The development of gallium nitride (GaN) light emitting devices has reached extraordinary echelons. As such, the characterization and analysis of the behavior of GaN materials is essential to the advancement of GaN technology. In this thesis, the effect of temperature on the optical and electrical properties of p-type GaN is investigated. The GaN samples used in this work were grown by various methods and studied by Kelvin probe and photoluminescence (PL) techniques. Specifically, the surface photovoltage (SPV) behavior and PL data were analyzed at different temperatures and illumination intensities. Using the SPV results, we show that p-type GaN exhibits n-type conductivity at low temperatures (80 K). If the sample is heated beyond a characteristic temperature, TC, the conductivity reverts to p-type. This temperature of conversion can be tuned by varying the illumination intensity. We explain this conductivity conversion using a simple, one-acceptor phenomenological model. Temperature-dependent PL measurements taken on Mg-doped p-type GaN layers show abrupt and tunable thermal quenching of the PL intensity. This effect is explained by a more complex model but with the same assertions, that the system must undergo a change in conductivity at low temperatures and under UV illumination. It is necessary to understand the observed behaviors, since the implications of such could have an effect on the performance of devices containing p-type GaN materials.

There is an understanding of surface photovoltage (SPV) behavior for GaN, yet little is known about the SPV behavior for AlGaN. In this work, a Kelvin probe was used to measure the SPV for p-type AlGaN. Very slow SPV transients were found in AlGaN, which could not be explained with a simple thermionic model. A possible explanation of this behavior is the segregation of impurities to the surface, which causes significant reduction of the depletion region width (down to 2 nm), with carrier tunneling and hopping becoming the dominant mechanisms responsible for the SPV transients. To verify this assumption, the near-surface defective region (about 40 nm) has been removed through the ICP-RIE process. After the etching, the SPV transients became fast and increased in magnitude by about 0.6 eV. By using the thermionic model, band bending was estimated to be -1 eV.

Steady-state and transient surface photovoltages in undoped GaN are studied in various environments (air, nitrogen, oxygen, vacuum) at room temperature and 400 K with a Kelvin probe attached to an optical cryostat. The results are explained within a phenomenological model accounting for the accumulation of photo-generated holes at the surface, capture of free electrons from the bulk over the near-surface potential barrier, and emission of electrons from surface states into the bulk. Mechanisms of surface photovoltage are discussed in detail. Photoadsorption and photodesorption of negatively charged species will either increase or decrease the surface potential and thus band bending. Oxygen is the assumed species responsible for the SPV changes in air ambient during continuous UV illumination. This variation in SPV will be confirmed with photoluminescence measurements.

In this work Scanning Kelvin Probe Microscopy (SKPM) was used to characterize surface states and device surface charging in nitride materials. Samples grown by Molecular Beam Epitaxy (MBE), Metal Organic Chemical Vapor Deposition (MOCVD) and Hydride Vapor Phase Epitaxy (HVPE) typically show a high surface band bending of about 1 eV. In an n-type sample with 3X1017 cm-3 carrier concentration, 1 eV upward band bending corresponds to 1.7X1012 cm-2 trapped charge density in the surface states. Under continuous ultraviolet (UV) illumination up to 0.6 eV surface photo voltage effect could be observed in some samples, which further indicates that surface band bending is very likely larger than 0.6 eV, i.e. close to 1 eV. Reactive Ion Etching (RIE)damage was observed to increase surface band bending by about 0.4 eV where as surface treatments in organic solvents and inorganic acids did not affect surface band bending significantly. These results indicate presence of high density of surface states in devices fabricated in nitride materials. Surface potential measurements immediately after turning off a reverse bias to the Schottky contact of a GaN Schottky diode as well as an AlGaN/GaN Hetero-junction Field Effect Transistor (HFET) show an increase of band bending near the Schottky contact edge. For an applied reverse bias of 4 V, about 0.5 eV increase of band bending was observed. This increase of band bending was caused by tunneling of electrons from the Schottky contact and their subsequent capture by surface states near the contact edge. In case of the HFET, the increase of band bending for a bias that caused no current flow through the device was similar to a bias that did. This showed that hot electron injection from the channel did not play a significant role in increasing surface band bending. The accumulated charge near the gate edge of a HFET can deplete the channel, which would cause the drain current to decrease. The total times of accumulation and dissipation of excess surface charge near the gate edge of the HFET were comparable to the time scales of drain current transients of current collapse and recovery. From this observation we attributed current collapse phenomena to charge accumulation near the edge of the reverse biased gate contact of a HFET.

Semiconductor-based gas sensors have been used for a wide range of applications over the last few decades. In this thesis, sensing properties of pure ZnO and Ga doped ZnO are investigated. There are three types of tested gas species, H2, O2 and NO, and three test temperatures, 300oC, 400oC and 500oC. After measurements of response to exposure to H2 and O2, it is concluded that Ga doped ZnO and ZnO are both n-type metal oxides. In measurements of NO, two test conditions were considered, the case with background O2 (10%) in the gas flow and the case without background O2. NO can be oxidized to NO2 or reduced to N2 and O2. The resistance of Ga doped ZnO and ZnO sensors always decreases for all exposures to NO except for the case in which the Ga doped ZnO sensor was exposed to NO in a background of O2 at 500 oC. In this special case, the resistance of Ga doped ZnO actually increases during exposure to low concentrations of NO (< 30 ppm). It is not clear whether the change in response direction is due to an n-p transition or different reactions between gas molecules and Ga doped ZnO. Work function measurements were therefore conducted to understand more about the electron transfer during gas exposure. The work function measurements suggest that there are probably several stages of interactions between gas molecules and Ga doped ZnO during each gas pulse exposure.

Atomic Force Microscopy (AFM) and Kelvin Probe Microscopy (KPM) are two surface characterization methods suitable for semiconductor nanocrystal applications. In this thesis work, an AFM system with KPM capability was developed and implemented. It was observed that, the effect of electrostatic interaction of the probe cantilever with the sample can be significantly reduced by using higher order resonant modes for Kelvin force detection. Germanium nanocrystals were grown on silicon substrate using different growth conditions. Both characterization methods were applied to the nanocrystal samples. Variation of nanocrystal sizes with varying annealing temperature were observed. Kelvin spectroscopy measurements made on nanocrystal samples using the KPM apparatus displayed charging effects.

There is a large number of measurement techniques that is used for a surface inspection and a characterization of different types of materials. One of these techniques is a contact potential difference (CPD) scanning technique. In this project a non-vibrating contact potential difference (nvCPD) method is utilized to measure a work function and a topographical structure of a sample surface. A sample is mounted on a spindle that rotates at high speed. A nvCPD sensor detects work-function variations during movement above the sample surface. There are certain factors that create difficulties during the measurement process. A nonplanar sample surface, the spindle wobble and an incline of a mounted sample impede the safe (without impacting the surface) scanning at a close distance. The goal of this thesis was to implement a height sensor as a feedback device to dynamically control and adjust a CPD sensor flying height. Since a CPD signal is inversely proportional to the flying height, minimization of this height will enhance the signal magnitude, the signal-to-noise ratio and the resolution of measurements.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23897号 / 工博第4984号 / 新制||工||1778(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 山田 啓文, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Dans un contexte normatif toujours plus sévère concernant les rejets automobiles polluants, la substitution des aciers par des alliages d’aluminium dans les structures des véhicules est en plein essor. Ce projet de thèse, qui s’inscrit dans un programme de développement de la société Constellium, cible plus précisément les alliages d’aluminium de la série 7xxx (Al-Zn-Mg) qui, malgré leurs propriétés mécaniques élevées, peuvent présenter une sensibilité à la corrosion sous contrainte (CSC) liée au phénomène de fragilisation par l’hydrogène (FPH). La compréhension des mécanismes mis en jeu dans ce type d’endommagement constitue donc une première étape vers une optimisation métallurgique en vue d’une industrialisation future de ces alliages dans le secteur automobile. La première partie de ces travaux est consacrée à l’étude de l’influence de l’état métallurgique de l’alliage 7046 sur son comportement en CSC et à l’identification des mécanismes de dégradation. Un lien direct a pu être mis en évidence entre l’abattement des propriétés mécaniques et les modes de rupture actifs et la quantité d’hydrogène dans l’alliage. Les deux modes d’endommagement observés, intergranulaire-fragile et transgranulaire-fragile, ont respectivement été attribués à un enrichissement en hydrogène aux joints de grains et au piégeage de l’hydrogène au niveau des précipités intragranulaires. Les interactions entre l’hydrogène et les précipités fins d’une part et les dislocations d’autre part, identifiés comme deux hétérogénéités microstructurales critiques vis-à-vis de la FPH, ont été étudiées à une échelle plus locale dans la seconde partie du travail de thèse. Les essais ont été réalisés sur des échantillons modèles, chargés en hydrogène en milieu H2SO4 sous polarisation cathodique et la profondeur de pénétration de l’hydrogène a été évaluée par SKPFM (Scanning Kelvin Probe Force Microscopy). L’ensemble des résultats obtenus met en évidence : 1/ un effet « barrière » des précipités fins et des dislocations sur la diffusion de l’hydrogène en relation avec un abattement des propriétés mécaniques moins important, 2/ un transport possible de l’hydrogène par les dislocations et 3/ l’efficacité du SKPFM pour déterminer précisément des coefficients de diffusion apparents de l’hydrogène. Ces résultats ouvrent ainsi de nouvelles pistes vers la compréhension des mécanismes de CSC dans les alliages Al-Zn-Mg. / Automotive industry is increasingly affected by standards requiring a major cut of polluting emissions, leading R&D policies to focus on replacing steel by aluminum alloys. This thesis project, initiated by the manufacturer Constellium, focuses on 7xxx (Al-Zn-Mg) aluminum alloys known to have high mechanical properties but also to be susceptible to stress corrosion cracking (SCC) partly attributed to hydrogen embrittlement (HE). Understanding the mechanisms involved would be a first step towards a metallurgical optimization and a future industrialization of these alloys. The first part focuses on the SCC behavior of the 7046 aluminum alloy, related to its microstructure, and the identification of degradation mechanisms involved. A hydrogen amount – loss of mechanical properties relationship was highlighted. The damage observed was explained by the presence of hydrogen in the grain boundaries and by a trapping effect of the intragranular hardening precipitates, limiting the hydrogen diffusion to the grain boundaries. Interactions between hydrogen and hardening precipitates and dislocations, both identified as critical microstructural heterogeneities for HE, are studied at a local scale in a second part. The hydrogen effect was characterized by penetration depth measurements made by SKPFM (Scanning Kelvin Probe Force Microscopy) on “model” samples cathodically charged in H2SO4. The whole results finally highlight: 1/ a “shielding” effect of fine precipitates and dislocations on hydrogen diffusivity related to a lower susceptibility to HE, 2/ hydrogen transport by dislocations and 3/ the efficiency of SKPFM to precisely measure effective diffusion coefficients of hydrogen. These results lead to new opportunities to understand SCC mechanisms in Al-Zn-Mg alloys.