Poços e super-redes delta-doping tipo são sistemas semicondutores de interesse considerável tanto para a pesquisa básica como para aplicações em dispositivos. Neste trabalho desenvolvemos um novo método para o cálculo de potenciais e estruturas de bandas deste tipo de sistemas. O método baseia-se na expansão em ondas planas da equação da massa efetiva multibandas, usa matrizes de energia cinética de qualquer tamanho e leva em conta o potencial de troca e correlação de uma maneira mais rigorosa do que em trabalhos anteriores. São calculados perfis de potencial e estrutura de minibandas e subbandas bem como a posição do nível de Fermi de uma série de poços isolados e super-redes delta-doping tipo p. São estudadas também as diferenças entre super-redes delta-doping tipo p e tipo n. A partir deste método foi desenvolvido ainda um procedimento de cálculo de espectros de fotoluminescência dos poços estudados. Este procedimento baseia-se nas forças de oscilador das transições entre os buracos confinados no interior do poço e os elétrons livres da banda de condução. Ele é utilizado para calcular funções envelope, integrais de superposição e espectros de transições diretas e indiretas. Por fim, comparamos espectros calculados teoricamente com resultados experimentais extraídos da literatura. / p-type ro-doping quantum wells and superlattices are semiconductor systems of considerable interest for basic research and device applications. In this work, a method for calculating potentials and band structures of such systems is developed. The method relies on a plane wave expansion of the multiband effective mass equation, uses kinetic energy matrices of any size, and takes exchange correlation into account in a more rigorous way than this was done before. The method is used to calculate potential profiles, subband and miniband structures as well as Fermi level positions for a series of p-type delta-doping quantum wells and superlattices. The differences between n- and p-type delta-doping structures are studied. In addition to this we developed a procedure within this method to ca1culate photoluminescence (PL) spectra of the wells studied. It depends on the oscillator strength between the holes inside the wells and the free electrons on the conduction band. We use this procedure to calculate envelope functions, overlap integrals and direct and indirect transitions spectra. Finally, we compare our theoretical calculations of PL spectra with experimental results extracted from the literature.

Temos utilizado o método de Hartree-Fock-Roothaan, seguido da teoria de perturbação de segunda ordem, para a determinação das propriedades estruturais e eletrônicas dos aglornerados GaAs, G2As, GaAs2, Ga3As, Ga2As2, GaAs3, G4As, Ga3As2, Ga2As4, GaAs4, Ga3As3, G4Asa, Ga3As4, Ga4As4 e seus íons positivos e negativos. A estrutura de equilíbrio de cada um destes aglomerados foi determinada através de cálculos de otimização de geometria sem a imposição de vínculos espaciais de simetria sobre a função de onda. Uma vez determinadas as estruturas dos estados fundamentais destes aglomerados, obtivemos os valores de diversas propriedades eletrônicas e energéticas, como o potencial de ionização, a afinidade eletrônica, 0 bond-order, populações orbitais de Mulliken, carga sobre os átomos, natureza dos HOMO-LUMO, etc. Com estas informações, pudemos então descrever de forma detalhada cada um destes aglomerados e comparar nossos resultados com os existentes na literatura. Realizando uma analise conjunta dos resultados obtidos, deduzimos um padrão estrutural a ser seguido por estes pequenos aglomerados de GaAs, onde as formas embrionárias destes aglomerados têm SUM estruturas geométrica e eletrônica baseadas em configurações altamente simétricas, formadas pelos átomos de As. Os átomos adicionais de Ga entram em posições que favorecem um padrão de hibridização e ordenamento químico que tende ao padrão apresentado pelo cristal de GaAs. A passagem para uma estrutura em camadas e observada ocorrer ja no aglomerado estequiométrico com oito átomos. Utilizando o princípio de hard and soft acids and bases, estudamos a reatividade química do aglomerado Ga2As2 e da superfície GaAs[ll0], quando em interação com átomos externos. / Using the Hartree-Fock-Roothaan method, followed by second-order perturbation theory we determined the structural and electronic properties of the GaAs, Ga2As, GaAs2, Ga3As, Ga2As2, GaAs3, Ga4As, Ga3As2, Ga2As3, GaAs4, Ga3As3, Ga4As3, Ga4As4, Ga4As4 clusters and its positive and negative ions. The equilibrium structure for each of these clusters was determined throgh geometry optimization calculations, without spatial symmetry constraint on the wave function. Once we have determined the ground state structures of these clusters, the values of different electronic and structural properties were evaluated. This includes the ionization potential, electron affinity, bond-order, Mulliken populations, the nature of the HOMO-LUMO orbitals, etc. With these informations we described in detail each one of the clusters, and we compared our results with the experimental and theoretical published results. Analysing the assembly of the obtained results, we can deduce a structural pattern to be followed by these small clusters of GaAs, where the embrionary forms of these clusters have the geometric and electronic structures based on highly symmetrical configurations formed by the As atoms. The Ga aditional atoms enter in positions that enhance a hybridization and chemical ordering which tends to that presented by the bulk. The change for a layer structure is observed occur yet in the eight atoms stechiometric cluster. Using the hard and soft acids and bases principle, we have studied chemical reactivity of the Ga2As2 cluster and the GaAs[ll0] surface when in interaction with atoms.

Les boîtes quantiques sous formes de nanocristaux semi-conducteurs permettent de réaliser des matériaux à énergie de gap variable, propriété très intéressante pour les composants optoélectroniques. Ce travail est dédié à la création de nanocristaux de silicium dopés enfouis dans SiO2 et de nanocistaux binaires (InAs et GaAs) et ternaires d’InxGa1-xAs enfouis dans Si et à leurs caractérisations structurales, électriques et optiques. La synthèse par faisceaux d’ions permet d’avoir un contrôle de la quantité et de la taille des nanocristaux synthétisés. Des caractérisations structurales ont pu démontrer le dopage des nanocristaux de silicium avec le phosphore et l’arsenic à une concentration atomique moyenne de 8 %. Nous avons également montré la possibilité de moduler la taille et la composition chimique des nanocristaux d’InxGa1-xAs sur une large gamme à l’aide de la dose d’implantation et de la température de recuit. / Semiconductor nanocrystals can be used as quantum dots to produce band gap engineering by varying the nanocrystals size, which is a very interesting property for optoelectronic components. This work is dedicated to the creation of doped silicon nanocrystals embedded in SiO2 and binary (InAs and GaAs) and ternary nanocrystals of InxGa1-xAs embedded in Si and also to investigate their structural, electrical and optical properties. Ion beam synthesis allows a control of the nanocrystals amount and size. Structural characterizations were able to demonstrate the doping of silicon nanocrystals with phosphorus and arsenic at an average atomic concentration of 8 %. We have also shown the ability to modulate the size and the chemical composition of InxGa1-xAs nanocrystals in a large range by varying the implantation dose and the annealing temperature.

Depuis plus de 30ans, les chercheurs essaient de combiner le silicium et le GaAs. Le potentiel de l'intégration du GaAs sur Si est en effet considérable pour le remplacement des substrats coûteux de GaAs ou de Ge dans la fabrication de cellules PV, de photodétecteurs, de LED, de lasers…. Il en est de même pour le développement de nouveaux dispositifs opto- et électroniques par l'intégration monolithique de GaAs sur circuit silicium. Des défis majeurs persistant jusqu'à aujourd'hui doivent toutefois être surmontés.Dans le but de surmonter ces difficultés, nous proposons un concept intéressant qui permet l'hétéroépitaxie de III-V sur Si. Ce concept est basé sur la technique d’épitaxie latérale (ELO) par CBE depuis des ouvertures nanométriques réalisées dans un masque de silice ultra-mince. Cette technique nous a permis d’obtenir des microcristaux de GaAs sans défaut et parfaitement intégrés sur Si grâce à une nucléation depuis des ouvertures de très petits diamètres qui évitent la génération de dislocations dues au désaccord de maille. Le concept étant validé, nous avons poursuivi l’étude en utilisant une 2ème approche de nanostructuration technologique du masque et permettant la localisation des cristaux. L’obtention in fine d’une pseudo-couche de GaAs sur Si sans défaut ni contrainte serait particulièrement utile pour les diverses applications mentionnées. Seront donc présentés le concept d’intégration, puis les résultats de croissance par ces techniques, et des analyses matériaux complémentaire. Pour finir, sera détaillée la structure d’une cellule PV de GaAs/Si devant permettre d’atteindre un rendement de conversion de 29,2%, ainsi que les premiers résultats obtenus. / For over thirty years researchers have attempted to combine Si and GaAs. Alternative GaAs-on-Si substrates have a considerable market potential for replacing the costly GaAs or Ge substrate in producing traditional GaAs devices such as solar cells, photodetectors, LEDS, lasers, and microwave devices, and as a new technology for monolithic integration of GaAs elements and silicon integrated circuits. However, major challenges remaining until now must be overcome.In that way, we propose an interesting concept that allows III-V heteroepitaxy on silicon. This concept is based on the Epitaxial Lateral Overgrowth (ELO) by CBE from nanoscale holes through an ultra-thin silica layer. This technique allows us to obtain GaAs microcrystals without any defect and perfectly integrated on Si thanks to nanoscaled nucleation seeds which prevent dislocation generation due to lattice mismatch. The concept being validated, the study has continued using a 2nd approach of nanostructuration to allow crystal localization. The achievement of getting a GaAs pseudo-layer on silicon substrate without any defect or stain would be of great interest for the formerly mentioned applications.So the integration concept of III-V materials on silicon will be introduced, then growth resultants by these techniques, and material characterizations in order to qualify the integrated GaAs on silicon regarding to the opto- and electronic applications. Finally, the structure of a GaAs/Si tandem solar cell will be discussed. After proving this solar cell could reach a 29.2% conversion efficiency, first achievements will be revealed.

Confiner la lumière dans un volume réduit d'absorbeur photovoltaïque offre de nouvelles voies pour les cellules solaires à haute rendement. Ceci peut être réalisé en utilisant des nanostructures pour le piégeage optique ou des nanofils de semi-conducteurs. Dans une première partie, nous présentons la conception et la fabrication de cellules solaires ultra-minces (205 nm) en GaAs. Nous obtenons des résonances multiples grâce à un miroir arrière nanostructuré en TiO2/Ag fabriqué par nanoimpression, résultant en un courant de court-circuit élevé de 24,6 mA/cm². Nous obtenons le record d’efficacité de 19,9%. Nous analysons les mécanismes des pertes et nous proposons une voie réaliste vers un rendement de 25% en utilisant un absorbeur de GaAs de 200 nm d'épaisseur seulement. Dans une deuxième partie, nous étudions les propriétés de nanofils en GaAs crûs sur substrats Si et nous explorons leur potentiel comme absorbeur photovoltaïque. Un dopage élevé est souhaité dans les cellules solaires à nanofils en jonction coeur-coquille, mais la caractérisation à l'échelle d'un nanofil unique reste difficile. Nous montrons que la cathodoluminescence (CL) peut être utilisée pour déterminer les niveaux de dopage de GaAs de type n et p avec une résolution nanométrique. Les semi-conducteurs III-V de type n présentent une émission décalée vers le bleu, à cause du remplissage de la bande de conduction, tandis que les semi-conducteurs de type p présentent une émission décalée vers le rouge due à la réduction du gap. La loi de Planck généralisée est utilisée pour fitter tout le spectre et ainsi évaluer quantitativement le niveau de dopage. Nous utilisons également la polarimétrie de CL pour déterminer sélectivement les propriétés de phases wurtzite/zinc-blende d'un nanofil unique. Nous montrons enfin des cellules solaires fonctionnelles à nanofils de GaAs. Ces travaux ouvrent des perspectives vers une nouvelle génération de cellules photovoltaïques. / Confining sunlight in a reduced volume of photovoltaic absorber offers new directions for high-efficiency solar cells. This can be achieved using nanophotonic structures for light trapping, or semiconductor nanowires. First, we have designed and fabricated ultrathin (205 nm) GaAs solar cells. Multi-resonant light trapping is achieved with a nanostructured TiO2/Ag back mirror fabricated using nanoimprint lithography, resulting in a high short-circuit current of 24.6 mA/cm². We obtain the record 1 sun efficiency of 19.9%. A detailed loss analysis is carried out and we provide a realistic pathway toward 25% efficiency using only 200 nm-thick GaAs absorber. Second, we investigate the properties of GaAs nanowires grown on Si substrates and we explore their potential as active absorber. High doping is desired in core-shell nanowire solar cells, but the characterization of single nanowires remains challenging. We show that cathodoluminescence (CL) mapping can be used to determine both n-type and p-type doping levels of GaAs with nanometer scale resolution. n-type III-V semiconductor shows characteristic blueshift emission due to the conduction band filling, while p-type semiconductor exhibits redshift emission due to the dominant bandgap narrowing. The generalized Planck’s law is used to fit the whole spectra and allows for quantitative doping assessment. We also use CL polarimetry to determine selectively the properties of wurtzite and zincblende phases of single nanowires. Finally, we demonstrate successful GaAs nanowire solar cells. These works open new perspectives for next-generation photovoltaics.

Optical studies of heavily-doped GaAs:C grown at low temperature by molecular beam epitaxy were performed using room-temperature photoluminescence, infrared transmission, and Raman scattering measurements. The photoluminescence experiments show that in LT-GaAs:C films grown at temperatures below 400 °C, nonradiative recombination processes dominate and photoluminescence is quenched. When the growth temperature exceeds 400 °C, band-to-band photoluminescence emission appears. We conclude that the films change in character from LT-GaAs:C to normal GaAs:C once the growth temperature reaches 400 °C. Annealing, however, shows a different behavior. Once grown as LT-GaAs:C, this material retains its nonconducting nonluminescing LT characteristics even when annealed at 600 °C. The Raman-scattering measurements showed that the growth temperature and the doping concentration influence the position, broadening, and asymmetry of the longitudinal-optical phonon Raman line. We attribute these effects to changes in the concentration of interstitial carbon in the films. Also, the shift of the Raman line was used to estimate the concentration of arsenic-antisite defects in undoped LT-GaAs. The infrared transmission measurements on the carbon-doped material showed that only a fraction of the carbon atoms occupy arsenic sites, that this fraction increases as the growth temperature increases, and that it reaches about 100% once the growth temperature reaches 400 °C. The details of all these measurements are discussed. Infrared transmission and photoluminescence measurements were also carried out on heavily-doped GaAs:C films grown by molecular beam epitaxy at the standard 600 C temperature. The infrared results reveal, for dopings under 5 x 10⁹ cm⁻³, a linear relation between doping concentration and the integrated optical absorption of the carbon localized-vibrational-mode band. At higher dopings, the LVM integrated absorption saturates. Formation of C_As-C_As clusters is proposed as the mechanism of the saturation. The photoluminescence spectra were successfully analyzed with a simple model assuming thermalization of photoelectrons to the bottom of the conduction band and indirect-transition recombination with holes populating the degenerately doped valence band. The analysis yields the bandgap reduction and the Fermi-level-depth increase at high doping. / Ph. D.

L'intégration de composants discrets sur un système unique, tel une puce électronique, augmente les performances totales du système, fait apparaitre de nouvelles fonctionnalités et diminue les coûts associés à la fabrication des dispositifs. Ces améliorations, appliquées au secteur de la microélectronique, sont grandement responsables des avancements importants qu'ont connus les technologies de l'information et des communications au cours des dernières années. Puisque la fabrication de circuits photoniques intégrés nécessite l'intégration de structures ayant des bandes interdites différentes à partir d'une même puce semiconductrice, leur niveau d'intégration est bien inférieur que celui atteint pour un microprocesseur standard. Parmi les techniques ayant le potentiel de fabriquer des circuits photoniques intégrés monolithiquement, l'interdiffusion de puits quantique post-expitaxial contrôlée spatialement augmente la bande interdite d'une hétérostructure semiconductrice à l'intérieur de régions définies. Le processus d'interdiffusion, activé thermiquement, est accéléré par la diffusion d'impuretés et de défauts ponctuels tels que les lacunes et les interstitiels. L'hypothèse de départ de mes travaux de doctorat suppose que la radiation laser ultra-violette module la diffusion et la génération de défauts ponctuels dans les hétérostructures reposant sur les technologies à base de GaAs et d'InP et, conséquemment, contrôle spatialement l'interdiffusion de puits quantiques. Nous avons démontré que lorsque appliquée sur des hétérostructures à base de GaAs, l'irradiation laser excimère l'interdiffusion en favorisant la croissance d'un stresseur de surface qui empêche la diffusion des défauts ponctuels vers les puits quantiques. Nous avons souligné l'influence de la vapeur d'eau physisorbée sur la croissance du stresseur et avons déterminé la résolution spatiale de la technique. Dans les hétérostructures basées sur les technologies InP, même sous le seuil d'ablation, l'absorption des impulsions laser UV favorise la désorption des atomes de surface ce qui génère des défauts ponctuels en concentration excédentaire. Lors d'un recuit thermique, ces défauts ponctuels augmentent la vitesse de l'interdiffusion sous les régions irradiées.

In order to continue with metal-oxide-semiconductors (CMOS) transistor scaling and to reduce the power density, the channel should be replaced with a material having a higher electron mobility, such as a III-V semiconductor. However, the integration of III-V's is a challenge because these materials oxidize rapidly when exposed to air and the native oxide produced is characterized by a high density of defects. Deposition of high-k materials on III-V semiconductors using Atomic Layer Deposition (ALD) reduces the thickness of these oxides, improving the semiconductor/oxide interface quality and the transistor electrical characteristics. In this work, ALD is used to deposit two dielectrics, Al₂O₃ and TiO₂, on two III-V materials, GaAs and InGaAs, and in-situ X-ray photoelectron spectroscopy (XPS) and in-situ thermal programmed desorption (TPD) are used for interface characterization. Hydrofluoric acid (HF) etching of GaAs(100) and brief reoxidation in air produces a 9.0 ± 1.6 Å-thick oxide overlayer containing 86% As oxides. The oxides are removed by 1 s pulses of trimethylaluminum (TMA) or TiCl₄. TMA removes the oxide overlayer while depositing a 7.5 ± 1.6 Å thick aluminum oxide. The reaction follows a ligand exchange mechanism producing nonvolatile Al-O species that remain on the surface. TiCl₄ exposure removes the oxide overlayer in the temperature range 89°C to 300°C, depositing approximately 0.04 monolayer of titanium oxide for deposition temperatures from 89°C to 135°C, but no titanium oxide is present from 170°C to 230°C. TiCl₄ forms a volatile oxychloride product and removes O from the surface while leaving Cl atoms adsorbed to an elemental As layer, chemically passivating the surface. The native oxide of In(0.53)Ga(0.47)As(100) is removed using liquid HF and gas phase HF before deposition of Al₂O₃ using TMA and H₂O at 170°C. An aluminium oxide film with a thickness of 7.2 ± 1.2 Å and 7.3 ± 1.2 Å is deposited during the first pulse of TMA on liquid and gas phase HF treated samples, respectively. After three complete ALD cycles the thickness of the aluminum oxide film is 10.0 ± 1.2 Å on liquid HF treated and 6.6 ± 1.2 Å on gas phase HF treated surfaces. Samples treated with gas phase HF inhibit growth. Inhibition is caused by residual F atoms that passivate the surface and by surface poisoning due to the thicker carbon film deposited during the first pulse of TMA. On InGaAs covered by native oxide, the first TMA pulse deposits 9 Å of aluminum oxide, and reaches saturation at 13 Å after 15 pulses of TMA. The film grows by scavenging oxygen from the substrate oxides. Substrate oxides are reduced by the first pulse of TMA even at 0°C. At 0°C, on a 9 Å thick Ga-rich oxide surface, 1 pulse of TMA mainly physisorbs and a limited amount of aluminum oxide is deposited. At 0°C, 110°C, and 170°C, more aluminum oxide is deposited on surfaces initially containing As oxide, and larger binding energy (BE) shifts of the O 1s peak are observed compared to surfaces that contain Ga oxides only, showing that As oxides improve the nucleation of Al₂O₃.

This thesis presents a study of two-dimensional electron systems in GaAs-(Al,Ga)As heterojunctions and quasi-two-dimensional electron and hole systems in graphite within the quantum Hall effect regime of low temperature and high magnetic field. This thesis covers three main sets of experimental work as well as details of the experimental methods (chapter 2) used and the background theory behind the observed results (chapter 1). The first experimental results presented in this thesis in chapter 3 focus on contactless measurement of the equilibrium magnetisation of sample A2268, a ten layer multiple quantum well sample. Fitting the shape of dHvA oscillations at various temperatures to different models for the density of states, various properties of the system can be estimated, such as the shape of the disorder-broadened density of states and the presence of a background density of states between the Landau levels. Chapter 4 focuses on measurements of the decay of induced circulating currents in the quasi-dissipationless quantum Hall regime in two samples, V0049 and T73. The induced current is measured via contactless measurement of the associated magnetic moment. The magnitude of the induced current is found to be affected by the sweep rate of the magnetic field and also the distance of approach. The decay of the induced currents is observed at several temperatures and for different magnetic field sweep rates and distances of approach. Decays are observed for up to several days at time, far longer than previously possible. Information about the rate of decay can be used to build a picture of the decay mechanisms present in the quantum Hall regime. The presence of a power-law decay regime indicates many decay mechanisms contribute to the decay of a circulating current in the quasi-dissipationless quantum Hall regime. Chapter 5 focuses on both contactless magnetometry and transport experiments carried out on a graphite sample. The experiments aim to confirm or dispute recent claims of Dirac fermions in graphite. Experiments are carried out at temperatures in the range 30 mK to ~4 K and at two different angles to the applied magnetic field. Phase analysis of both Shubnikov de Haas and de Haas van Alphen oscillations is used to distinguish between normal and Dirac fermions. Observation of quantum Hall effect displays the presence of a half-integer quantum Hall staircase similar to that observed in graphene.

Molecules that contain linear alkane chains self-assemble on a variety of surfaces changing the degree of wetting, lubricity, and reactivity. We report on the reoxidation of GaAs(100) in air after adsorbing five alkanethiols (C$_n$H$_{2n+1}$-SH where $n=$ 3, 6, 12, 18, 20) and one alkanedithiol (HS-(CH$_2$)$_8$-SH) deposited from the liquid phase. The alignment of the alkane chains forms a self-assembled layer, however, air diffuses readily through the carbon layer and reaches the surface. The impact of alignment is to improve the bonding of sulfur with the surface atoms which reduces the oxidation rate based on fitting the data to a reaction-diffusion model. The layer thickness and molecular density scale linearly with the number of carbon atoms in the alkane chain. The thickness of the alkanethiolate (RS$^{-}$) layer grows by $0.87 \pm 0.06$ {\AA} for each C atom in the chain and the surface density by $0.13 \pm 0.03$ molecule per nm$^2$ per C atom up to a coverage of 5.0 molecules/nm$^2$ for $n=20$ or 0.8 monolayer. The surface coverage increases with length because interactions between methylene (CH$_2$) groups in neighboring chains reduce the tilt angle of the molecules with the surface normal. The tight packing yields areas per alkanethiolate as low as 20 \AA$^2$ for $n=20$. The amount of C in the layer divided by the chain length is approximately constant up to $n=12$ but increases sharply by a factor of 2-4$\times$ for $n=18$ and 20 based on the C 1s x-ray photoelectron spectroscopy (XPS) peak. Fourier transform infrared (FTIR) spectroscopy shows that the asymmetric methylene stretch shifts continuously to lower wavenumber and the relative peak area increases sharply with the length of the alkane chain. Fitting the data to a reaction-diffusion model shows that for times less than 30 min the surface oxide coverage does not depend on the thickness of the self-assembled layer nor the diffusivity of oxygen through the layer. Instead increasing the layer thickness makes more S available for bonding with the predominately As termination and reduces the rate coefficient for reaction of oxygen with the GaAs surface.