water splitting. The PEC performance of these devices was investigated by linear scan voltammetry (LSV), chronoamperometry tests, and gas evolution measurements. The results were consistent with the quantified dopant concentrations. The current density of n-InGaN NWs doped at TSi = 1120 oC was nine times higher than the undoped NWs. Additionally, the doped NWs exhibited stoichiometric hydrogen and oxygen evolution. By doping Mg into InGaN and GaN segments separately, the p-InGaN/p-GaN NWs demonstrated improved PEC performance, compared with undoped-InGaN/p-GaN and n-InGaN/n-GaN NWs. The p-InGaN/p-GaN NWs exhibited a highly stable current density at ~-9.4 mA/cm2 for over ten hours with steady gas evolution rates (~107 μmol/cm2/hr for H2) at near a stoichiometric ratio (H2: O2~ 1.8:1). This study demonstrated that optimizing the doping level and appropriate band engineering of III-nitride NWs is crucial for enhancing their PEC water splitting performance.

For more than seventy years, semiconductor devices have functioned as the cornerstone for technological advancement, and as the defining transition into the information age. The III-Nitride family of semiconductors, in particular, underwent an impressive maturation over the past thirty years, which allowed for efficient light- emitting devices, photo-detectors, and power electronic devices. As researchers try to push the limits of semiconductor devices, and in particular, as they aim to design ultraviolet light emitters and high threshold power devices, the search for new materials with high band gaps, high breakdown voltages, unique optical properties, and variable lattice parameters is becoming a priority. Two interesting candidates that can help in achieving the aforementioned goals are the wurtzite BAlN and BGaN alloy systems, which are currently understudied due to difficulties associated with their growth in epitaxial settings. In our research, we will investigate the band alignment between BAlN and BGaN alloys, and other wurtzite III-Nitride semiconductors from first principle simulations. Through an understanding of band alignment types and a quantification of the band offset values, researchers will be able to foresee the applicability of a particular interface. As an example, a type-I band alignment with a high conduction band offset and a low valence band offset is a potential electron blocking layer to be implemented in standard LED designs. This first principle investigation will be aided by simulations using Density Functional Theory (DFT) as implemented in the Vienna Ab Initio Simulation Package (VASP) environment. In addition, we will detail an experiment from the literature that uses X- ray Photoelectron Spectroscopy on multiple samples to infer and quantify the band alignment between different materials of interest to us. We aim in this study to anticipate the band alignment in interfaces involving materials at the cutting edge of research. Our hope is to set a theoretical ground for future experimental studies on this same matter in parallel to the current efforts to improve the quality and stability of wurtzite BAlN and BGaN alloy crystals.

A strong argument can be made that physics is, at its core, the study of symmetries. Nonlinear optics is certainly no exception, with an enormous number of distinct processes each depending in its own way on the underlying symmetries of the physical system, the light, or of nature itself. Restricting ourselves to optical harmonic generation, we will explore three unique physical systems as well as three symmetries. In each case, the controlled breaking of that symmetry will lead to optical enhancements, novel nonlinearities, or deep physical insights. Beginning with silicon metasurfaces, we will explore the effects of even and odd spatial symmetries in optical systems. The periodic breaking of this symmetry will lead us to the highly engineerable physics of bound states in the continuum. By studying the harmonic emission from an atomic gas in the volume surrounding the metasurface, we will come to understand that significant nonlinear optical enhancements can be engineered with any linewidth and at any wavelength. In the context of the two-dimensional material hexagonal boron nitride, we will investigate and break crystal inversion symmetries. Using an intense laser tuned to the phonon resonance of hexagonal boron nitride, large amplitude anharmonic ionic motions will provide us a powerful degree of control over the internal symmetries of the system at an atomic level. Breaking this symmetry, we measure short-lived even-order nonlinearities that would otherwise be forbidden in equilibrium. Our observations for second- and third- harmonic generation are confirmed by time-dependent density functional theory. Those simulations further extend the understanding of this symmetry-breaking effect to even higher order processes. Lastly, single-crystal graphene and graphite provide an ideal platform through which to explore time-reversal symmetry. Chiral photons, or optical beams with ellipticity and handedness, are well known to break time-reversal symmetry. While applying high-power, chiral light to graphene, the breaking of time-reversal lifts a degeneracy of the K and K’ valleys in the momentum space Brillouin zone. Lifting this degeneracy, we unveil underlying spatial symmetry properties of graphene in odd-order third- and fifth- harmonic generation which should otherwise be unobservable. We also show experimentally, for the first time, that valley polarization and population can be extracted using our technique.

No description available.

Silicon nitride thin films are of interest in the biomedical engineering field due to their biocompatibility and favorable tribological properties. Evaluation and understanding of the properties of these films under diverse loading and failure conditions is a necessary prerequisite to their use in biomedical devices. Three wafers of silicon nitride-coated silicon were obtained from Lawrence Livermore National Laboratory and used to create 96 samples. Samples were subjected to nanoindentation testing to evaluate the mechanical properties of the film. Samples were subjected to nanoimpact testing to compare the damage resistance of the film to separate nanoimpact types. Samples were subjected to nanoscratch testing to evaluate the consistency of the critical load of the film. Results showed that there were no significant differences in the mechanical properties of the film across the tested groups. There was a significant difference observed in the rate of damage to the film between pendulum oscillation nanoimpact testing and sample oscillation nanoimpact testing, with the former causing more damage with all experiment variables controlled for. Results showed that the critical load measure for the film was significantly different between different nanoscratch test parameters. The conclusions from this study will support future work for in vitro and in vivo testing of ceramic thin films for biomedical applications.

Presented thesis is focused on the study of properties of Ga and GaN nanostructures on graphene. In the theoretical part of the thesis a problematics of graphene and GaN fabrication is discussed with a focus on the relation of Ga and GaN to graphene. The experimental part of the thesis deals with the depositions of Ga on transferred CVD-graphene on SiO2. The samples are analyzed by various methods (XPS, AFM, SEM, Raman spectroscopy, EDX). The properties of Ga on graphene are discussed with a focus on the surface enhanced Raman scattering effect. Furthermore, a deposition of Ga on exfoliated graphene and on graphene on a copper foil is described. GaN is fabricated by nitridation of the Ga structures on graphene. This process is illustrated by the XPS measurements of a distinct Ga peak and the graphene valence band during the process of nitridation.

<p>QC 20150603</p>

Hexagonal molybdenum nitride (δ-MoN) is one of the hardest superconductors, and its superconducting properties depend on the crystalline structure and the substrate of use. Herein, a versatile growth method has been utilized to grow single-crystalline (SC) δ-MoN thin films on any arbitrary substrate of interest. SC δ-MoN films have been achieved on amorphous substrates via the transfer of MoS2 precursors followed by chemical phase conversion. The transferred SC δ-MoN film on an amorphous SiO2/Si substrate exhibits superconductivity at Tc = 4.75 with an upper critical field Hc2(0) = 8.24 K. The effect of the transfer process was assessed by directly growing SC δ-MoN on an Al2O3 substrate, which showed enhanced superconductivity properties due to the nonuniformity in film thickness that the transfer process induces. The crystalline structure effect on superconductivity was studied by directly growing amorphous δ-MoN film on an amorphous SiO2/Si substrate. The amorphous film showed degraded superconducting behavior and confirmed that disorders in the crystal structure suppress superconductivity. The upper critical fields of the non-transferred δ-MoN films exceeded their Pauli paramagnetic limits, which could give rise to the existence of the Ising pairing effect, but further studies are needed to confirm this behavior.

High electron mobility transistors (HEMTs) have long been studied for high frequency and high-power application. Among widely known high electron mobility transistors, AlGaN/GaN HEMTs are having the upper hand due to high electron mobility of the GaN channel. Over the times, issues like current collapse, gate leakage, self-heating and gate lag have questioned the performance and reliability of these devices. In the recent years, engineers have come up with newer architectures to address some of these issues. Inserting a high-k dielectric oxide layer in the gate stack proved to be an effective solution to mitigate gate leakage, reduce interfacial traps and improve optimal working conditions. This work aims to study the reliability aspect of these so-called metal-oxide-semiconductor high electron mobility transistors (MOS-HEMT) specifically, HfO2 and HfZrO2 MOS-HEMTs. It was found through numerical simulations that though HfO2 and HfZrO2 dielectrics were able to mitigate gate leakage current, they tend to accumulate more heat in the channel region with respect to the conventional silicon nitride (SiN) passivated counterparts. Moreover, few asymmetric structures were proposed where silicon nitride was placed in the dielectric layer along with HfO2/HfZrO2. In this study it was found that these asymmetric structures showed superior thermal performance while showing near-zero gate leakage current.

Photocatalytic solar fuel generation is the most green, sustainable and viable approach to deal with both the ever-growing energy crisis and environmental issues, simultaneously. The work presented in this thesis is focused on the development of new organic carbonaceous semiconductors, typically, carbon quantum dots (CQDs) and graphitic carbon nitride (g-C3N4), and porphyrin small molecules and their hybrids with graphitic carbon nitride, meanwhile, their application in the field of photocatalytic solar fuel generation. In the chapter 1, a general review about background and mechanism of photocatalytic solar fuel generation are introduced first. Next, the features and developments of porphyrin and graphitic carbon nitride for the photocatalytic redox reaction are discussed. In chapter 2, the synthesis, characterization methods and photocatalytic experiment in details are described. In chapter 3, gram-scale CQDs are facilely synthesized by simple thermal treatment of citric acid monohydrate, and microporous 1D nanorods of g-C3N4 are prepared through template-free chemical approach. The photocatalytic properties of 1D protonated g-C3N4 (HCN) modified with different amount of CQDs were evaluated by the rate of H2- evolution under visible light irritation. The results demonstrate that g-C3N4/CQDs with the optimal CQDs amount of 0.25 wt.% afford the highest H2-production rate of 382 μmol h-1 g-1 with apparent quantum yield (AQY) of 1.9% which was about 3-fold of pure g- C3N4. The composite g-C3N4/CQDs show a remarkable stability against the photocorrosion within a continuous experiment period over 12h. The enhanced photocatalytic H2-production activity could be attribute to the intimate interface between CQDs and g-C3N4, which not only significantly improves the visible-light absorption, but also prolongs the lifetime of charge carriers and suppresses the recombination of photogenerated electron-hole pairs. This work showed that low-cost and metal-free CQDs could be an efficient photosensitizer to promote photocatalytic hydrogen generation. In chapter 4, we reported a new array of push-pull isomeric naphthalimide- porphyrins (ZnT(p-NI)PP) to investigate the effect of naphthalimide and molecular constitution on light driven hydrogen evolution from water splitting. These compounds were synthesized by integration of four naphthalimide moieties on meso-substituion of porphyrin macrocycle through para phenyl linker. Porphyrins were characterized by UV- Vis, Fluorescence and DFT calculations and compared with those of zinc tertapheylporphyrin (ZnTPP). When these porphyrins were employed as photocatalyst for the photocatalytic hydrogen production (PHP) with platinum co-catalyst, they delivered high hydrogen efficiency compared to that of ZnTPP. Particularly, ZnT(p-NI)PP exhibited 203 times higher hydrogen efficiency than the ZnTPP. This could be ascribed to the efficient exciton dissociation into holes and electrons at the photoexcited state of ZnT(p-NI)PP and then electrons were transferred to the proton through platinum. These results indicate that introduction of naphthalimide at meso-position of porphyrin through para phenyl linker is a versatile strategy to improve the photocatalytic hydrogen evolution of porphyrin based materials. In addition, the other two isomeric naphthalimide conjugated porphyrins through meta-and ortho-phenyl linker, ZnT(m-NI)PP and ZnT(o-NI)PP are also developed for photocatalytic H2 production. The para-linked isomer, ZnT(p-NI)PP delivered a much higher H2 production rate of 973 μmol h−1g -1 compared to that of ZnT(m-NI)PP (597 μmol h−1g −1) and ZnT(o-NI)PP (54 μmol h−1g −1), respectively. This could be attributed to the efficient intramolecular energy transfer from the naphthalimide to the porphyrin ring. In chapter 5, a series of NP/g-C3N4 hybrids of graphitic carbon nitride (g-C3N4) with naphthalimide-porphyrin (ZnT(p-NI)PP, labelled as NP) have been developed for photocatalytic hydrogen production. Planar naphthalimide-porphyrins are adsorbed onto flexible two-dimensional g-C3N4 through π-π stacking, which are characterized by scanning electronic microscopy and X-ray photoelectron spectroscopy. Except for its function as photosensitizer, NP in the hybrids could efficient inhibit the charge recombination by electron transfer for the lower lowest unoccupied molecular orbital of NP than g-C3N4, whereas facilitate energy transfer from g-C3N4 donor to NP acceptor for efficient overlap of emission spectrum of NP and absorption of g-C3N4. As a result, the hybrid containing weigh ratio of 2% NP (2%NP/g-C3N4) exhibits an enhanced photocatalytic hydrogen production rate (HPR) of 2297 μmol g−1 h −1, while pristine g- C3N4 shows a HPR of 698 μmol g−1 h −1. The 2%NP/g-C3N4 shows the best performance when compared with the reported hybrids of g-C3N4 with Zn(II) -tetrakis(4- carboxylphenyl) porphyrin (ZnTCPP/g-C3N4) and Zn(II)-tetrakis(4- hydroxyphenyl)porphyrin (ZnTHPP/g-C3N4) in photocatalytic hydrogen production under the same conditions. In the chapter 6, the future work on photocatalytic CO2 reduction, perspectives and conclusions are included