abstract: Recently a new materials platform consisting of semiconductors grown on GaSb and InAs substrates with lattice constants close to 6.1 A was proposed by our group for various electronic and optoelectronic applications. This materials platform consists of both II-VI (MgZnCdHg)(SeTe) and III-V (InGaAl)(AsSb) compound semiconductors, which have direct bandgaps spanning the entire energy spectrum from far-IR (~0 eV) up to UV (~3.4 eV). The broad range of bandgaps and material properties make it very attractive for a wide range of applications in optoelectronics, such as solar cells, laser diodes, light emitting diodes, and photodetectors. Moreover, this novel materials system potentially offers unlimited degrees of freedom for integration of electronic and optoelectronic devices onto a single substrate while keeping the best possible materials quality with very low densities of misfit dislocations. This capability is not achievable with any other known lattice-matched semiconductors on any available substrate. In the 6.1-A materials system, the semiconductors ZnTe and GaSb are almost perfectly lattice-matched with a lattice mismatch of only 0.13%. Correspondingly, it is expected that high quality ZnTe/GaSb and GaSb/ZnTe heterostructures can be achieved with very few dislocations generated during growth. To fulfill the task, their MBE growth and material properties are carefully investigated. High quality ZnTe layers grown on various III-V substrates and GaSb grown on ZnTe are successfully achieved using MBE. It is also noticed that ZnTe and GaSb have a type-I band-edge alignment with large band offsets (delta_Ec=0.934 eV, delta_Ev=0.6 eV), which provides strong confinement for both electrons and holes. Furthermore, a large difference in refractive index is found between ZnTe and GaSb (2.7 and 3.9, respectively, at 0.7 eV), leading to excellent optical confinement of the guided optical modes in planar semiconductor lasers or distributed Bragg reflectors (DBR) for vertical-cavity surface-emitting lasers. Therefore, GaSb/ZnTe double-heterostructure and ZnTe/GaSb DBR structure are suitable for use in light emitting devices. In this thesis work, experimental demonstration of these structures with excellent structural and optical properties is reported. During the exploration on the properties of various ZnTe heterostructures, it is found that residual tensile strains exist in the thick ZnTe epilayers when they are grown on GaAs, InP, InAs and GaSb substrates. The presence of tensile strains is due to the difference in thermal expansion coefficients between the epilayers and the substrates. The defect densities in these ZnTe layers become lower as the ZnTe layer thickness increases. Growth of high quality GaSb on ZnTe can be achieved using a temperature ramp during growth. The influence of temperature ramps with different ramping rates in the optical properties of GaSb layer is studied, and the samples grown with a temperature ramp from 360 to 470 C at a rate of 33 C/min show the narrowest bound exciton emission peak with a full width at half maximum of 15 meV. ZnTe/GaSb DBR structures show excellent reflectivity properties in the mid-infrared range. A peak reflectance of 99% with a wide stopband of 480 nm centered at 2.5 um is measured from a ZnTe/GaSb DBR sample of only 7 quarter-wavelength pairs. / Dissertation/Thesis / Ph.D. Physics 2012

A isolação elétrica de estruturas semicondutoras de InP e GaAs através de bombardeamento com íons foi estudada. Amostras de InP semi-isolante e tipo-p foram implantadas com íons P+ para produzir excesso de átomos de fósforo na ordem de 0,1%. Recozimento em ambiente de argônio no intervalo de temperatura de 400ºC a 600ºC e tempo de 30s foram feitos em sistema de tratamento térmico rápido. Medidas de efeito Hall com temperatura variável (12-300K) foram usadas para a caracterização elétrica. Uma alta concentração de portadores livres negativos foi observada. A existência destes elétrons foi atribuída a criação de anti-sítios PIn com energia acima do mínimo da banda de condução. A dependência da resistência de folha de camadas δ tipo-p de GaAs com a dose irradiada de íons de He+ foi investigada. A dose de limiar (Dth) para isolação elétrica depende da energia dos íons implantados e da concentração inicial da camada condutiva. A estabilidade térmica da isolação aumenta com o aumento da dose de irradiação e depende da razão entre a concentração de armadilhas criadas durante o bombardeamento e a concentração inicial de portadores livres. A isolação observada foi atribuída principalmente a introdução de anti-sítios AsGa e defeitos relacionados. A máxima estabilidade térmica para camadas δ tipo-p em GaAs foi de 550ºC, para doses maiores do que 10Dth. Os resultados deste trabalho podem ser usados para isolação de diferentes dispositivos discretos e integrados de InP e GaAs. / Electrical isolation of InP and GaAs structures by ion bombardment was studied. Semi-insulating and p-type InP were implanted with P+ ions to produce an excess of phosphorous atoms in the order of 0.1 at. %. Subsequent annealing in Ar ambient in the temperature interval 400ºC – 600ºC were performed for 30s in rapid thermal annealing system. Room temperature and variable temperature (12-300 K) Hall-effect measurements have been used for electrical characterization. A large amount of negative free carriers have been observed after the thermal treatments. These electrons are contributed to the creation of PIn anti-site with energy level above the minimum of the conduction band. The dose dependence of sheet resistance of p-type δ-doped GaAs structures irradiated by He+ ions was investigated. It was found that the threshold dose (Dth) for electrical isolation of the structures was determined by the energy of ions and by the concentration of initial doping. The thermal stability of isolation rises as the irradiation dose increases and is dependent on the ratio of trap centers concentration, created during the bombardment, to the initial concentration of free carriers. The isolation was attributed mainly to the introduction of AsGa anti-site related defects. The maximum thermal stability for p-type δ conductive layers in GaAs was of 550 0C for doses higher than 10 Dth. The results of this work can be used for isolation of different InP and GaAs discrete and integrated devices.

Ce travail examine des nanofils III-V synthétisés en mode vapeur-liquide-solide, une goutte liquide catalysant la croissance unidimensionnelle. En conjuguant expériences d’épitaxie par jets moléculaires, caractérisations structurales et analyses théoriques, j'étudie et clarifie plusieurs questions cruciales. L’une d'elles est le contrôle de la phase cristalline, qui s’avère souvent un mélange de segments cubiques et hexagonaux. Au moyen d’une analyse probabiliste de la séquence d'empilement de nanofils d’InP, je montre que la sélection de phase est déterminée non seulement par les conditions de croissance mais aussi par des interactions entre monocouches. Je souligne et discute le rôle de l'énergie de bord du germe qui médie la formation de chaque monocouche. On sait par ailleurs que le caractère abrupt des interfaces dans les hétérostructures axiales est limité par l’accumulation de matière dans la goutte (effet réservoir). J'étudie la formation de telles hétérostructures dans des nanofils de GaAs auto-catalysés en utilisant un second élément des groupes V (P) ou III (Al). Les profils compositionnels des insertions ternaires sont analysés à la résolution atomique. Les interfaces se révèlent soit plus larges (GaAsP) soit plus étroites (AlGaAs) qu’attendu et la morphologie du front de croissance dépend de la supersaturation. Je montre que, dans les deux cas, la largeur d’interface peut être réduite à quelques monocouches et je suggère d’autres améliorations. Enfin, je présente mes tentatives pour réaliser des nanofils ultraminces de GaAs et GaP et je discute du contrôle de la croissance à l’échelle d’une monocouche par réduction du caractère stochastique de la nucléation. / This work investigates III-V nanowires synthesized via the vapor-liquid-solid method, whereby a catalyst droplet promotes one-dimensional growth. By combining molecular beam epitaxy experiments, structural characterization and theoretical analyses, I study and clarify several critical issues. One of them is the control of the crystal phase, which is frequently found to be a mix of cubic and hexagonal segments. By performing a probabilistic analysis of the stacking sequence of InP nanowires, I show that phase selection is determined not only by growth conditions but also by interactions between layers. I highlight and discuss the role of the edge energy of the nucleus that mediates the formation of each monolayer. Another important problem is the formation of axial heterostructures, which interface sharpness is severely limited by material accumulation in the droplet (‘reservoir effect’). To this end, I study the formation of such heterostructures in Ga-catalyzed GaAs nanowires using either a second group V element (P) or a second group III element (Al). The composition profiles of the ternary insertions are analyzed with monolayer resolution. The interface widths are found to be larger (GaAsP) or narrower (AlGaAs) than expected, and the morphology of the growth front depends on supersaturation. In both cases, I demonstrate that the interface width can be reduced to a few monolayers and suggest further improvements. Attempts to achieve ultrathin GaAs and GaP nanowires that would permit lateral quantum confinement are presented. Finally, I consider the possibility of minimizing the stochastic character of nucleation ultimately to control the growth of single monolayers.

Les nanostructures de semiconducteurs II-VI ont de nombreuses applications en microélectronique, optoélectronique et photonique. Notamment, les boites quantiques II-V peuvent servir de source de photons uniques. Dans cette étude, nous nous sommes intéressés à la caractérisation chimique et structurale des nanostructures de semiconducteurs II-VI (boites quantiques (BQs) auto-organisées, nanofils II-VI et III-V …) par sonde atomique tomographique (SAT). Dans un premier temps, nous avons optimisé les conditions d’analyse des semiconducteurs III-V et II-VI par SAT. Ensuite, nous avons étudié les compositions chimiques des interfaces II-VI/III-V en montrant la formation d’un composé Ga2.7Se3 à l’interface ZnSe/GaAs et un mélange de cations (Ga, Zn) à l’interface ZnTe/InAs. Les mesures de compositions chimiques et des tailles des boites quantiques en trois dimensions par SAT ont permis de faire une corrélation avec les mesures optiques. Nous nous sommes aussi intéressés à l’étude des mécanismes de croissance des nanofils GaAs et ZnTe ainsi que des BQs (CdTe) insérés dans des nanofils ZnTe en analysant la composition chimique des catalyseurs, les BQs dans les nanofils aussi que la base des nanofils. Ces mesures montrent que les boites quantiques sont formées d’un fort mélange CdxZn1-xTe. Un scénario basé sur la diffusion de surface a été proposé pour expliquer la croissance ainsi que le mélange entre Zn/Cd pour les BQs insérées dans les nanofils. / Nanostructures of II-VI nanostructure have many applications in microelectronics, optoelectronics and photonics. For example, II -V quantum dots have shown the ability to be a source of single photons. In this work, we performed in the chemical and structural characterization of nanostructures of II-VI semiconductors (self- organized quantum dots (QDs), nanowires II-VI and III- V ...) by atom probe tomography (APT). Firstly, the analysis conditions of III-V and II- VI semiconductors by APT were optimized. Then, we studied the chemical composition of II-VI/III-V interfaces and showed the formation of a Ga2.7Se3 compound at the ZnSe/GaAs interface and the (Ga, Zn) cations mixing at the ZnTe/InAs interface. The measurements of the chemical composition and the sizes of quantum dots in three dimensions by APT allowed making a correlation with optical measurements. We studied also growth mechanisms of GaAs, ZnTe nanowire and the CdTe QDs inserted in ZnTe nanowires by analyzing the chemical composition of the catalysts QDs and nanowires basis. These measurements show that the quantum dots are formed of a strong mixing of CdxZn1-xTe. A scenario based on surface diffusion has been proposed to explain the growth and the mixing between Zn/Cd for the QDs.

Ce travail de thèse présente les résultats d'une étude des propriétés physiques de semi-conducteurs à faible gap et des caractéristiques de dispositifs de type antenne photoconductrice fabriquée sur de tels matériaux photoconducteurs. Le but de la présente étude est de développer un dispositif amélioré d'émission et de détection de radiation THz pulsée pour des systèmes de spectroscopie THz compacts requérant d'être couplés à des sources laser émettant à 1550 nm. Des antennes photoconductrices ont été fabriquées sur un substrat photoconducteur (InGaAs et InGaAsP) dont les propriétés physiques ont été modifiées via un procédé de fabrication nécessitant l'implantation d'ions lourds à haute énergie suivit d'un recuit thermique rapide. Ce procédé de fabrication a déjà été mis au point dans le cadre d'un précédent travail de thèse: il donne lieu à une structure recristallisée inhomogène en profondeur qui présente un faible temps de vie des photoporteurs (< 1ps), une grande résistivité ( >1000 Ωcm) et une mobilité de Hall ( >300 cm2V-1s-1) convenable pour la fabrication de dispositifs THz. Dans le cadre du présent travail, une meilleure corrélation entre les propriétés structurales et électroniques du matériau photoconducteur, obtenu selon différentes conditions expérimentales d'implantation et de recuit, a été établie. L'effet des propriétés physiques du substrat sur les caractéristiques des antennes photoconductrices a également été discuté. Le temps de vie et la mobilité des photoporteurs ainsi que la résistivité du matériau ont été déterminés pour différentes conditions de fabrication des substrats photoconducteurs. Des courbes de photoconductivité en fonction de la fréquence des différentes substrats photoconducteurs ont été obtenues à partir des mesures pompe optique - sonde THz. Deux sortes d'implantion ionique ont été effectuées, soit une implantion avec ions de Fe et une co-implantation de Fe et de P. Cette co-implantion vise à maintenir un équilibre stoechiométrique pour les matériaux ternaires. Différentes températures de recuit thermique rapide ont été utilisées. Pour caractériser le degré de cristallisation de chaque matériau et la taille de grain moyenne de ceux-ci, des mesures d'absorption par ellipsométrie ont été effectuées. Le choix des conditions expérimentales pour la fabrication du substrat de base des antennes repose sur une implantation d'ions de Fe avec une énergie de plus de 2.5 MeV suivi d'un recuit à 500 degrés Celsius conférant au semi-conducteur une mobilité de >5 cm2V-1s-1. Avec cette optimisation des paramètres physiques, un spectromètre térahertz a été réalisé avec deux antennes photoconductrices quaternaire couplées à un laser opérant à 1550 nm. Une plage dynamique de plus de 65 dB allant à 3 THz est obtenue avec une bande passante pouvant atteindre plus de 1.5 THz à 20 dB. L'optimisation des matériaux ternaires (InGaAs) et quaternaires (InGaAsP) à des fins de spectroscopie térahertz est présentée avec différents types d'implantations et de recuit thermique. Selon les résultats de la présente étude, le matériau quaternaire présente les meilleures caractéristiques pour le développement d'un spectromètre térahertz compact et entièrement fibré.

Multilayer structures of AlxIn1-xAsySb1-y/GaSb (0.37 £ x £ 0.43, 0.50 £ y £ 0.52), grown by molecular beam epitaxy on GaSb (100) substrates were characterized using variable temperature Hall and Shubnikov-de Haas techniques. For nominally undoped structures both p and n-type conductivity was observed. The mobilities obtained were lower than those predicted by an interpolation method using the binary alloys; therefore, a detailed analysis of mobility versus temperature data was performed to extract the appropriate scattering mechanisms. For p-type samples, the dominant mechanism was ionized impurity scattering at low temperatures and polar optical phonon scattering at higher temperatures. For n-type samples, ionized impurity scattering was predominant at low temperatures, and electron-hole scattering dominated for both the intermediate and high temperature range. Analyses of the Shubnikov-de Haas data indicate the presence of 2-D carrier confinement consistent with energy subbands in GaAszSb1-z potential wells. Epilayers of GaAs1-xSbx (0.19<x<0.71), grown by MBE on semi-insulating GaAs with various substrate orientations, were studied by absorption measurements over the temperature range of 4-300 K. The various substrate orientations were chosen to induce different degrees of spontaneous atomic ordering. The temperature dependence of the energy gap (Eg) for each of these samples was modeled using three semi-empirical relationships. The resulting coefficients for each model describe not only the temperature dependence of Eg for each of the alloy compositions investigated, but also for all published results for this alloy system. The effect of ordering in these samples was manifested by a deviation of the value of Eg from the value of the random alloy. The presence of CuPt-B type atomic ordering was verified by transmission electron diffraction measurements, and the order parameter was estimated for all the samples investigated and found to be larger for the samples grown on the (111) A offcut orientations. This result strongly suggests that it is the A steps that contribute to the formation of the CuPt-B type ordering in the GaAs1-xSbx alloy system.

Un système autonome est composé d’une interface capteur, d’un contrôleur numérique, d’une interface de communication et d’une source d’énergie et sa consommation doit être inférieure à environ 100 microW. Pour réduire la consommation de puissance, des nouveaux composants, les Green Transistor ont fait leur apparition sous différentes topologies, modes de fonctionnement et matériaux alternatifs au silicium. L’interface de communication est composée d’un transistor possédant de grandes performances électriques sous faible alimentation. Les topologies retenues sont le transistor à haute mobilité électronique (HEMT) et le transistor à effet de champ métal/oxyde/semi-conducteur (MOSFET) et seuls les matériaux de la filière III-V à faible énergie de bande interdite, faible masse effective et grande mobilité électronique devraient permettre d’atteindre ces objectifs. Des technologies de HEMTs antimoniés AlSb/InAs ainsi que des MOSFETs InGaAs ont été développées. Les mesures de transistors HEMTs AlSb/InAs ont montré des performances au dessus de 100GHz à 10mW/mm à température ambiante et cryogénique et nous pouvons espérer des transistors où 1mW/mm à 10GHz. Or, les courants de grille importants et la conservation d’un rapport d’aspect élevé dans une structure HEMT limitent la réduction du facteur de mérite puissance-fréquence. Ainsi, la technologie de transistors de type MOS InGaAs a été caractérisée durant ces travaux et les résultats dynamiques sont prometteurs (fT =120GHz, Lg=200nm) même si le processus de fabrication n’est pas complètement optimisé. Une perspective de ce travail est l’utilisation de matériaux antimoines pour la réalisation de MOSFET ultra faible consommation. / An autonomous system is composed of a sensor, a digital controller, a communication interface and an energy source. Its consumption should be less than about 100 microW. To reduce power consumption, new components called the Green transistors have appeared in various topologies, operating modes and alternative materials to silicon. The communication interface consists of a transistor with high performances at low power supply. The topologies used are the high electron mobility transistor (HEMT) and the metal-oxide-semiconductor field-effect transistor (MOSFET) and only III-V-based channels with low bandgap energy, low effective mass and high electron mobility should achieve these goals. Antimonide based HEMTs (AlSb/InAs) and InGaAs MOSFETs technologies have been developed. Measurements of transistors AlSb /InAs HEMTs showed performance above 100GHz at 10mW/mm at room and cryogenic temperatures and transistors which 1mW/mm equals to 10GHz can be expected. However, significant gate currents and a high aspect ratio in a HEMT structure limit the reduction the factor of merit between the power and the cut-off frequency. Thus, the technology of InGaAs MOSFET has been characterized during this work and the RF results are promising (fT = 120GHz, Lg = 200nm) even if the process fabrication is not fully optimized. A perspective of this work is the use of antimonide materials for the realization of ultra low power MOSFET.

abstract: This dissertation focuses on the structural and optical properties of III-V semiconductor materials. Transmission electron microscopy and atomic force microscopy are used to study at the nanometer scale, the structural properties of defects, interfaces, and surfaces. A correlation with optical properties has been performed using cathodoluminescence. The dissertation consists of four parts. The first part focuses on InAs quantum dots (QDs) embedded in a GaInP matrix for applications into intermediate band solar cells. The CuPt ordering of the group-III elements in Ga0.5In0.5P has been found to vary during growth of InAs QDs capped with GaAs. The degree of ordering depends on the deposition time of the QDs and on the thickness of the capping layer. The results indicate that disordered GaInP occurs in the presence of excess indium at the growth front. The second part focuses on the effects of low-angle off-axis GaN substrate orientation and growth rates on the surface morphology of Mg-doped GaN epilayers. Mg doping produces periodic steps and a tendency to cover pinholes associated with threading dislocations. With increasing miscut angle, the steps are observed to increase in height from single to double basal planes, with the coexistence of surfaces with different inclinations. The structural properties are correlated with the electronic properties of GaN epilayers, indicating step bunching reduces the p-type doping efficiency. It is also found that the slower growth rates can enhance step-flow growth and suppress step bunching. The third part focuses on the effects of inductively-coupled plasma etching on GaN epilayers. The results show that ion energy rather than ion density plays the key role in the etching process, in terms of structural and optical properties of the GaN films. Cathodoluminescence depth-profiling indicates that the band-edge emission of etched GaN is significantly quenched. The fourth part focuses on growth of Mg-doped GaN on trench patterns. Anisotropic growth and nonuniform acceptor incorporation in p-GaN films have been observed. The results indicate that growth along the sidewall has a faster growth rate and therefore a lower acceptor incorporation efficiency, compared to the region grown on the basal plane. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

This thesis addresses barriers to the widespread adoption of high-efficiency photovoltaic devices through the use of innovative semiconductor materials and device design. The feasibility of various strategies is explored through experimental characterization and modeling of semiconductor materials and devices. High-efficiency photovoltaic devices are made from epitaxially grown III-V semiconductor materials. Epitaxial devices are highly sensitive to lattice mismatch between the epi-layers and the substrate, requiring sophisticated substrate engineering or growth strategies to access materials outside of the lattice-matched regime. One promising strategy involves the electrochemical porosification of germanium on a lattice-mismatched silicon substrate to create a compliant interface for high-quality epitaxial growth of Ge, GaAs, and other equivalent-bandgap III-V semiconductors on silicon. This results in a threading dislocation density of ~10^4 cm^-2, a reduction of 4 to 6 orders of magnitude compared to direct epitaxy of germanium on silicon. This technology could enable the development of highly efficient III-V multi-junction photovoltaic devices on cost-effective silicon substrates that benefit from well-established commercial supply chains. In the first part, I present characterization of the electrical properties of porous germanium. Experimental measurements revealed conductivities ranging from 0.6 to 33 (x10^-3) Ohm^-1 cm^-1, depending on the morphology. The relationship between the electrical properties and the morphology is described using an electrostatic model that can be generalized to other porous semiconductors including silicon. For a compliant interface designed to integrate a standard triple-junction solar cell onto a silicon substrate, the porous Ge/Si layers are predicted to introduce < 0.01 Ohm cm^2 of series resistance to the device, which is sufficiently low for concentrated photovoltaic applications. Optoelectronic device modelling of the triple-junction solar cell on silicon demonstrates that III-V triple-junction solar cells fabricated on silicon using this compliant Ge/Si porous interface could achieve 93% of the efficiency of a comparable defect-free device. The remainder of this thesis is concerned with the design and characterization of photovoltaic devices optimized for monochromatic illumination, known as photonic power converters. Most commercially available photonic power converters are based on GaAs and are suitable for short-range photonic power transmission through optical fiber (< 1 km). Extended reach power-over-fiber systems require the use of photonic power converters that are compatible with longer-wavelength light, which travels further in optical fiber. One candidate material for this application is the semiconductor quaternary alloy InAlGaAs lattice-matched to InP for photonic power converter operation in the telecommunications O-band, near 1310 nm. I describe the design and characterization of multi-junction InAlGaAs/InP photonic power converters grown by molecular beam epitaxy, including the analysis of material properties and characterization of single- and dual-junction devices under 1319-nm laser illumination. Optically thick devices are found to be diffusion-limited and device simulations suggest that non-radiative recombination is significant. The performance of InAlGaAs tunnel diodes, which act as interconnections for the absorbing junctions within a multi-junction device, is demonstrated to be highly dependent on the growth temperature, with peak tunneling current densities exceeding 1200 A/cm^2 in the best measured devices. In addition to molecular beam epitaxy-grown InAlGaAs/InP devices, I also characterize single-junction O-band photonic power converters grown by metal-organic vapour phase epitaxy with two alternative absorber materials. A lattice-matched InGaAsP/InP device is compared to a more cost-effective lattice-mismatched GaInAs device grown on GaAs using a metamorphic buffer layer. Both devices are measured under 1319-nm laser illumination with a variety of beam sizes and peak efficiencies of 52.9% and 48.8% were measured for the InGaAsP/InP and the metamorphic-GaInAs/GaAs devices respectively. At illumination powers exceeding 100 mW, the performance begins to degrade with increasingly non-uniform illumination, indicating that illumination profiles should be as uniform as possible to maximize device performance.

No description available.