Neste trabalho, estudamos as propriedades eletrônicas e estruturais de super-redes InP/In IND. 0.53 Ga IND. 0.47As dopadas fortemente com Si (densidade equivalente no bulk superior a 4.4 x 10 POT. 18cm POT. -3). O espectro de Fourier das oscilações de Shubnikov-de Haas apresenta um dubleto característico de elétrons que populam uma minibanda de energia, assim como uma freqüência de oscilação associada a elétrons confinados em uma camada superficial bidimensional (elétrons de Tamm). Verificamos que, para descrever o espectro de energia dos elétrons da minibanda, o modelo de Kronig-Penney é em geral suficiente porém, para descrever adequadamente os estados de Tamm é necessário recorrer a um cálculo auto-consistente completo. A boa resolução do dubleto associado aos elétrons que populam a minibanda de energia permitiu extrair as mobilidades quânticas dos elétrons associados aos hodógrafos extremais (\"cintura\" e \"pescoço\") da mini-superfície de Fermi. O tratamento de dados foi efetuado com a utilização de procedimentos especialmente desenvolvidos, que apresentam a vantagem de não necessitar da utilização de filtros de Fourier sofisticados. A detecção do estado de Tamm nas oscilações de Shubnikov-de Haas é inétida por se tratar de estados de Tamm degenerados. Por ser a mobilidade quântica dos elétrons de Tamm quase duas vezes maior do que a mesma mobilidade para os elétrons da minibanda, em campos magnéticos fracos as oscilações de Shubnikov-de Haas são dominadas pelos elétrons de Tamm, apesar da quantidade de elétrons de Tamm corresponder a apenas em torno de 10% do total de portadores livres em nossas amostras. As super-redes InP/In IND. 0.53 Ga IND. 0.47As:Si apresentam, também, grande redução de portadores livres com a diminuição do período das super-redes. A perda de portadores livres é de 60% quando o período é diminuído em 20%. Esta redução está correlacionada com a quantidade de átomos de ) dopantes que recai na camada interfacial de InAs IND. X P IND. 1-X que se forma quando InP é depositado sobre In IND. 0.53 Ga IND. 0.47As. Um estudo de um conjunto de 8 amostras nos permitiu estimar que a espessura da camada interfacial é de aproximadamente 20 ANGSTRONS. Os dados experimentais indicam que os átomos de Si que recaem nas camadas interfaciais, ao invés de formarem doadores rasos, formam centros profundos com energia de ativação superior a 50 meV. / In this work the electronic and structural properties of InP/In IND. 0.53 Ga IND. 0.47As superlattices heavily doped with Si (bulk equivalent density greater than 4.4 x 10 POT. 18cm POT. -3) were studied. The Fourier spectrum of the Shubnikov-de Haas oscillations presents a double peak characteristic of electrons which populate the first miniband of the energy spectrum, and an additional peak associated to electrons confined in a two-dimensional surface layer (Tamm electrons). We verified that the Kronig-Penney model is, in general, a good approximation to describe the energy spectrum of electrons in the miniband. However, to describe adequately the Tamm states, it is necessary to resort to a full self-consistent calculation of the energy levels in the effective mass approximation. The well-resolved doublet associated to the electrons in the miniband allowed us to extract the quantum mobilities associated to both extremal orbits of the Fermi mini-surface (belly and neck). The data analysis was done by using specially developed procedures, which have the advantage of not requiring the use of sophisticated Fourier filters. The detection of Tamm states throught Shubnikov-de Haas oscillations was done for the first time in superlattices in which the Tammm states are degenerate. On account of the fact that the quantum mobility of the Tamm electrons is about a factor of two greater than the quantum mobility of the miniband electrons, the Shubnikov-de Haas oscillations are dominated by electrons from the Tamm states, especially at weak magnetic fields, despite of the fact that the amount of Tamm electrons is only about 10% of the total amount of free carriers in our sample. The InP/In IND. 0.53 Ga IND. 0.47As:Si superlattices also display a strong reduction in the amount of free carriers when the period of the superlattice decreases. This reduction reaches 60% when the superlatticess period is decreased by only 20%. This reduction correlates with the amount of doping atoms that fall into the interfacial layer InAs IND. X P IND. 1-X which is formed when InP is grown on In IND. 0.53 Ga IND. 0.47As. A study of a set of 8 samples allowed us to estimate that the interfacial layer is approximately 20 ANGSTRONS thick. The experimental data indicate that the Si atoms which fall into the interfacial form deep levels with an activation energy larger than 50 meV.

Les diodes électroluminescentes (DEL) à base de GaN ont déjà été commercialisées comme solution économique d’éclairage, étant donné que les multi-puits quantiques (MQW) basés sur InGaN/GaN peuvent être conçus pour produire de la lumière dans toute la gamme spectrale visible. Pour obtenir une émission de lumière blanche, la conversion à base de phosphore conduit à une faible efficacité due à la perte de Stokes et peut également produire un faible indice de rendu des couleurs (IRC). Par conséquent, pour une efficacité élevée et une lumière blanche avec un IRC élevé, la génération de lumière blanche par combinaison rouges-vertes-bleues (RGB) est nécessaire. La DEL bleue basée sur InGaN/GaN présente une bonne performance aujourd'hui. La DEL rouge à base de III-phosphure est également très efficace. Cependant, avec des longueurs d'onde intermédiaires pour l'émission de spectre vert, l'efficacité des dispositifs diminue avec l'augmentation de la composition d’indium (In) dans la région active à cause de l'épitaxie selon la direction de GaN communément utilisée (0001-Ga). Ce «green-gap» est le principal obstacle pour obtenir une DEL blanche sans phosphore. Les structures DEL non ou semi-polaires pourraient être une solution pour réduire ou omettre le problème de polarisation, cependant, une croissance plus facile de bonne qualité cristalline avec moins d'étapes de fabrication font que la croissance de la direction (0001-Ga) est toujours commercialement prometteuse. Par conséquent, une conception de structure optimisée pour atténuer la polarisation et augmenter l'émission optique provenant d'hétéro-structures élaborées dans cette direction de croissance est toujours demandée. Les structures de DEL classiques multi-puits quantiques (MQW) InGaN/GaN sont développées sur une template GaN et utilisent du GaN comme couches barrières. Cependant, notre objectif a été de faire croître des MQW à contenu élevé avec des barrières InGaN sur une nouvelle template InGaN appelé «semi-bulk» (SB). La réalisation de la thèse est de simuler, décroître par épitaxie en phase vapeur organométallique (MOVPE) et de fabriquer la structure de DELs à haute teneur en In dans les barrières MQW avec InGaN, crues sur une template InGaN «semi-bulk» de haute qualité, et qui émettent dans le spectre du bleu au vert / GaN-based light-emitting diodes (LEDs) have already been commercialized for solid-state lighting, since the InGaN/GaN-based multi-quantum-well (MQW) of LEDs can be designed to produce light in the entire visible spectral range. To obtain white LED, phosphor-based down-conversion results in low efficiency due to Stokes loss and also can yield low colour rendering index (CRI). Hence, for highly efficient and with high CRI white light, generation of white light by monolithic red-green-blue (RGB) combination is necessary. InGaN/GaN-based blue LED has good performance now-a-days. III-phosphides based red LED has also achieved good efficiency. However, with intermediary wavelengths for green spectra emission, the efficiency of devices from epitaxy grown along the commonly used (0001-Ga) direction of GaN decreases with increasing indium (In) content in the active region and this “green-gap” is the main obstacle to get phosphor-free white LEDs. Non- or semi-polar LED structures could be a solution to reduce or omit the polarization problem, however, easier growth of good crystal quality and fewer processing steps make (0001-Ga) direction growth still commercially promising. Therefore, optimized structure design to alleviate polarization and enhance optical emission from hetero-structures grown along this direction growth is still in demand. The conventional InGaN multi-quantum-well (MQW) LED structures are grown on GaN buffer and use GaN as barrier layers. However, the objective of this thesis has been to grow high In-content MQWs with InGaN barriers on a novel so called “semi-bulk” (SB) InGaN buffer. The achievement of the thesis was to simulate, grow by metalorganic vapour phase epitaxy (MOVPE) and process LED structure with high In-content in the MQW with InGaN barriers, grown on high quality “semi-bulk” InGaN buffer, that will emit in the blue to green spectra. 70 nm thick high crystal quality InGaN SB buffer was obtained with 5% In-content. On top of this, In0.15Ga0.85N/In0.05Ga0.95N MQW was grown followed by 200 nm optimized p-GaN. The room temperature IQE was 67.5% at 460 nm emission wavelength. The processed LED chips yielded turn-on voltage less than 3 V with leakage current of ~10-3 A. In0.25Ga0.75N/ In0.05Ga0.95N MQW was also realized on InGaN SB with 7% In, with emission peak at ~530 nm

Ce travail porte sur la croissance par MOVPE et l’étude de structures à base de nanofilsde ZnO, semi-conducteur à large bande interdite directe (3,37 eV) qui possède un fort po-tentiel pour les applications optoélectroniques. Des observations systématiques par MEBet TEM de nanofils de ZnO crûs sur saphir, sous différentes conditions, renseignent surla formation de ces nanostructures et notamment sur l’importance de la polarité du ma-tériau. Les observations structurales par TEM révèlent l’absence de défaut étendu dansles nanofils. Dans un second temps, la croissance de structures à puits quantiques coeur-coquilles ZnO/ZnMgO est étudiée. L’imagerie de cathodoluminescence révèle l’émis-sion de puits quantiques axiaux (avec effet stark confiné) et radiaux. L’optimisation dela composition en Mg des barrières ZnMgO permet d’éviter la relaxation plastique dansles nanofils et montre une amélioration très significative de la tenue en température del’émission de photoluminescence des puits quantiques radiaux. Le rendement quantiqueinterne des meilleures structures est estimé à 54%. Enfin, la localisation de la croissancesur substrats structurés est démontrée. La morphologie ainsi que le taux de remplissagedes nanofils sont comparés en fonction de la polarité de la couche de germination utilisé,de la taille et de l’espacement des ouvertures pratiquées dans le masque. L’ensemble deces briques technologiques ouvre la voie à la réalisation de LEDs à base de nanofils ZnO. / This work deals with the MOVPE growth and the study of ZnO based structures,which is a direct and large gap semiconductor (3.37 eV) with a high potential for op-toelectronics applications. Systematic SEM and TEM observations of ZnO nanowires onsapphire grown under various conditions help us to understand growth mechanism, andmore particularly the role of the polarity in formation of nanowires. Structural TEM ob-servations reveal the lack of dislocations or stacking fault in nanowires. In a second hand,the growth of ZnO/ZnMgO core-shell structure with quantum wells is studied. Cathodolu-minescence mapping exhibit both radial and axial quantum wells emission with quantumconfinement and quantum confined stark effect, respectively. Mg composition is optimi-zed to avoid plastic relaxation in nanowires structure, which allow us to obtain internalquantum efficiency as high as 54%. Finally, the selective area growth is demonstrated onpatterned substrates. Morphology and efficiency of ZnO nanowires growth is compare asa function of seed layer polarity and size of holes in the mask. These technological stepsopen the way to ZnO nanowires based LEDs devices.

Neste trabalho, estudamos as propriedades eletrônicas e estruturais de super-redes InP/In IND. 0.53 Ga IND. 0.47As dopadas fortemente com Si (densidade equivalente no bulk superior a 4.4 x 10 POT. 18cm POT. -3). O espectro de Fourier das oscilações de Shubnikov-de Haas apresenta um dubleto característico de elétrons que populam uma minibanda de energia, assim como uma freqüência de oscilação associada a elétrons confinados em uma camada superficial bidimensional (elétrons de Tamm). Verificamos que, para descrever o espectro de energia dos elétrons da minibanda, o modelo de Kronig-Penney é em geral suficiente porém, para descrever adequadamente os estados de Tamm é necessário recorrer a um cálculo auto-consistente completo. A boa resolução do dubleto associado aos elétrons que populam a minibanda de energia permitiu extrair as mobilidades quânticas dos elétrons associados aos hodógrafos extremais (\"cintura\" e \"pescoço\") da mini-superfície de Fermi. O tratamento de dados foi efetuado com a utilização de procedimentos especialmente desenvolvidos, que apresentam a vantagem de não necessitar da utilização de filtros de Fourier sofisticados. A detecção do estado de Tamm nas oscilações de Shubnikov-de Haas é inétida por se tratar de estados de Tamm degenerados. Por ser a mobilidade quântica dos elétrons de Tamm quase duas vezes maior do que a mesma mobilidade para os elétrons da minibanda, em campos magnéticos fracos as oscilações de Shubnikov-de Haas são dominadas pelos elétrons de Tamm, apesar da quantidade de elétrons de Tamm corresponder a apenas em torno de 10% do total de portadores livres em nossas amostras. As super-redes InP/In IND. 0.53 Ga IND. 0.47As:Si apresentam, também, grande redução de portadores livres com a diminuição do período das super-redes. A perda de portadores livres é de 60% quando o período é diminuído em 20%. Esta redução está correlacionada com a quantidade de átomos de ) dopantes que recai na camada interfacial de InAs IND. X P IND. 1-X que se forma quando InP é depositado sobre In IND. 0.53 Ga IND. 0.47As. Um estudo de um conjunto de 8 amostras nos permitiu estimar que a espessura da camada interfacial é de aproximadamente 20 ANGSTRONS. Os dados experimentais indicam que os átomos de Si que recaem nas camadas interfaciais, ao invés de formarem doadores rasos, formam centros profundos com energia de ativação superior a 50 meV. / In this work the electronic and structural properties of InP/In IND. 0.53 Ga IND. 0.47As superlattices heavily doped with Si (bulk equivalent density greater than 4.4 x 10 POT. 18cm POT. -3) were studied. The Fourier spectrum of the Shubnikov-de Haas oscillations presents a double peak characteristic of electrons which populate the first miniband of the energy spectrum, and an additional peak associated to electrons confined in a two-dimensional surface layer (Tamm electrons). We verified that the Kronig-Penney model is, in general, a good approximation to describe the energy spectrum of electrons in the miniband. However, to describe adequately the Tamm states, it is necessary to resort to a full self-consistent calculation of the energy levels in the effective mass approximation. The well-resolved doublet associated to the electrons in the miniband allowed us to extract the quantum mobilities associated to both extremal orbits of the Fermi mini-surface (belly and neck). The data analysis was done by using specially developed procedures, which have the advantage of not requiring the use of sophisticated Fourier filters. The detection of Tamm states throught Shubnikov-de Haas oscillations was done for the first time in superlattices in which the Tammm states are degenerate. On account of the fact that the quantum mobility of the Tamm electrons is about a factor of two greater than the quantum mobility of the miniband electrons, the Shubnikov-de Haas oscillations are dominated by electrons from the Tamm states, especially at weak magnetic fields, despite of the fact that the amount of Tamm electrons is only about 10% of the total amount of free carriers in our sample. The InP/In IND. 0.53 Ga IND. 0.47As:Si superlattices also display a strong reduction in the amount of free carriers when the period of the superlattice decreases. This reduction reaches 60% when the superlatticess period is decreased by only 20%. This reduction correlates with the amount of doping atoms that fall into the interfacial layer InAs IND. X P IND. 1-X which is formed when InP is grown on In IND. 0.53 Ga IND. 0.47As. A study of a set of 8 samples allowed us to estimate that the interfacial layer is approximately 20 ANGSTRONS thick. The experimental data indicate that the Si atoms which fall into the interfacial form deep levels with an activation energy larger than 50 meV.

Effiziente und erneuerbare Wasserstofferzeugung ist eine der entscheidenden Herausforderungen für eine von fossilen Brennstoffen unabhängige Gesellschaft. Tandem-Absorber-Strukturen, die auf verdünnt Stickstoff-haltigem GaPN/Si(100) basieren, sind vielversprechend für die Wasserstoffproduktion mittels direkter solarer Wasserspaltung. Ihre Herstellung mittels metallorganischer Gasphasenepitaxie (MOVPE) ist anspruchsvoll, insbesondere bezüglich gezielter Präparation der Grenzflächen. Wegen der geringen Gitterfehlanpassung eignen sich pseudomorphe GaP/Si(100) Strukturen als Quasisubstrate für weitere Integration anderer III-V Halbleiter. In der vorliegenden Arbeit wird die atomare Ordnung von Si(100) und GaP(N)/Si(100) Oberflächen, sowie der vergrabenen GaP/Si(100) Heterogrenzfläche in situ mit Reflexions-Anisotropie-Spektroskopie (RAS) untersucht. RAS Ergebnisse werden dabei mit Ergebnissen komplementärer Methoden der Oberflächenanalytik im Ultrahochvakuum (UHV) verglichen, beispielsweise mit niederenergetischer Elektronenbeugung (LEED) und Röntgenphotoelektronenspektroskopie (XPS). Die Präparation nahezu eindomäniger, dimerisierter Si(100) Oberflächen gelingt erfolgreich in MOVPE Atmosphäre mit Hintergrundverunreinigungen von (Ga, P) und kann in situ mit RAS kontrolliert werden. Die Untergitterorientierung des GaP Films kann dabei über (i) die Dimerorientierung des Si Substrats, (ii) das (Ga,P) chemische Potential während der Nukleation und (iii) über Modifikation der Si-Oberfläche mit As gesteuert werden. Aus der Korrelation zeitaufgelöster RAS- und XPS-Messungen sowie Dichtefunktionaltheorie-Rechnungen kann unter typischen Prozessbedingungen auf die kinetisch limitierte Bildung einer Si-P Grenzfläche geschlossen werden. Im Anschluss an eine nur wenige Atomlagen dicke GaP Nukleationsschicht können Antiphasen-Unordnungs-freie GaPN/Si(100) Oberflächen präpariert werden. Diese rekonstruieren analog zu GaP/Si(100) Oberflächen, wenn überschüssiger N vermieden wird. / Renewable and efficient generation of hydrogen is one of the key challenges towards a society being independent from fossil fuels. Tandem absorber structures based on dilute nitride GaPN/Si(100) are promising candidates regarding hydrogen evolution by direct solar water splitting. Their production by metalorganic vapor phase epitaxy (MOVPE) is challenging, particularly regarding specific preparation of the interfaces. Due to the small lattice mismatch, GaP/Si(100) structures are suitable as quasisubstrates for further integration of III-V semiconductors. In the present work, the atomic order of Si(100) and GaP(N)/Si(100) surfaces, as well as of the buried GaP/Si(100) heterointerface is studied in situ with reflection anisotropy spectroscopy (RAS). RAS results are benchmarked to results from complementary surface science techniques in ultrahigh vacuum (UHV), such as low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Preparation of almost single-domain dimerized Si(100) surfaces succeeds in MOVPE ambient containing (Ga, P) background residuals and can be controlled in situ with RAS. The sublattice orientation of the GaP films can thereby be selected (i) via the dimer orientation on the Si substrate, (ii) via the (Ga,P) chemical potential during nucleation, or (iii) via modification of the Si surface with As. Correlating time-resolved RAS and XPS measurements as well as density functional theory calculations, for typical process conditions it can be concluded on a kinetically limited formation of a Si-P interface. Subsequent to a GaP nucleation layer, which is only few atomic layers thick, GaPN/Si(100) surfaces free of antiphase disorder can be prepared. These reconstruct in analogy to GaP/Si(100) surfaces if excess N is avoided.

Cette thèse s’intéresse à l'intégration sur Si de cellules solaires III-V à simple et double jonction par épitaxie en phase vapeur aux organo-métalliques (MOVPE). Les dispositifs photovoltaïques ont été réalisés avec des matériaux accordés sur InP. L'objectif était d'abord d'obtenir des dispositifs performants sur des substrats InP, puis de les intégrer sur une structure avec un paramètre de maille différent, en évaluant les effets sur les performances photovoltaïques. Ceci a nécessité la réalisation et l'optimisation de plusieurs étapes de fabrication.Tout d'abord, nous avons réalisé une cellule InP à simple jonction, qui peut correspondre à la cellule top dans notre structure tandem. Cela était également nécessaire pour mettre en place un processus de fabrication pour toutes les cellules suivantes. Les conditions de croissance ont été optimisées en profitant des techniques de caractérisation des matériaux telles que la XRD, l’analyse C-V et le SIMS. En optimisant les épaisseurs et les niveaux de dopage des différentes couches du dispositif, ainsi que le procédé en salle blanche, nous avons obtenu une efficacité de conversion de 12.9%, avec un FF de 84.3%. Nous avons démontré que l'utilisation d'une couche fenêtre en AlInAs au lieu de l’InP peut augmenter l'efficacité à 13.5%, malgré une légère réduction du FF (81.4%). La même procédure a ensuite été étendue à la réalisation d'une cellule solaire InGaAs comme cellule bottom du dispositif tandem. Nous avons obtenu un rendement de 11.4% et un FF de 74.5%.En parallèle, des jonctions tunnels capables de relier électriquement les deux sous-cellules dans un dispositif tandem ont été étudiées. En particulier, nous avons concentré notre attention sur les conditions de croissance de l'anode de la jonction, qui a été fabriquée en AlInAs et dopée avec le précurseur CBr4. Les réactions chimiques d’un tel précurseur avec le précurseur de l’Al et l’In nécessitaient une importante réduction de la température de croissance à 540 °C. En déterminant les effets des flux sur la composition et les niveaux de dopage du composé, nous avons obtenu un dopage élevé de +4x1019 cm-3. En obtenant un niveau équivalent pour la cathode InP:S, nous avons réalisé un dispositif présentant un Jp de 1570 A/cm2, capable de fonctionner dans des conditions de concentration solaire élevée. En combinant finalement les trois dispositifs présentés dans une cellule tandem, nous avons pu obtenir un rendement global de conversion de 18.3%, avec un FF de 83.9%.Un template approprié pour l'intégration III-V/Si a été déterminé en testant plusieurs possibilités fournies par différents partenaires. Les caractérisations XRD et AFM ont démontré qu'un template InP/GaP/Si fourni par la société NAsP était la meilleure option. Ceci a été confirmé par la croissance d'une cellule InP à simple jonction sur le template. La techno sur un substrat Si a été rendu possible en déplaçant le contact arrière de la cellule sur la face avant du dispositif, ce qui a nécessité la mise au point d'un ensemble approprié de masques photolithographiques. La réussite de l’intégration des cellules solaires III-V sur Si a été confirmée par le photocourant produit. Celui-ci correspond à environ 60% de la valeur obtenue sur les substrats InP. De plus, les caractéristiques J-V mesurées donnent une tendance de type diode, démontrant la validité de l'approche proposée. / This thesis focuses on III-V/Si integration of single- and dual-junction solar cells by Metalorganic Vapor Phase Epitaxy (MOVPE). The photovoltaic devices were made with materials lattice matched to InP. The goal was to firstly obtain efficient devices on InP substrates and then to integrate them on a structure with a different lattice parameter, by evaluating the effects on the photovoltaic performances. This required the realization and the optimization of several manufacturing steps.Firstly, we realized an InP single junction device, which may correspond to the top cell of our tandem structure. This was also necessary to set up a manufacturing process for all the next cells. The growth conditions were optimized by taking advantage of material characterization techniques such as XRD, C-V profiling and SIMS. By optimizing thicknesses and doping levels of the various layers of the device, as well as the clean room process, we obtained a conversion efficiency of 12.9%, with a FF of 84.3%. We demonstrated that the use of an AlInAs window layer instead of InP may increase the efficiency to 13.5%, despite a slight reduction in FF (81.4%). The same procedure was then extended to the realization of an InGaAs solar cell as the bottom component of the tandem device. We obtained an efficiency of 11.4% and a FF of 74.5%.In parallel, tunnel junctions able to electrically connect the two subcells in a tandem device were studied. In particular, we focused our attention on the growth conditions of the junction anode, which was made in AlInAs and doped with CBr4 precursor. The particular chemical interactions that such a precursor has with Al precursor and In required a relevant reduction of growth temperature to 540 °C. By determining the effects of the flows on composition and doping levels of the compound, we obtained a high doping of +4x1019 cm-3. By obtaining an equivalent level for the InP:S cathode, we realized a device presenting a Jp of 1570 A/cm2, able to work under high solar concentration conditions. By finally combining the three presented devices in a tandem cell, we could obtain an overall conversion efficiency of 18.3%, with a FF of 83.9%.A proper template for III-V/Si integration was determined by testing several possibilities provided by different partners. XRD and AFM characterizations demonstrated that an InP/GaP/Si template provided by NAsP Company was the best option. This was confirmed by the growth of an InP single junction cell over the template. The processing over a Si substrate was made possible by shifting the rear contact of the cell on the front side of the device, which required the development of a proper set of photolithographic masks. The successful integration of the III-V solar cells on Si was confirmed by the relevant produced photocurrent. This corresponds to around 60% of the value obtained on InP substrates. Furthermore, the measured J-V characteristics show a diode-like trend, which demonstrates the validity of the proposed approach.

Cette thèse est une contribution à l'étude de composés semiconducteurs InX Al1-X N à forte teneur en Indium. Ces composés présentent des propriétés très intéressantes pour des applications dans le domaine de l'amplification des hyperfréquences. L'objectif principal de la thèse est de définir des hétéro-structures de type AlGaInN / GaN, pour transistors à Effet de Champ Piézoélectrique (HEMT), épitaxiées sur substrats de saphir, silicium, et SiC, optimisées en vue de l'amplification hyperfréquence. Dans la première partie, nous étudions la croissance épitaxiale de couches minces du composé binaire GaN, en phase vapeur, à partir de précurseurs organométalliques (MOVPE), dans des conditions optimisées pour obtenir des couches fortement résistives. La deuxième partie est consacrée à l'étude de structures HEMT AlGaN/GaN sur SiC et sur silicium. Sur SiC, nous montrons la forte influence des propriétés du substrat sur les propriétés électriques des structures HEMT. Nous avons étudié une structure nouvelle incluant une fine couche de AlN entre les couches AlGaN et GaN et évalué les performances de transistors HEMT AlGaN/GaN et AlGaN/AlN/GaN sur SiC et sur Silicium (111). La partie suivante est consacrée à la croissance de composés ternaires InAlN. Nous avons étudié l'influence de la température de croissance et du rapport V/III sur les propriétés structurales de InAlN. Les conditions optimales ont été utilisées pour la réalisation de structures HEMT InAlN/AlN/GaN. Nous démontrons l'influence considérable de la couche AlN sur les propriétés électriques de ces structures. Enfin, nous discutons les performances obtenues sur des transistors à effet de champ InAlN/AlN/GaN sur SiC / This work reports on the metal-organic vapor phase epitaxy and on the characterisation of III-N GaInAlN heterostructures for High Electron Mobility Transistors. In a first part, the heteroepitaxy of semiinsulating GaN layers on sapphire, SiC and silicon is presented as the basis for the subsequent growth of III-N HEMT structures. The influence of suitable nucleation layers on the properties of GaN is presented and discussed. A second part deals with AlGaN/GaN HEMT structures grown on SiC and on Si (111) wafers. The influence of SiC substrate properties on the electrical performances of AlGaN/GaN HEMT is presented. A novel structure, including a thin AlN interlayer between the GaN buffer layer and the AlGaN barrier layer has also been introduced. The section is completed by device results obtained on selected heterostructures. A study of the impact of selected growth parameter (i.e. growth temperature, V/III ratio) on the structural and surface properties of InAlN layers is then presented. The optimized conditions have been used for the growth InAlN/AlN/GaN HEMT structures which have been thoroughly characterized. The electrical properties of the structures were found to be strongly dependent on the growth conditions of the AlN interlayer (e.g. deposition time, V/III ratio). Finally, state of the art device results obtained with InAlN/AlN/GaN heterostructures are presented

[pt] Substratos de germânio (Ge) são utilizados para o crescimento de dispositivos optoeletrônicos III-V, como células solares. Porém, o Ge é uma matéria-prima crítica devido à sua disponibilidade limitada. Além disso, o substrato de Ge representa cerca de 30-40 por cento dos custos totais de uma célula solar de junção tripla. Neste trabalho, foram crescidas amostras e células solares III-V sobre substratos de Ge com diferentes tecnologias (tec). Três diferentes tecs foram investigadas: 1) utilizando substratos de Ge com camadas porosas para crescer materiais III-V, sendo que a camada porosa é retirada para que o substrato possa ser reutilizado; 2) utilizando substratos mais finos e com menos processos de finalização da superfície, o que a deixa mais rugosa comparada a substratos comerciais; 3) substituindo o substrato de Ge por substratos alternativos que compreendam outros elementos, como um substrato de Si onde é depositado um buffer metamórfico de SiGe, no qual o parâmetro de rede foi ajustado até o chegar no de Si0.1Ge0.9. Os substratos utilizados não são perfeitos como os substratos comerciais de Ge e podem gerar defeitos nas camadas de III-V subsequentes. Para investigar a influência desses substratos nas camadas III-V foram crescidas heteroestruturas duplas (HED) de AlGaInAs/GaInAs nos substratos das tecs 1 e 2 e HED de AlGaAs/GaAs nos substratos da tec 3. Suas propriedades foram avaliadas com AFM para obter a rugosidade média quadrática e possíveis defeitos da superfície, catodoluminescência para estimar a densidade de defeitos na estrutura e Electron Channeling Contrast Imaging para identificar os tipos de defeitos encontrados com CL. Além disso, para as amostras crescidas sobre os substratos tec 1, suas composições e espessuras foram investigadas por XRD e com fotoluminescência resolvida no tempo avaliou-se o tempo de vida dos elétrons. Nos substratos das tecs 2 e 3 também foram crescidas células solares de junção tripla, que foram processadas e caracterizadas por curvas I-V e EQE. Os resultados obtidos com todas as tecs levam a uma perspectiva otimista para um futuro com células solares mais baratas e que utilizem menos Ge. / [en] Germanium (Ge) substrates are used for the growth of III-V optoelectronic devices such as solar cells. However, Ge is a critical raw material due to its limited availability. Furthermore, Ge substrate accounts for about 30-40 percent of the total costs of a triple junction solar cell. In this work III-V samples and solar cells were grown on Ge substrates with different technologies (techs). Three different techs were investigated: 1) using Ge substrates with porous layers to grow III-V materials, in which the porous layer is removed so that the substrate can be reused; 2) using thinner substrates and with fewer surface finishing processes, which makes it rougher compared to commercial substrates; 3) replacing the Ge substrate with alternative substrates that comprise other elements, such as a Si substrate where a metamorphic SiGe buffer is deposited, in which the lattice parameter is gradually adjusted until it reaches Si0.1 Ge0.9. The substrates used are not as perfect as commercial Ge substrates and can generate defects in the subsequent III-V layers. To investigate the influence of these substrates on III-V layers, double heterostructures (DH) of AlGaInAs/GaInAs were grown on the substrates of techs 1 and 2 and DH of AlGaAs/GaAs on the substrates of tech 3. Their properties were evaluated with AFM to obtain the root mean square roughness and possible surface defects, cathodoluminescence to estimate the density of defects in the structure and Electron Channeling Contrast Imaging to identify the types of defects found with CL. Furthermore, for samples grown on tech 1 substrates, the compositions and thicknesses were evaluated by XRD, and with time-resolved photoluminescence, the lifetime of the electrons was evaluated. Triple junction solar cells were also grown on techs 2 and 3 substrates, which were processed and characterized by I-V and EQE curves. The results obtained with all tecs lead to an optimistic perspective for a future with cheaper solar cells that use less Ge.

[pt] Neste trabalho tem sido investigado a presença de defeitos em células solares de banda intermediária (IB) de GaAs con pontos quânticos (PQs) de InAs. As três células estudadas contêm camadas de separação entre as camadas de PQs, as quais foram crescidas à diferentes temperaturas, e camadas delgadas de recobrimento dos PQs de diferentes espessuras. As eficiências de conversão de energia destas células foram medidas previamente, sendo que a célula com camadas de separação crescidas à 700 graus C e com camadas de recobrimento de 3 nm é a mais eficiente (6.9 por cento). As outras duas células com camadas de recobrimento de 6 nm apresentam menores eficiências: uma, com camadas separadoras crescidas à 700 graus C, com 5.1 por cento, e a outra, com camadas separadoras crescidas à 630 graus C, com 2.8 por cento. Estudos de DLTS e Laplace DLTS mostram que há um grande número de defeitos em altas concentrações na célula menos eficiente, enquanto nas outras duas células só é detetado o mesmo defeito EL2 em menores concentrações. Portanto, a redução dos defeitos induz o incremento da eficiência das células IB. Amostras adicionais foram crescidas e estudadas pelas mesmas técnicas, entre elas, três células solares com estruturas idênticas às das células IB, mas sem PQs, e quatro amostras GaAs mono-camada dopadas com carbono e silício, similares às camadas de contacto p e n das células IB. Do estudo das três células sem PQs foi possível determinar que alguns defeitos nas células IB são induzidos pelas condições de crescimento dos PQs ou são induzidos pela temperatura de crescimento das camadas separadoras. O estudo das amostras mono-camada indicou a presença de defeitos nos contatos p e n que podem armadilhar os portadores foto-excitados nas células sob operação e, portanto, limitar a eficiência delas. Os resultados deste trabalho contribuem para desenvolver novas estratégias para crescimento epitaxial de células IB no laboratório LabSem na PUC-Rio. / [en] Defects present in structures of intermediate band (IB) solar cells of GaAs with InAs quantum dots (QDs) grown by MOVPE have been investigated. The three studied IB solar cells differ in the growth temperature of the spacer layers that separate the InAs QD layers in the active region and the thickness of the thin layer that capping each QD layer. Previously, the energy conversion efficiencies of these cells were measured and the cell with the highest spacer layer-growth temperature (700 C degrees) and thinner capping layer (3 nm) showed the highest efficiency, about 6.9 percent. The cells with thicker capping layers (6 nm) showed lower efficiencies, one of them, with spacer layers grown at 700 C degrees, reaching 5.1 percent, and the other one, with spacer layers grown at 600 C degrees, reaching only 2.8 percent. In this work, DLTS and Laplace DLTS studies show that the cell with the lowest efficiency has the largest number and highest concentrations of defects, unlike the other two cells, which have only one trap, EL2, in lower concentrations. These results demonstrate that the different growth conditions are determinant for the formation of defects and that the defect reduction leads to the increase of the IB solar cell efficiencies. Other samples were also grown and studied by the same techniques: three solar cells with identical structure as the IB solar cells, but without QDs, and individually doped GaAs samples that represent the p and n contact sides of the IB solar cells. From the study of the cells without QDs, the origin of some defects in the IB solar cells was found to be related to the QD growth conditions or related to the spacer layer-growth temperature. The study of the GaAs samples indicated the presence of defects in the p and n sides that could trap photo-excited carriers collected through these contacts during cell operation and thus reduce the efficiency. The results of this work allow developing new strategies to improve the epitaxial growth quality of IB solar cells in the laboratory of semiconductors LabSem of PUC-Rio where the studied samples were grown.

Cette thèse portait sur la caractérisation électrique et optique de nouveaux matériaux à base d'alliages III-N pour l’optoélectronique et la mise en œuvre de procédés de réalisation des contacts ohmiques et Schottky sur ces alliages. Le premier volet de cette thèse de concernait la maîtrise des contacts métalliques, particulièrement délicate dans le cas de ces matériaux à large bande interdite où il faut optimiser les prétraitements de surface, la métallisation multicouches et les procédés de recuit. Nous avons développé des procédés à relativement basse température (entre 200°C et 500°C) et étudié l'influence du prétraitement chimique et des paramètres du recuit et on a pu trouver des conditions permettant d'obtenir des contacts Ti/Al avec une excellente ohmicité et des contacts Schottky Au et Pt avec des paramètres de conduction permettant de réaliser des dispositifs fonctionnels. Le second volet de cette thèse concernait l'étude des propriétés électroniques et structurales de l'alliage BGaN, nouveau matériau élaboré au laboratoire par MOVPE. La caractérisation électrique a montré pour la première fois une augmentation drastique de la résistivité associée à une diminution de la concentration des porteurs libres lorsqu'on augmente la composition de bore dans BGaN. Grâce à des mesures de la résistivité du BGaN en fonction de la température et en utilisant un modèle qui prend en compte l'ensemble des interactions, cette augmentation de la résistivité a été discutée et interprétée en terme de compensation des dopants résiduels. En outre une très intéressante corrélation a pu être effectuée avec les résultats de la spectroscopie Raman via le couplage phonon-plasmon / This thesis work concerns the electrical and optical characterization of new III-N nitride alloys for optoelectronics and the optimization of ohmic and Schottky contacts on these materials. The first part of this thesis was related to the realization of metallic contacts, particularly difficult for these high bandgap materials, by the optimization of the surface treatment, multi-layer metallization and thermal annealing. We developed annealing processes at relatively low temperature (between 200°C and 500°C) and studied the effect of the chemical treatment and annealing in order to find the optimal conditions for ohmic contacts. We obtained for instance Ti/Al contacts with an excellent ohmicity and used Pt to process Schottky functional diodes. The second part of this thesis was related to the study of the electronic and structural properties of the new BGaN alloy grown by MOVPE in our laboratory. The electric characterization showed for the first time a dramatic increase in the resistivity associated to the decrease of the free carriers’ concentration when the composition of boron in BGaN increases. The variation of the resistivity in BGaN with respect to the temperature was analyzed by using a theoretical model which takes into account the free carriers’ interaction with impurities and phonons and the variation of resistivity with boron in BGaN was discussed in this framework and linked to a compensation phenomenon of the residual dopants. On the other hand a very interesting correlation was carried out between Raman and electrical results through the phonon-plasmon coupling