Diese Arbeit befasst sich mit den optischen Eigenschaften von dünnen GaN-Schichten gewachsen in verschiedenen Orientierungen. Hierbei werden die optischen Eigenschaften von verspannten M- und A-plane sowie unverspannten C-plane GaN-Schichten untersucht und die Ergebnisse im Rahmen von Bandstrukturberechnungen diskutiert. Im Rahmen dieser Arbeit werden die Bandstrukturverschiebungen theoretisch mittels eines k.p-Näherungsansatzes untersucht. Diese Bandverschiebungen beeinflussen sowohl die Übergangsenergien als auch die Oszillatorstärken. Man findet, dass die C-plane Schicht im Falle einer isotropen Verspannung in der Filmebene keine Anisotropie der optischen Polarisation zeigt. In beiden Fällen zeigen die drei Übergänge von den drei oberen Valenzbändern in das untere Leitungsband andere Polarisationseigenschaften als die entsprechenden Übergänge in C-plane GaN-Schichten. Es wird beobachtet, dass für einen bestimmten Wertebereich der Verspannung in der Filmebene diese Übergänge nahezu vollständig x-,z- bzw. y-artig polarisiert sind. Die verwendeten Schichten wurden auch mittels Transmissionspektroskopie untersucht. Im Falle der M-plane GaN-Schichten können zwei fundamentale Übergänge identifiziert werden, wobei der elektrische Feldvektor E des einfallenden Lichtes einmal parallel (z-Polarisation) und einmal senkrecht (x-Polarisation) auf der c-Achse steht. Die M-plane GaN-Schicht besitzt unterschiedliche Dielektrizitätskonstanten für z-Polarisation und x-Polarisation, welche zu zusätzlichem Dichroismus und Doppelbrechung führen. Als Resultat findet eine Filterung der Polarisation für einfallendes, linear polarisiertes Licht statt. Die elektrische Feldkomponente mit x-Polarisation wird stärker absorbiert als die Komponente mit z-Polarisation. Diese Polarisationsfilterung äußert sich für schmalbandiges Licht in Form einer Drehung der Polarisationsebene in Richtung der c-Achse, wobei ein maximaler Rotationswinkel von 40 Grad gefunden wurde. / In this work, we focus on the optical response of GaN thin films grown along various orientations. The optical properties of strained M- and A- and unstrained C-plane GaN thin films are investigated, and the results are explained with help of band-structure calculations. We calculate the strain-induced band-structure modification using the k.p perturbation approach. The valence-band (VB) states are modified affecting both the transition energies as well as the oscillator strengths. We observe that C-plane GaN does not show any in-plane polarization anisotropy, when an isotropic in-plane strain is applied. For the case of M- and A-plane GaN, one expects to see an in-plane polarization anisotropy even for the unstrained case. Additionally, the in-plane strain significantly changes the band structure and the symmetry of the VB states. The three transitions, involving electrons in the conduction band (CB) and holes in the top three VBs, will exhibit a very different polarization characteristic than the ones for C-plane GaN. These transitions are predominantly x, z, and y polarized, respectively, for a certain range of in-plane strain values, present in our samples. For M-plane GaN thin films, two fundamental transitions can be identified, which occur when the electric field vector E is perpendicular (x-polarization) and parallel c (z-polarization). These transitions give rise to a transmittance spectrum separated by 50 meV at room temperature with respect to each other. This result in a polarization filtering of an incident linearly polarized light beam after transmission, because the electric field component with x-polarization is more strongly absorbed than with z-polarization. This filtering manifests as a rotation of the polarization vector toward the c axis and can be as large as 40 degrees for an initial angle of 60 degrees, for our samples.

Diese Arbeit befasst sich mit der Keimbildung und den Wachstumsmechanismen von GaN-Nanodrähten (NWs), die mittels Molekularstrahlepitaxie (MBE) hergestellt wurden. Die Hauptneuheiten dieser Studie sind der intensive Gebrauch von in-situ Messmethoden und der direkte Vergleich zwischen katalysatorfreien und katalysatorinduzierten NWs. In der MBE bilden sich GaN-NWs auf Silizium ohne Katalysator. Auf Saphir dagegen wachsen NWs unter den gleichen Bedingungen nur in der Anwesenheit von Ni-Partikeln. Die Nukleationsprozesse sind für beide Ansätze fundamental verschieden. In dem katalysatorinduzierten Ansatz reagiert Ga stark mit den Ni-Keimen, deren Kristallstruktur für das Nanodraht-Wachstum entscheidend sind, während in dem katalysatorfreien Ansatz bildet N eine Zwischenschicht mit Si vor der ausgeprägten GaN-Nukleation. Mittels beider Ansätze wachsen einkristalline wurtzite GaN-NWs in Ga-polarer Richtung. Allerdings sind unter denselben Wachstumsbedingungen die katalysatorinduzierten NWs länger als die katalysatorfrei gewachsenen und enthalten viele Stapelfehler. Im Vergleich sind die katalysatorfreien größtenteils defektfrei und ihre Photolumineszenz ist viel intensiver als jene der katalysatorinduzierten NWs. Alle diese Unterschiede können auf den Katalysator zurückgefürt werden. Die Ni-Partikel sammeln die an den Nanodraht-Spitzen ankommenden Ga-Atome ef?zienter ein als die unbedeckte oberste Facette im katalysatorfreien Fall. Außerdem können Stapelfehler sowohl aus der zusätzlichen Festkörperphase des Ni-Katalysators als auch aus der Verunreinigung der NWs mit Katalysatormaterial resultieren. Solch eine Kontaminierung würde schließlich nicht-strahlende Rekombinationszentren verursachen. Somit mag die Verwendung von Katalysatorkeimen zusätzliche Möglichkeiten bieten, das Wachstum von NWs zu kontrollieren. Jedoch sind sowohl die strukturellen als auch die optischen Materialeigenschaften der katalysatorfreien NWs überlegen. / This work focuses on the nucleation and growth mechanisms of GaN nanowires (NWs) by molecular beam epitaxy (MBE). The main novelties of this study are the intensive employment of in-situ techniques and the direct comparison of self-induced and catalyst-induced NWs. On silicon substrates, GaN NWs form in MBE without the use of any external catalyst seed. On sapphire, in contrast, NWs grow under identical conditions only in the presence of Ni seeds. The processes leading to NW nucleation are fundamentally different for both approaches. In the catalyst-assisted approach, Ga strongly reacts with the catalyst Ni particles whose crystal structure and phases are decisive for the NW growth, while in the catalyst-free approach, N forms an interfacial layer with Si before the intense nucleation of GaN starts. Both approaches yield monocrystalline wurtzite GaN NWs, which grow in the Ga-polar direction. However, the catalyst-assisted NWs are longer than the catalyst-free ones after growth under identical conditions, and they contain many stacking faults. By comparison the catalyst-free NWs are largely free of defects and their photoluminescence is much more intense than the one of the catalyst-assisted NWs. All of these differences can be explained as effects of the catalyst. The seed captures Ga atoms arriving at the NW tip more efficiently than the bare top facet in the catalyst-free approach. In addition, stacking faults could result from both the presence of the additional solid phase constituted by the catalyst-particles and the contamination of the NWs by the catalyst material. Finally, such contamination would generate non-radiative recombination centers. Thus, the use of catalyst seeds may offer an additional way to control the growth of NWs, but both the structural and the optical material quality of catalyst-free NWs are superior.

Hybride anorganisch/organischen Systeme können die individuellen Vorteile, etwa eine hohe elektronische Mobilität in anorganischen und starke Licht-Materie-Wechselwirkung in organischen Halbleitern, kombinieren. Ein sinnvoller Nutzen dieser Heterostrukturen benötigt ein umfassendes Verständnis der Grenzfläche. Zwei Grenzflächenprozesse werden in dieser Arbeit behandelt. Förster-Resonanzenergietransfer (FRET) wird zwischen einem InGaN/GaN Quantengraben und dem Polymer Cn-ether PPV untersucht. Trotz des hohen internen elektrischen Feldes im Quantengraben, ist effizienter Energietransfer möglich, solange andere nicht-strahlende Zerfallsprozesse unterdrückt werden. Dies wird mittels temperaturabhängiger PL und PLE Spektroskopie gezeigt. PLE demonstriert eine eindeutige Erhöhung der Emission des Akzeptors. Bei höheren Temperaturen dominieren nicht-strahlende Zerfallskanäle. Ladungstransfer wird zwischen MoS2 und dem Molekül H2Pc untersucht. Die Kombination mit organischen Molekülen kann die Funktionalität von MoS2 erweitern. Photoelektronenspektroskopie (PES) zeigt einen Typ-II Heteroübergang an der MoS2/H2Pc Grenzfläche. Angeregte Elektronen gehen von den H2Pc Molekülen in die MoS2 Monolage über, wie mittels einer Verkürzung der PL Lebenszeit von H2Pc gezeigt wird. Photostrommessungen demonstrieren zudem, dass die transferierten Elektronen zu einer erhöhten Photoleitfähigkeit beitragen. Zusätzlich werden auch einzelne 2D Übergangsmetall Dichalkogenide (TMDCs) untersucht. Um TMDCs von hoher Qualität herzustellen, wurde intern eine Wachstumsmethode entwickelt. Mittels PL Spektroskopie werden die so hergestellten Schichten charakterisiert. Die Vielseitigkeit der Methode wird anhand des Wachstums von Mischkristallen und Heterostrukturen gezeigt. Der Einfluss der dielektrischen Funktion des Substrates wird erforscht. Durch die Kombination von PES und Reflexionsmessungen kann eine gleichzeitige Abnahme sowohl der Bandlücke als auch der Exzitonen Bindungsenergie gezeigt werden. / Hybrid inorganic/organic systems can combine the advantages of both materials such as high carrier mobilities in inorganic semiconductors and large light-matter interaction in organic ones. In order to benefit from these heterostructures, a thorough understanding of the interface is needed. Two processes occurring at the interface are looked at in this thesis. Förster resonance energy transfer (FRET) is studied between a single InGaN/GaN quantum well and the polymer Cn-ether PPV. Despite the large internal electric fields in the quantum well, efficient FRET is possible as long as other non-radiative decay channels are suppressed. This is shown by temperature dependent PL and PLE spectroscopy. PLE spectra clearly demonstrate an enhanced light emission from the acceptor. At elevated temperatures, non-radiative decay pathways become dominant. Excited-state charge transfer is studied on MoS2 in combination with the molecule H2Pc. The combination with molecules can extend the functionality of MoS2. Photoelectron spectroscopy (PES) reveals a type II energy level alignment at the MoS2/H2Pc interface. Excited electrons are transferred from H2Pc to MoS2, deduced from a shortening of the H2Pc PL decay time. Photocurrent spectra further show that the transferred electrons contribute to an enhanced photoconductivity. Additionally, bare 2D transition-metal dichalcogenides (TMDCs) are studied. In order to fabricate high-quality TMDC monolayers, a growth method was developed in-house. The grown monolayers are characterised by optical spectroscopy. The versatility of the method is demonstrated by the growth of alloys and heterostructures. The influence of the substrate dielectric function is investigated by comparing band-gaps measured by PES with the exciton transition energies obtained by reflectance measurements. An almost equal reduction in both energies with the substrate dielectric constant is seen.

In dieser Dissertation wird zum einen die ultraschnelle Ladungsträgerkinetik in einem Galliumnitrid (GaN)-basierten Übergitter, zum anderen die piezoelektrische Elektron-Phonon-Wechselwirkung kohärenter zonengefalteter Phononen in Galliumarsenid (GaAs)-basierten Übergittern behandelt. Mittels spektral- und zeitaufgelöster Photolumineszenzmessungen an einem n-dotierten GaN/Al0,18Ga0,82N Übergitter mit Parametern ähnlich derer in optoelektronischen Bauelementen wurde die defektbedingte Ladungsträgerkinetik untersucht, die innerhalb von ca. 150 ps durch den Einfang in tiefe, nichtstrahlende Rekombinationszentren beeinflusst wird. Die Untersuchung einer Passivierung mit Siliziumnitrid zur Verhinderung von Degradationseffekten zeigte ein stabiles optisches Langzeitverhalten bei gleichzeitiger Zunahme nichtstrahlender Defekte. Ferner wurde mit spektral aufgelöster Anrege-Abfrage-Spektroskopie eine Einfangkinetik auf einer Zeitskala von 150 - 200 fs in Defektzustände nahe der Übergitterbandkante gemessen, gefolgt von der Abkühlung der Ladungsträger durch Phononemission innerhalb weniger Pikosekunden bei Raumtemperatur und 35 ps bei 5 K. Kohärente zonengefaltete Phononen wurden mit Anrege-Abfrage-Spektroskopie an zwei AlAs/GaAs-Übergittern untersucht, die in [100]-, bzw. [111]-Richtung gewachsen wurden. Dies ermöglicht die (gezielte) Untersuchung der piezoelektrischen Elektron-Phonon-Kopplung, da diese für longitudinal-akustischen Phononen nur in der [111]-Probe existiert. Die Amplitude kohärenter Phononen mit einem Wellenvektor von q=0 in der [111]-Probe fällt verglichen mit denen in der [100]- und der [111]-Probe mit q≠0 signifikant schneller ab. Kohärente Phononen verursachen in der [111]-Probe bei q=0 ein makroskopisches piezoelektrisches Feld, welches Ladungsträger beschleunigt, die durch Reibung kohärente Phononen dämpfen. Bei hohen Ladungsträgerdichten unterdrückt die Abschirmung der induzierten piezoelektrischen Felder diese zusätzliche Dämpfung. / In this dissertation, the ultrafast carrier dynamics in a gallium nitride (GaN)-based superlattice as well as the piezoelectric electron-phonon-coupling of coherent zone-folded phonons in gallium arsenide (GaAs)-based superlattices are addressed. Using spectrally and time-resolved photoluminescence experiments on an exemplary n-doped GaN/Al0.18Ga0.82N superlattice with parameters similar to those in optoelectronic devices, we investigated the defect-related carrier kinetics, that are affected by trapping in saturable nonradiative recombination centers on time scales of ~150 ps. The investigation of a passivation with silicon nitride to prevent degradation effects show a long-term optical stability with a concomitant increase in non-radiative defect densities. Furthermore, spectrally resolved pump-probe spectroscopy was used to measure trapping kinetics into defect states near the conduction band minimum on a time scale of 150 – 200 fs. These kinetics are followed by carrier cooling through phonon emission within a few picoseconds at room temperature and within 35 ps at 5 K. Coherent zone-folded phonons were studied with pump-probe spectroscopy on two AlAs/GaAs superlattices grown in [100] and [111] direction, respectively. This allows the specific investigation of the piezoelectric electron-phonon interaction, since this exists for longitudinal acoustic phonons only in the [111] sample. The amplitude of coherent phonons with a wave vector of q=0 in the [111] sample decays significantly faster than in the [100] and the [111] samples with q≠0. Coherent phonons in the [111] sample cause a macroscopic piezoelectric field to which the photogenerated electron-hole plasma couples. Friction of the accelerated carriers provides the additional damping mechanism. High carrier densities screen the induced piezoelectric field, thus reducing the damping mechanism via the piezoelectric interaction.

La fabrication des composants semi-conducteurs à base de nitrure de gallium (GaN) connaît actuellement une grande expansion. Ce matériau, par ces propriétés physico-chimiques intéressantes, est un très bon candidat pour la fabrication des composants de puissance à haute fréquence de fonctionnement. Dans la pratique, avant d’intégrer ces composants dans un système électronique, l’analyse de leur fiabilité est une étape nécessaire pour valider la technologie de fabrication utilisée. L’objectif de ce travail est la détermination des mécanismes physiques responsables de la dégradation des performances des Transistors à Haute Mobilité Electronique (HEMT) à base d’hétérostructures AlGaN/GaN et AlInN/GaN. Dans un premier temps, la caractérisation en régime statique des composants, par des mesures de courant et de capacité à différentes températures, nous a permis de repérer certaines anomalies dans les caractéristiques des composants. Cette non-idéalité liée aux effets thermiques semble provenir des mécanismes de piégeage des porteurs par les défauts dans le matériau. Dans le but d’analyser ces mécanismes, des mesures de spectroscopie de défauts profonds (DLTS) ont été effectuées sur la capacité de type Schottky du contact de la grille. L’étape suivante a consisté à mesurer les pièges profonds dans les HEMTs par DLTS en courant de drain, de façon à déterminer quels défauts influencent directement le courant dans ces dispositifs. Cette étude a été effectuée sur différents composants avec différentes géométries pour analyser au mieux le comportement de ces pièges. L’étude du contact de grille est aussi une étape importante pour déterminer les origines de défaillance des composants. Pour cela, nous avons réalisé une étude approfondie sur les différents mécanismes de transport à travers la barrière métal/semi-conducteur. Cette étude nous a permis de conclure sur la stabilité du contact de grille après les tests de vieillissement accélérés. / The manufacture of semiconductor components based on gallium nitride (GaN) is currently undergoing a major expansion. This material, by his physical and chemical attractive properties, is a very good candidate for the manufacture of high power and hign frequency operating components. In practice, before integrating these components in an electronic system, the analysis of reliability is a necessary step to validate the used manufacturing technology. The objective of this work is to determine physical mechanisms responsible for the performance degradation of high electron mobility transistors (HEMT) based on AlGaN/GaN and AlInN/GaN heterostructures. At first, the static characterization of the components, by current and capacitance measurements at different temperatures, allowed us to identify anomalies in the characteristics. This non-ideality due to thermal effects seem to come from the trapping mechanisms of carriers by defects in the material. In order to analyze these mechanisms, deep levels transient spectroscopy measurements(DLTS) were carried out on the Schottky contact of the gate. The next step was to measure the deep traps in HEMTs by DLTS on drain current, in order to identify defects directly related to the current in these devices. This study was performed on different components with different geometries to analyze the behavior of these traps. The study of the gate contact is an important step in determining the origin of component failure. For this, we conducted a deep study on different transport mechanisms across the metal/semiconductor barrier. This study allowed us to conclude on the stability of the gate contact after the accelerated aging tests.

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.

No description available.

Cette thèse est consacrée à l’étude de l’outil d’épitaxie HVPE (Hydride Vapour Phase Epitaxy) pour la synthèse avec et sans catalyseur de nanofils semiconducteurs GaN et GaAs. Une étude systématique de l’influence des conditions expérimentales sur la croissance des fils de GaN est effectuée, afin de démontrer la faisabilité de cette croissance sur la surface des substrats saphir plan-c et silicium sans aucun traitement de la surface préalablement à la croissance. Nous avons démontré la croissance par VLS-HVPE, de nanofils de GaN de diamètres constants de 40 à 200 nm, de longueurs supérieures à 60 μm et présentant des qualités optique et cristallographique remarquables. Pour les nanofils de GaAs, la stabilité, inédite, de la phase cubique zinc-blende pour des diamètres de 10 nm a été démontrée par le procédé de croissance VLS-HVPE sur des longueurs de quelques dizaines de micromètres. Les mécanismes de croissance sont discutés à partir des diagrammes de phase et de la physique de la croissance HVPE qui met en oeuvre des précurseurs gazeux chlorés. Pour les semiconducteurs III-V, cette étude permet d’envisager des applications liées aux nanofils longs qui jusque là n’étaient exploitées que pour le silicium. Ces travaux montrent que dans le contexte des Nanosciences, la HVPE, outil épitaxial à fortes vitesses de croissance, mérite une audience élargie, et peut s’inscrire comme un outil complémentaire efficace aux procédés MOVPE et MBE pour le façonnage contrôlé de la matière à l’échelle nanométrique. / This thesis is devoted to the study of HVPE (Hydride Vapour Phase Epitaxy) method of growing GaN and GaAs nanowires with and without catalyst. A systematic study of the influence of the growth conditions on GaN formation was performed in order to demonstrate the feasibility of this growth on c-plane sapphire and silicon substrates without preliminary treatment of the surface. We have demonstrated by VLS-HVPE the growth of the GaN nanowires with constant diameters of 40 to 200 nm and of length up to 60 μm, while they possess remarkable optical and crystal quality. The newly observed stability of the zinc blende structure for GaAs nanowires with diameters of 10 nm has been described by the VLS-HVPE process, for lengths of few tens of micrometers. The growth mechanisms are discussed based on the phase diagram and the physics of near-equilibrium HVPE using chloride precursors. For III-V semiconductors, the study allows us to consider applications related to long nanowires that, at present, are used only for silicon. This work shows that in the context of Nanoscience, the fast growth HVPE method deserves a wider audience and thus could be considered as an effective complementary tool to MOVPE and MBE processes for the controlled shaping of matter on the nanoscale.

Group III-A nitrides (GaN, AlN, InN and alloys) are materials of considerable contemporary interest and currently enable a wide variety of optoelectronic and high-power, high-frequency electronic applications. All of these applications utilize device structures that employ a single or multiple hetero-junctions, with material compositions varying across the interface. For example, the workhorse of GaN based electronic devices is the high electron mobility transistor (HEMT) which is usually composed of an AlGaN/GaN hetero-junction, where a two-dimensional electron gas (2DEG) is formed due to differences in polarization between the two layers. In addition to such hetero-junctions in the same material family, formation of hetero-interfaces in nitrides begins right from the epitaxy of the very first layer due to the lack of native substrates for their growth. The consequences of such "dissimilar" hetero-junctions typically manifest as large defect densities at this interface which in turn gives rise to defective films. Additionally, if the substrate is also a semiconductor, the electrical properties at such dissimilar semiconductor-nitride hetero-junctions are particularly important in terms of their influence on the performance of nitride devices. Nevertheless, the large defect densities at such dissimilar 3D-3D semiconductor interfaces, which translate into more trap states, also prevents them from being used as active device layers to say nothing of reliability considerations arising because of these defects. Recently, the advent of 2D materials such as graphene and MoS2 has opened up avenues for Van der Waal’s epitaxy of these layered films with practically any other material. Such defect-free integration enables dissimilar semiconductor hetero-junctions to be used as active device layers with carrier transport across the 2D-3D hetero-interface. This thesis deals with hetero-epitaxial growth platforms for reducing defect densities, and the material and electrical properties of dissimilar hetero-junctions with the group III-A nitride material system.

Les potentialités du nitrure de gallium (GaN) et notamment de l'hétérostructure AlGaN/GaN, semiconducteur à large bande interdite, en font un matériau particulièrement intéressant en électronique de puissance, notamment pour des applications haute tension, haute température et haute fréquence. L'objectif de ce travail de thèse était de développer et d'optimiser l'étape d'isolation de la grille lors la réalisation de transistors MIS-HEMT de puissance sur hétérostructure AlGaN/GaN, le but étant de réduire les courants de fuite de grille sans perturber les propriétés du transistor. Après avoir évaluation, le choix s'est porté sur l'alumine Al2O3 déposé par ALD comme diélectrique de grille. L'étude s'est d'abord concentrée sur l'analyse de l'influence de traitements, chimiques ou plasma, sur la contamination de la surface d'AlGaN au travers d'analyses XPS et AFM. Puis, l'influence du diélectrique de grille a été évalué à travers la réalisation et la mesure électrique de dispositifs, diodes et transistors, en variant les méthodes de dépôt par ALD. Enfin, l'impact d'un recess par gravure ICP-RIE partielle ou complètes de la barrière d'AlGaN sous la grille a été étudiée. La réalisation d'un HEMT passe par l'étape critique du dépôt du diélectrique de grille sur le semiconducteur, et le contrôle de la qualité de l'interface " diélectrique/AlGaN " est donc une étape fondamentale car elle influe sur les propriétés électriques du composant. Ce contrôle comprend le traitement de surface du semiconducteur, mais aussi la nature et la technique de dépôt du diélectrique. Ainsi il apparaît à travers l'étude qu'un traitement de surface à l'ammoniaque à haute température est le plus efficaces pour retirer les contamination en oxydes natifs. Les mesures électriques, C(V) et Id(Vg), ont quant à elle montrés la supériorité de la PEALD par rapport à un dépôt thermique conventionnel. Ceci peut s'expliquer par le fait que le plasma oxygène qui entre jeu lors du dépôt de l'alumine par PEALD semble nettoyer la surface lors des premiers cycles, retirant notamment la contamination carbone. Cela permet d'avoir une meilleure interface entre l'alumine et le semi-conducteur, limitant les pièges à l'interface et dans l'oxyde. Cela a réduit de manière considérable les courants de fuite de grille, sans détériorer la qualité et la rapidité de la transition entre l'état on et off. De plus, les HEMTs réalisé étant de type normally-off, le recess de grille par gravure ICP-RIE a été implémenté afin de rendre moins négative la tension de pincement. Cela a été réalisé avec succès, notamment avec la réalisation d'un composant de type noramlly-off grâce à un recess total de la barrière d'AlGaN sous la grille. Des résultats à l'état de l'art ont été obtenus à travers une approche simple, et un processus de création de transistors robuste et hautement reproductible, avec une réduction importante des courants de fuite de grille et une pente sous le seuil record. Afin de compléter l'étude il conviendra par la suite de réaliser des études de fiabilité, notamment à travers des mesures dynamiques pour évaluer notamment les phénomènes de dégradation du Ron. / With its large band gap, Gallium Nitride (GaN) semiconductor is one of the most promising materials for new power devices generation thanks to its outstanding material properties for high voltage, temperature and frequency applications. The main objective of this thesis was the development and optimization of the insulating step taking place in the elaboration of MIS-HEMT transistors on an AlGaN/GaN heterstroctructure. In order to reduce gate leakage currents without degrading the device properties, alumina Al2O3 deposited by ALD was chosen as a gate dielectric. The study was first centered on the influence of surface treatments, chemical or plasma, regarding surface contamination. Their impact was analyzed through XPS and AFM. Secondly, electrical measures were performed on complete MIS-HEMT diodes and transistors to evaluate the influence of the alumina insulating layer depending on the ALD deposition method. Lastly, partial and full recess of the AlGaN barrier was studied via ICP-RIE etching. The gate dielectric deposition is one of the crucial steps intervening in the HEMT creation process. The quality and control at the Al2O2/AlGaN interface being paramount, it will directly influence the device's electric properties. This involves control ing the semiconductor surface, but also the nature and deposition technique of the dielectric. As such, an ammonia-based treatment at high temperature appears to be the most efficient in reducing native oxygen contamination. Regarding electric performances, C(V) and Id(Vg) measures showed the superiority of PEALD compared to traditional thermal ALD deposition. This can be explained by the fact that the oxygen plasma used as oxydant during the alumina deposition by PEALD seems to clean the surface during the first cycles, mostly by reducing carbon contamination. This allowed to achieve a better interface between the semiconductor and the insulting layer, thus limiting traps at the interface or in the oxyde. This allows to considerably reduce gate leakage currents, without degrading the quality and transition sharpness between the on and off state. Moreover, the realized HEMTs being normally-off, gate recess etching via ICP-RIE was implemented in order to make the threshold voltage less negative. This was successfully achieved, especially through the realization of a normally-off transistors thanks to a full recess of the AlGaN barrier under the gate. State of the art results were achieved through a simple approach, and a robust and highly reproducible transistor elaboration process, with great reduction of gate leakage currents and a record sub-threshold slope. In order to complete the study, it will be necessary in the future to proceed to viability studies, especially through dynamic electric evaluation, in order to evaluate for instance Ron degradation phenomenons.