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Le travail de la thèse s’articule sur le développement d’un nouveau type de capteurs de gaz à base des matériaux semi-conducteurs III-Nitrure (Les nitrures de gallium). Ces matériaux présentent de nombreux avantages qui pourraient être utilisées pour concevoir des capteurs NOx sensibles et sélectifs pour le contrôle des pollutions émises par la ligne d’échappement Diesel. Afin de limiter et déduire les gaz polluants émis par les moteurs à explosion en générale et les moteurs Diesel en particuliers (NO, NO2, NH3, CO, …), différentes normes européennes ont été établies. Pour respecter ces normes, plusieurs modifications sur les moteurs et les lignes d’échappement des véhicules ont été effectuées (filtres à particules, catalyseurs, capteurs NOx, …). Les capteurs NOx utilisés actuellement sont à base d’électrolyte solide. Ils sont basés dans leur fonctionnement sur la mesure de la concentration d’oxygène présente dans le gaz d’échappement qui permet de son tour l’estimation de la concentration totale des gaz NOx (mesure indirecte). Ces capteurs ne détectent pas le NH3 à la sortie de la ligne d’échappement, et ne donnent pas une information précise sur le rapport entre NO et NO2 (manque de sélectivité) qui est un facteur important pour le bon fonctionnement de catalyseur sélectif SCR (amélioration de rendement) ; d’où la nécessité d’un capteur de gaz plus performant et en particulier sélectif afin d’améliorer les systèmes de contrôle, de post-traitement et de diagnostic. Notre approche consiste à utiliser un transistor HEMT (High Electron Mobility Transistor) à gaz bidimensionnel d’électrons à base de nitrure de Gallium avec l’association d’une couche fonctionnelle à la place de la grille. L’interaction des molécules de gaz avec cette couche fonctionnelle donne une signature (variation de signal de sortie) spécifique pour chaque type de gaz qui aide à l’amélioration de la sélectivité. Le projet contient deux parties : l’optimisation de la structure choisie et l’optimisation de la couche fonctionnelle afin d’obtenir une détection sélective entre les différents gaz polluants. Cette technologie est intéressante pour développer des capteurs de gaz grâce aux possibilités de détecter des faibles variations de tensions et aux possibilités de fonctionnement dans des environnements sévères. La thèse de doctorat s’inscrit dans le cadre de l’OpenLab materials and processes en collaboration entre le laboratoire Georgia-Tech lorraine et l’entreprise Peugeot-Citroën PSA / The work of the thesis focuses on the development of a new type of gas sensors based III-Nitride semiconductor materials (gallium nitrides). These materials have many advantages that could be used to develop sensitive and selective NOx sensors for the control of pollution emitted by diesel exhaust line. To limit the polluting gases emitted by internal combustion engines in general and diesel in particular (NO, NO2, NH3, CO, ...), different European standards have been established. To meet these standards, anti-pollution systems (consisting of particle filters, catalysts, NOx sensors, ... etc) are used. NOx sensors currently used in automobiles are based on a solid electrolyte. Their operation is based on the measurement of the oxygen concentration. This enables an estimate of the total concentration of NOx gas (indirect measurement) after filtering NOx from O2 and decomposing NOx into O2. These sensors do not detect NH3 at the outlet of the exhaust line, and do not give accurate information on the relationship between NO and NO2 (lack of selectivity) which is important factor for an optimal functioning of selective catalyst (SCR performance improvement). Hence there exists a need for a more efficient and selective in particular gas sensor to improve the control systems, post-treatment and diagnosis. Our approach is to use a HEMT (High Electron Mobility Transistor) transistor based on gallium nitride with a combination of a functional layer instead of the gate. The interaction of the gas molecules with the functional layer gives a signature (output signal variation) specific for each type of gas that helps to improve the selectivity. The project contains two parts: the optimization of the chosen structure and the optimization of the functional layer in order to achieve selective detection between various gaseous pollutants. This technology is interesting for development of gas sensors through the possibility of detection low voltage variations and the possibility of operating in harsh environments. The thesis is part of OpenLab "Materials and Processes" in a collaboration between Georgia Tech-CNRS laboratory and the PSA Peugeot-Citroen Group

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22449号 / 工博第4710号 / 新制||工||1736(附属図書館) / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 川上 養一, 教授 野田 進, 教授 山田 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Group III-nitride semiconductors are well suited for the fabrication of devices including visible-ultraviolet light emitting diodes, high-temperature and high-frequency devices. The wurtzite III-nitride based heterostructures grown along polar c-direction have large internal electric fields due to discontinuities in spontaneous and piezoelectric polarizations. For optoelectronic devices, such as light-emitting diodes and laser diodes, the internal electric field is deleterious as it causes a spatial separation of electron and hole wave functions in the quantum wells, which decreases emission efficiency. Growth of GaN-based heterostructures in alternative orientations, which have reduced (semipolar) or no polarization (nonpolar) in the growth direction, has been a major area of research in the last few years. The correlation between structural, optical and transport properties of semipolar and nonpolar III-nitride would be extremely useful. The thesis focuses on the growth and characterizations of semipolar and nonpolar III-nitride heterostructures by plasma-assisted molecular beam epitaxy. Chapter 1 provides a brief introduction to the III-nitride semiconductors. The importance of semipolar and nonpolar III-nitride heterostructures over conventional polar heterostructures has been discussed. Chapter 2 deals with the descriptions of molecular beam epitaxy system and working principles of different characterization tools used in the present work. Chapter 3 addresses the molecular beam epitaxial growth of nonpolar (1 1 -2 0) and semipolar (1 1 -2 2) GaN on sapphire substrates. An in-plane orientation relationship is found to be [0 0 0 1] GaN || [-1 1 0 1] sapphire and [-1 1 0 0] GaN || [1 1 -2 0] sapphire for nonpolar GaN on r-sapphire substrates. Effect of growth temperature on structural, morphological and optical properties of nonpolar GaN has been studied. The growth temperature plays a major role in controlling crystal quality, morphology and emission properties of nonpolar a-plane GaN. The a-plane GaN shows crystalline anisotropy nature and it has reduced with increase in the growth temperature. The surface roughness was found to decrease with increase in growth temperature and film grown at 760°C shows reasonably smooth surface with roughness 3.05 nm. Room temperature photoluminescence spectra show near band emission peak at 3.434 -3.442 eV. The film grown at 800 ºC shows broad yellow luminescence peak at 2.2 eV. Low temperature photoluminescence spectra show near band emission at 3.483 eV along with defect related emissions. Raman spectra exhibit blue shift due to compressive strain in the film. An in-plane orientation relationship is found to be [1 -1 00] GaN || [1 2-1 0] sapphire and [-1 -1 2 3] GaN || [0 0 0 1] sapphire for semipolar GaN on m-plane sapphire substrates. The surface morphology of semipolar GaN film is found to be reasonably smooth with pits on the surface. Room temperature photoluminescence shows the near band emission (NBE) at 3.432 eV, which is slightly blue shifted compared to the bulk GaN. The Raman E2 (high) peak position observed at 569.1 cm1. Chapter 4 deals with the fabrication and characterizations of Au/nonpolar and Au/semipolar GaN schottky diodes. The temperature-dependent current–voltage measurements have been used to determine the current mechanisms in Schottky diodes fabricated on nonpolar a-plane GaN and semipolar GaN epilayers. The barrier height (φb) and ideally factor (η) estimated from the thermionic emission model are found to be temperature dependent in nature indicate the deviations from the thermionic emission (TE) transport mechanism. Low temperature I-V characteristics of Au/ GaN Schottky diode show temperature independent tunnelling parameter. Barrier heights calculated from XPS are found to be 0.96 eV and 1.13 eV for Au/nonpolar GaN and Au/semipolar GaN respectively. Chapter 5 demonstrates the growth of InN on r-sapphire substrates with and without GaN buffer layer. InN film and nanostructures are grown on r-sapphire without GaN buffer layer and they are highly oriented along (0002) direction. The electron microscopy study confirms the nanostructures are vertically aligned and highly oriented along the (0001) direction. The Raman studies of InN nanostructures show the SO modes along with the other possible Raman modes. The band gap of InN nanostructures is found to be 0.82 eV. InN grown with a-plane GaN buffer shows nonpolar orientated growth. Growth temperature dependent studies of nonpolar a-plane InN epilayers are carried out. The valence band offset value is calculated to be 1.31 eV for nonpolar a-plane InN/GaN heterojunctions. The heterojunctions form in the type-I straddling configuration with a conduction band offsets of 1.41 eV. Chapter 6 deals with the temperature dependent I-V characteristics of the nonpolar a-plane (1 1 -2 0) InN/GaN heterostructures. The measured values of barrier height and ideality factor from the TE model show the temperature dependent variation. The double Gaussian distribution has mean barrier height values ( ϕb ) of 1.17 and 0.69 eV with standard deviation (σs ) of 0.17 and 0.098 V, respectively. The modified Richardson plot ln (Is/T2)-q2σ2/2k2T2 ) versus q/kT in the temperature range of 350 – 500 K, yielded the Richardson constant of 19.5 A/cm2 K2 which is very close to the theoretical value of 24 A/cm2 K2 for n-type GaN. The tunneling parameters E0 found to be temperature independent at low temperature range (150 –300 K). Chapter 7 concludes with the summary of present investigations and the scope for future work.