Cette thèse est principalement axée sur le développement des matériaux III-N pour les transistors de puissance HEMTs, ainsi que les multipuits quantiques et les applications optroniques qui en découlent dans une moindre mesure. Suite à un rappel des propriétés des nitrures, des différentes applications possibles, du principe de la MOCVD et des différentes caractérisations retenues pour ce travail, nous avons traité dans un premier temps la croissance de GaN à basse température, c'est-à-dire en dessous de 1050degres C. La fabrication de multipuits impliquant l’alternance des couches de GaN et d'InAlN ou InGaAlN nous contraint de travailler à ces températures ce qui génère l’apparition d’un défaut en surface du GaN que l’on nomme V-defect. Une étude expérimentale poussée nous a permis de comprendre comment apparaissent et évoluent ces défauts selon les paramètres de croissance. Un modèle basé sur les énergies de surface à pu être élaboré et explique l’évolution de ces défauts. Ensuite nous avons défini l'influence de nombreux paramètre de croissance par MOCVD et tiré, des multiples tendances mises en relief, des modèles et explications justifiant telle ou telle propriété physique et chimique du matériau. En aval, ce sont des caractérisations électriques et principalement des mesures de résistivités qui ont été traitées afin de comparer la performance de nos échantillons à base d'indium à ceux de type AlGaN/GaN. Le problème de la pollution au gallium dans les réacteurs MOCVD verticaux a été mis en évidence et nous avons proposé différentes solutions pour la limiter, voire l’annihiler. Pour terminer ce sont des couches de protection à base de SiN et GaN que nous avons tenté de développer afin de protéger nos alliages à base d’indium pour la suite des étapes technologiques nécessaires à la fabrication d’un composant par exemple. / This thesis is mainly focused on the development of III-N materials for HEMTs power transistors, as well as quantum wells and optronics applications that result to a lesser extent. Following a reminder of the properties of nitrides, the different possible applications, the principle of the MOCVD and the different characterizations used for this work, we first treated the growth of GaN at low temperature, that is to say below 1050degres C. The manufacture of multiple quantum wells involving the alternation of GaN and InAlN or InGaAlN layers forces us to work at these temperatures, which generates the appearance of a defect in surface of the GaN which is called V-defect. An advanced experimental study allowed us to understand how these defects appear and evolve according to the growth parameters. A model based on surface energies could be developed and explains the evolution of these defects. Then we defined the influence of many MOCVD growth parameters by MOCVD and derived, from the multiple trends highlighted, the models and explanations justifying this or that physical and chemical property of the material. Downstream, these are electrical characterizations and mainly resistivity measurements that have been processed to compare the performance of our indium-based samples to those of AlGaN/GaN type. The problem of gallium pollution in vertical MOCVD reactors has been highlighted and we have proposed different solutions to limit or even annihilate it. Finally, we have tried to develop protective layers based on SiN and GaN in order to protect our indium-based alloys for the next technological steps required to manufacture a component, for example.

Au sein de la Thématique Nanoform, Axe Nanosciences, ICB, nous réalisons la croissance de nanostructures hybrides 1D, 2D et 3D à base de TiO2 par MOCVD. Nos travaux portent sur l’aspect théorique de la formation de ces nanostructures (modèles de croissance et cinétique, structure et texture) et l’étude des propriétés photoélectriques, optiques, physicochimiques ainsi que sur le développement d’applications de ces structures dans le domaine de la physique (random laser), de la photocatalyse, de l’énergie (cellules solaires). Sous certaines conditions parfaitement maitrisées, nous obtenons des structures à base de TiO2, étonnamment originales jamais décrites dans la littérature : feuilles, tiges, canaux, creusets, nanostructures originales COHN (COaxiales Heterostructures Nanowires) Nos travaux précédents ont permis d’identifier l’origine probable de ces structures : utilisation de catalyseurs ferromagnétiques en présence d’un chauffage à induction. L’étude de ce mécanisme est totalement nouvelle. / Within the Nanoform Theme, Ax Nanosciences, ICB, we realize the growth of 1D, 2D and 3D hybrid nanostructures based on TiO2 by MOCVD. Our work deals with the theoretical aspect of the formation of these nanostructures (growth and kinetic models, structure and texture) and the study of photoelectric, optical and physicochemical properties as well as the development of applications of these structures in physics (random laser), photocatalysis, energy (solar cells). Under certain perfectly controlled conditions, we obtain original TiO2 structures not yet described in the literature: membranes, rods , canals, crucibles, COHN (COaxiales Heterostructures Nanowires). Our previous work made it possible to identify the probable origin of these structures: use of ferromagnetic catalysts in the presence of induction heating. The study of this mechanism is totally new.

In this dissertation, GaN growth on porous templates by metalorganic chemical vapor deposition (MOCVD) was studied. The motivation of this research is pursuing an effective reduction of defects in GaN by its submicron-scale and nano-scale epitaxial lateral overgrowth (ELO) on these porous templates, which included porous TiN/GaN (P-TiN), imprint lithography patterned Ti/GaN (IL-Ti), carbon-face nano-porous SiC (C-PSC), and silicon-face nano-porous SiC (Si-PSC). The porous TiN/GaN was formed in situ in MOCVD reactor by annealing a Ti-covered GaN seed layer. This simplicity makes the GaN ELO on the P-TiN more cost-efficient than the conventional ELO which requires ex situ photolithography and/or etching. Both the GaN nano-ELO and the GaN micron-ELO could be realized on P-TiN by controlling the GaN nucleation scheme. The reduction efficacy of edge threading dislocation (TD) was ~15 times. The optical characterization indicated that the non-radiative point-defects in GaN grown were reduced significantly on the P-TiN.The imprint lithography patterned Ti/GaN had uniformly distributed submicron Ti pads on GaN seed layer. These Ti pads acted as GaN ELO masks. The TD reduction efficacy of the IL-Ti was only ~2 due to the low coverage of Ti (~25%) on the GaN seed layer and the low pressure (30 Torr) employed during GaN ELO. Even with a small reduction of TDs, the point-defects in GaN were effectively lowered by the IL-Ti. Hydrogen polishing, sacrificial oxidation, and chemical mechanical polishing were employed to remove surface damage on the PSC substrates. Nitrogen-polarity GaN grown on the C-PSC was highly dislocated because the rough surface of C-PSC induced strong misorientation between GaN nucleation islands. The efficacy of Si-PSC on defect reduction primarily depended on the GaN nucleation schemes. A high density of GaN nano-nucleation-islands was required to realize the GaN nano-ELO extensively. With such a nucleation scheme, the GaN grown on Si-PSC had a ~20 times reduction on the density of the mixed and screw TDs compared with control sample. This growth method is promising for effective defect reduction within a small GaN thickness. Reducing the GaN nucleation density further lowered the TD density but also diminished the efficacy of Si-PSC. These results were explained by a growth model based on the mosaic structure of GaN.

La présence de bactéries et biofilms est une préoccupation permanente dans de nombreux domaines. Ils sont à l’origine de nombreux faits d’actualité qui ont un coût important pour le système de santé. L’objectif de notre travail visait à élaborer des films nanocomposite transparents contenant des particules métalliques nanométriques d'élément antibactérien (Ag ou Cu) immergées dans une matrice d’oxyde (TiO₂). La méthode de dépôt DLI-MOCVD (Direct Liquid Injection-Metal Organic Chemical Vapor Deposition) a été employée pour élaborer les films composites. Ce procédé permet le contrôle de la fraction molaire des précurseurs injectés dans le réacteur CVD et de revêtir des supports 3D (poreux). La croissance et la structure du dioxyde de titane (TiO₂) sont influencées par la présence du précurseur contenant l’élément antibactérien. La fraction molaire du précurseur (Ag ou Cu) modifie les caractéristiques physico chimiques et structurales des dépôts. L'activité antibactérienne est mesurée selon la norme JIS Z 2801:2000 avec S. aureus et E. coli en l’absence de lumière. Des essais antibactériens spécifiques ont été optimisés afin d'évaluer leur activité proche de condition réelle. La composition des dépôts influence fortement l’activité antibactérienne d’inactif à bactéricide. Des corrélations entre la microstructure et la composition des films et leurs propriétés antibactériennes sont discutées. / The presence of bacteria and biofilms is permanent concern in many fields. Their presences are at the origin of many events which have high costs for the health system. In this objective, this work aimed to elaborate transparent nanocomposite thin films which are composed of nanometric metallic particles of antibacterial element (Ag or Cu) embedded in an oxide matrix (TiO₂). The DLI-MOCVD process (Direct Liquid Injection-Metal Organic Chemical Vapour Deposition) was used to elaborate these thin films. This process allows the quantity of precursors injected into the CVD reactor to be controlled and porous body to be coated. The growth mechanisms and the structure of the Titanium dioxide (TiO₂) are influenced by the presence of the organic precursor which contains the antibacterial element. The mole fraction of precursor (Ag or Cu) modifies the physico-chemical and structural properties of films. The antibacterial activity was tested according to the standard JIS Z 2801: 2000 with S. aureus and E. coli without light Specific tests were optimised in order to evaluate their activity in environments more representative. The composition of coatings impacts strongly the antibacterial activities from inactive to bactericidal properties. Correlations between the microstructure and composition of films and their antibacterial properties are discussed.

Zugl.: Duisburg, Essen, Univ., Diss., 2007

This thesis investigates different material systems and processing technology for high temperature compatible laser diodes used in volume applications within the 1.3-μm telecom wavelength window. Laser diodes built from such materials are much desired in order to eleminate the need for active temperature control needed in current systems, which significantly increases both complexity, size and cost. The structures were grown by Metal-Organic Chemical Vapor Deposition (MOCVD) and the evaluation of materials was performed using different characterization methods such as High-Resolution X-Ray Diffraction (HR-XRD), Photoluminescence (PL), Time-Resolved Photoluminescence (TR-PL). Fabrication and evaluation of Fabry-Perot lasers with different geometries was used to check the material quality and temperature performance. A novel in-situ etching technique was developed for the use i future more advanced, buried hetrostructure lasers. The first studied materials system was AlGaInAsP/InGaAsP/InP. To handle a 5-element material with the precision required, modelling of the materials and heterostructure properties was performed. The addition of Al to the InGaAsP barrier allows better electron confinement with little change in valence band properties. The optimum aluminium content was found to be about 12%. Although the effect of Al could be identified, it was not sufficient with T0 of only 90 K only up to 60 °C. A second materials system InGaP/InAsP/ InP initially looked quite promising from a materials and quantum well design point of view but encountered severe problems with the device integration and further work was discontinued. The main effort was therefore was devoted to a third materials system: AlGaInAs/AlGaInAs/InP. This material system is not unknown but has hitherto not found a widespread application for fibre optic applications. In this work, the MOCVD growth of 1.3 μ;m quantum well laser structures was optimized and ridge waveguide laser devices with excellent temperature performance was fabricated (T0 = 97 K at 85 °C). A ridge waveguide laser was identified as suitable structure since it requires only a single epitaxial growth, thus avoiding the main problem of oxidation of Al based buried structures. The dynamic performance was excellent up to 110 °C and the device fabrication is highly reliable (lifetime >7000 h). This high yield uncooled ridge Fabry-Perot laser process has now been transferred to production and is applied in short length 10 Gb/s multimode links. In order to further improve the usefulness of the Al-containing materials in even higher performance devices needed in future applications developments towards fully buried heterostructure device geometry were also pursued. To overcome difficulty of oxidation of Al containing layers at the mesa walls an in-situ etching technique was implemented. Different chemistry approaches were investigated and the first results of lasers devices were reported. / QC 20100930

The marriage of synthetic chemistry to materials science has been well documented in the last decade. The design, synthesis, and utilization of chemical precursors in the MOCVD of electronic materials in particular has received a lot of attention in both academic and industrial circles. The maintenance of this symbiotic relationship is pursued in this work in the hope of discovering chemical forerunners for high-dielectric metal oxide materials. Specifically, it is of interest to isolate chemical precursors for ZTT, a recent entry into the field of high-k composites. The primary theme of this dissertation is the exploration of the design and synthesis of molecular precursors that possess more than one of the cations found in the final ZTT film. The approach taken to obtain such precursors, referred to in this work as same-source precursors, is to investigate the implementation of the anionic stannylamine ligand, -N(SnMe3)2 in the preparation of heterometallic coordination complexes. The ultimate goal is to procure volatile, low molecular weight compounds that possess more than one of the metals found in ZTT (tin, titanium, and/or zirconium). The reason for choosing stannylamine ligands is two-fold. First, as was alluded to above, such ligands might provide convenient access to heterometallic complexes possessing tin as one of the metal constituents. Second, since the coordination chemistry of stannyl amines is relatively unexplored compared to alkyl- and silylamine ligands, it is important from a fundamental standpoint to investigate the synthetic utility of this ligand type. With this motivation in mind, the results reported here accomplishe two major objectives: 1) the synthesis and characterization of a variety of metal complexes coordinated by stannylamines and 2) the design, synthesis, and utilization of heterometallic precursors for use in the MOCVD of ZTT. Thus, in the course of a synthetic investigation towards the goal of same-source ZTT precursors for use in MOCVD processes, a number of metal coordination complexes possessing stannylamine ligands have been synthesized and fully characterized. Consequently, the library of known compounds containing these ligands has been significantly expanded and a novel route to volatile, heterobimetallic aminoalkoxide species has been developed.

The objective of this thesis is to discuss the solutions investigated by AMDG (Advanced Materials and Devices Group) to reduce the "efficiency droop" effect that occurs in III-Nitrides Light Emitting Diodes (LEDs) when driven at high injection current densities. The efficiency droop refers to a decrease of the LED light emission efficiency when increases the current density from low values ~10 A/cm2 to higher values >100A/cm2. Many scientific papers have been written about the possible reasons for this phenomenon. Therefore, this thesis will discuss the different effects suspected to contribute to the droop, and discuss LED structure modifications studied by Dr. Dupuis' research group to reduce their impact. In addition to a description of a conventional LED structure, a discussion of the device fabrication process will be provided including the solutions investigated in our group to improve LED performance. Because measurement is critical to our studies, a description of the equipment used by the AMDG will be provided, e.g., the Electroluminescence (EL) and Photoluminescence (PL) test stations, Atomic Force Microscopy (AFM) for surface topology, TLM for metallic contact resistivity, X-Ray diffraction for crystal quality and epitaxial layer structure, and Hall-Effect measurement for doping concentration characterization and material resistivity. Because the IQE gives us a direct assessment of the active region's crystal quality, the setup and operation of a new Temperature-Dependent PL (TD-PL) system to measure the Internal Quantum Efficiency (IQE) was the main focus of this research. The External Quantum Efficiency (EQE) is measured using electroluminescence measurements. The EL measurements involve the acquisition of the emitted light spectrum along with different processed data such as the Full-Width at Half Maximum (FWHM) of the spectral intensity, the peak wavelength, output power, etc., which allows a comparison of the different LED structure performances. Within this work, a new LabVIEW© program (called QuickTest 2.0) has been developed in order to automate the instrumentation setup and improve both the speed and accuracy of EL acquisition. A brief description of the G language used by the LabVIEW© software will be provided along with the objective and motivation for upgrading the program, the general features of the program, and a comparison of spectrum acquisition and processed data results. The benefit for the research in the AMDG was to reduce measurement time, improve efficiency, supply a more user-friendly front-panel, and to enable transfer to other computers.

The engineering of carrier dynamics in the MQW active region by modifying the p-type layers in the III-nitride based visible LEDs is described in this dissertation. It was found that the holes are preferentially injected into the QW adjacent to the p-InxGa1-xN layer with lower Indium mole fraction. Enhanced hole transport with increasing Indium mole fraction in the p-InxGa1-xN:Mg layer has been shown by analyzing the EL spectra. The improved hole transport and corresponding uniform distribution was achieved presumably by the potential barrier near the p-type layer and the MQW active region resulting in a modified kinetic energy of holes which creates a hole-transport-favorable environment in the MQW active region. At the same time, the limited hole injection due to the potential barrier for holes can be overcome under high injection conditions. The InAlN layers are widely used as an alternative high quality electron blocking layer in InGaN/GaN based visible LED structures. However, the Ga auto-incorporation of the InAlN layers has been recently reported during the growth of epitaxial layers by both MOCVD and MBE. The possible origins and a mechanism of Ga auto-incorporation of InAlN epitaxial layers were systematically investigated in this dissertation. It was found that the Ga-containing deposition on a wafer susceptor/carrier is the most dominant precursor for Ga auto-incorporation and the deposition on surrounding surfaces of quartz parts in a growth chamber is the other dominant source, while the effect of stainless-steel parts and interdiffusion of Ga atom from GaN underlayer are not critical. In addition, Mg or Cp2Mg in the growth chamber during InAl(Ga)N layer growth facilitates the auto-incorporation of Ga by modifying deposition conditions of GaN on the surrounding surfaces and the wafer susceptor/carrier. Based on experimental data of various cases, the Ga-containing deposition on any hot surfaces, which are also exposed to Indium precursor to form a liquid phase, is believed to be major origins of Ga auto-incorporation. In an effort to enhance the light extraction efficiency (LEE) in the LEDs, the direct patterning on the top surface of a LED structure, using laser interference ablation technique, has been studied in this dissertation. The 2-dimensional hexagonal lattice array of surface patterns was generated by direct irradiation of the laser source which is the interference of three laser beams onto the top p-GaN surface, without deterioration of electrical property of p-type layer and optical properties of MQW active region. The experimental results showed approximately 20 % improved LEE of the laser-patterned LED structure compared to the conventional LED structure without surface textures. Furthermore, the theoretical calculation using Monte-Carlo ray-tracing simulation confirmed the enhancement of LEE of the laser-patterned LED structure.

Stuttgart, Univ., Diplomarbeit, 2004.