Cette thèse porte sur la conversion thermoélectrique de nanofils semi-conducteurs désordonnés en configuration de transistor à effet de champ.On considère d’abord le régime de transport élastique à basse température. En utilisant un modèle d'Anderson 1D, on dérive des expressions analytiques pour le coefficient Seebeck typique d’un nanofil en fonction de la tension de grille, et on montre que celui-ci augmente fortement en bord de bande. Ces résultats sont confirmés par un calcul numérique du Seebeck, basé sur un algorithme de fonctions de Green récursif.On considère ensuite le régime inélastique où les électrons, assistés par les phonons, sautent entre états localisés. En résolvant numériquement le réseau de résistances aléatoires de Miller-Abrahams, on montre que le coefficient Seebeck peut atteindre des valeurs très élevées au voisinage des bords de bande du nanofil. La théorie de percolation de Zvyagin étendue au cas unidimensionnel nous permet de décrire qualitativement nos résultats. Par ailleurs, les échanges de chaleur entre électrons et phonons en bord de bande entraînent la formation de points chauds et froids à la surface du substrat, qui pourraient être utilisés pour le refroidissement de circuits électroniques. Cet effet est étudié pour un ensemble de fils en parallèle. Le facteur de puissance et la figure de mérite de ces systèmes sont aussi estimés.Enfin, on étudie un système général à trois terminaux en réponse linéaire. On calcule les coefficients de transport locaux et non-locaux, et les figures de mérite généralisées, puis l'on discute à l'aide de deux exemples la possibilité d’améliorer la performance d’une machine thermique quantique générique. / This thesis is focused on thermoelectric conversion in disordered semiconductor nanowires in the field effect transistor configuration. We first consider a low temperature regime, when electronic transport is elastic. For a 1D Anderson model, we derive analytical expressions describing the typical thermopower of a single nanowire as a function of the applied gate voltage, and we show that it is largely enhanced at the nanowire band edges. Our results are confirmed by numerical simulations based on a Recursive Green Function calculation of the thermopower. We then consider the case of inelastic transport, achieved by phonon-assisted hopping among localized states (Variable Range Hopping). By solving numerically the Miller Abrahams random resistor network, we show that the thermopower can attain huge values when the nanowire band edges are probed. A percolation theory by Zvyagin extended to nanowires allows to qualitatively describe our results. Also, the mechanism of heat exchange between electrons and phonons at the band edges lead to the generation of hot and cold spots near the boundaries of a substrate. This effect, of interest for cooling issues in microelectronics, is showed for a set of parallel nanowires, a scalable and hence promising system for practical applications. The power factor and figure of merit of the device are also estimated.Finally, we characterize a general three-terminal system within the linear response (Onsager) formalism: we derive local and non-local transport coefficients, as well as generalized figures of merit. The possibility of improving the performance of a generic quantum machine is discussed with the help of two simple examples.

Cette thèse présente des mesures de transport électronique dans des systèmes quasi-unidimensionnels (quasi-1D) sous champ magnétique intense. Deux systèmes différents présentant un confinement électrique quasi-1D ont été considérés: les peapods de carbone (C60@SWCNTs) et les nanofils d'InAs. L’objectif de ces travaux consiste à sonder les propriétés électroniques spécifiques de ces systèmes quasi-1D par les mesures de magnétotransport sur les nano-objets uniques. Dans les deux cas, les expériences sous champs magnétiques intenses ont été accompagnée par des caractérisations structurales et des mesures de conductance à champ magnétique nul.L'encapsulation de diverses molécules à l'intérieur de nanotubes de carbone (CNTs), comme par exemple les fullerènes C60, constitue une des voies prometteuses vers l'accordabilité de la conductance des CNTs. Parmi la grande variété des nanotubes de carbone remplis, les peapods représentent une structure hybride pionnière découvert en 1998. Depuis lors, leur structure électronique a fait l’objet d’études théoriques controversées avec un nombre limité de réalisations expérimentales. Dans cette thèse, les propriétés électroniques des peapods individuels ont été étudiés en combinant les mesures de spectroscopie micro-Raman et de magnétotransport sur les mêmes échantillons. Nous avons constaté que les C60 encapsulés modifient fortement la structure de bande électronique des nanotubes semi-conducteurs au voisinage du point de neutralité de charge. Cette modification comprend un déplacement rigide de la structure électronique et un remplissage partiel de la bande interdite. Nous avons aussi montré que l’excitation UV sélective des fullerènes conduit à une forte modification du couplage électronique entre les C60 et le CNT induite par la coalescence partielle des C60 et de leur distribution à l'intérieur du tube. Les résultats expérimentaux sont supportés par des simulations numériques de la densité d'états et de la conductance des nanotubes de carbone avec des fullerènes fusionnés à l'intérieur (K. Katin, M. Maslov).Les nanofils semiconducteurs (sc-NWs) font l'objet de recherches actives depuis ces dix dernières années. Ils représentent des systèmes modèles pour l’étude des propriété électronique objet quasi-1D. Ils représentent en outre des possibilités de modulation de la structure de bande aussi que de contrôle de la densité de porteurs. Dans ce domaine de recherche, les nanofils semi-conducteurs à base de composes III-V tel que InAs, ont une place particulière en raison de la faible masse effective des porteurs de charge. Nous avons étudié la conductance de nanofils individuels dans une large gamme de champs magnétiques (jusqu'à 60T). Les mesures en champ nul et en champ faible ont démontré un transport faiblement diffusif dans ces nanofils. Les mesures de transport sous champ magnétique intense ont révélé une forte chute de la conductance au dessus d'un champ critique qui s'élève clairement avec l'énergie de Fermi. Cet effet est interprété par la perte de canaux de conduction une fois que toutes les sous-bandes magnéto-électriques, décalés vers les hautes énergies par le champ magnétique, ont traversé l'énergie de Fermi. Les calculs de structure de bande préliminaires (Y-M. Niquet), en prenant en compte les confinements latéraux et magnétiques, sont en bon accord qualitatif avec les résultats observés dans le régime de champ magnétique intense. Ce résultat est la première observation des effets de structure de bande dans les expériences de magnéto-transport sur les sc-NWs / The scope of this thesis is related to the electronic properties of quasi 1D systems probed by high field magnetotransport. Two different systems exhibiting quasi-1D confinement have been considered: carbon C60 peapods (C60@SWCNTs) and InAs semiconductor nanowires. The magnetotransport measurements on single nano-objets have been used to investigate the specific electronic structure of these 1D systems. In both cases, the high magnetic fields experiments have been supported by structural characterisation and conductance measurements at zero field.The encapsulation of various molecules inside carbon nanotubes (CNTs), as for instance C60 fullerenes encapsulated in SWCNT, constitutes promising routes towards the tunability of the CNT conductance. Among the wide variety of filled CNTs, peapods represent a pioneer hybrid structure discovered in 1998. Since that time, their electronic structure has been subjected to intense and controversial theoretical studies together with a limited number of experimental realizations. In this thesis the electronic properties of individual fullerene peapods have been investigated by combining micro-Raman spectroscopy and magnetotransport measurements on the same devices. We bring evidence that the encapsulated C60 strongly modify the electronic band structure of semiconducting nanotubes in the vicinity of the charge neutrality point, including a rigid shift and a partial filling of the energy gap. In addition by playing with a selective UV excitation of the fullerene, we demonstrate that the electronic coupling between the C60 and the CNT is strongly modified by the partial coalescence of the C60 and their distribution inside the tube. The experimental results are supported by numerical simulations of the Density of States and the conductance of CNTs with coalesced fullerenes inside (K. Katin, M. Maslov).Semiconductor nanowires (sc-NWs) are being the subject of intense researches started a decade ago. They represent model systems for the exploration of the electronic properties inerrant to the quasi1-D confinement. Moreover they offer the possibility to play with band structure tailoring and carrier doping. In this direction III-V sc-NWs such as InAs NWs have played a particular role due to the small electron effective mass. We have studied the high magnetic field conductance of single nanowires. Prior to the high field measurements, the zero and low field investigations have demonstrated a weakly diffusive regime of the carrier transport in these wires. The high field investigations have revealed a drastic conductance drop above a critical field, which clearly rises with the Fermi energy. This effect is interpreted by the loss of conducting channels once all the magneto-electric subbands, shifted toward the high energy range by the magnetic field, have crossed the Fermi energy. Preliminary band structure calculations (Y-M. Niquet), taking into account the lateral and magnetic confinements, are in fairly good qualitative agreement with the observed result in the high field regime. This result is the first observation of band structure effects in magneto-transport experiments on sc-NWs

Physical and functional properties of advanced nano-composite materials and biological structures are determined by self-organized atoms and molecules into nanostructures and in turn by microscopic organization of the nanostructures into assemblies of higher structural complexity. Therefore, microscopes are indispensable tools for structural investigations at various levels of organization. In this work, novel nonlinear optical microscopy methods were developed to non-invasively study structural organization at the nanoscopic and microscopic levels. Atomic organization of semiconductor nanowires, molecular organization of amylose biocrystallites in starch granules, and microscopic organization of several photosynthetic organisms was elucidated. The structure of ZnSe nanowires, key components in many modern nanodevices, was investigated using polarization harmonic generation microscopy. Based on nonlinear optical properties of the different crystal lattices, zinc blende and wurtzite nanowires were differentiated, and the three-dimensional orientation of the zinc blende nanowires could be found. The structure of starch granules, a model biocrystal, important in food as well as health sciences, was also investigated using polarization harmonic microscopy. The study was combined with ab initio calculations using the crystal structures of amylose A and B, revealing that second harmonic signals originate from the hydroxide and hydrogen bonds in the starch granules. Visualization of several photosynthetic organisms including the green algae, Chlamydomonas reinhardtii, two species of cyanobacteria, Leptolyngbya sp. and Anabaena sp., aggregates of light-harvesting pigment-protein complexes as well as chloroplasts from green plants were also explored, revealing that future nonlinear microscopy applications could include structural studies of cell walls, the Chlamydomonas eyespot, and photosynthetic membranes. In this study, several nonlinear optical microscopy modalities were developed for quantitative structural investigations of nano and micro-sized architectures. Non-invasive extraction of crystallographic information in microscopic samples will have a number of potential benefits, for example, in clinical applications, allowing observations of disease states inside tissues without the need for biopsy. Industrial nanotechnology will benefit from fast determination of nanostructures with nonlinear microscopy that will improve quality of nanodevices.

Physical and functional properties of advanced nano-composite materials and biological structures are determined by self-organized atoms and molecules into nanostructures and in turn by microscopic organization of the nanostructures into assemblies of higher structural complexity. Therefore, microscopes are indispensable tools for structural investigations at various levels of organization. In this work, novel nonlinear optical microscopy methods were developed to non-invasively study structural organization at the nanoscopic and microscopic levels. Atomic organization of semiconductor nanowires, molecular organization of amylose biocrystallites in starch granules, and microscopic organization of several photosynthetic organisms was elucidated. The structure of ZnSe nanowires, key components in many modern nanodevices, was investigated using polarization harmonic generation microscopy. Based on nonlinear optical properties of the different crystal lattices, zinc blende and wurtzite nanowires were differentiated, and the three-dimensional orientation of the zinc blende nanowires could be found. The structure of starch granules, a model biocrystal, important in food as well as health sciences, was also investigated using polarization harmonic microscopy. The study was combined with ab initio calculations using the crystal structures of amylose A and B, revealing that second harmonic signals originate from the hydroxide and hydrogen bonds in the starch granules. Visualization of several photosynthetic organisms including the green algae, Chlamydomonas reinhardtii, two species of cyanobacteria, Leptolyngbya sp. and Anabaena sp., aggregates of light-harvesting pigment-protein complexes as well as chloroplasts from green plants were also explored, revealing that future nonlinear microscopy applications could include structural studies of cell walls, the Chlamydomonas eyespot, and photosynthetic membranes. In this study, several nonlinear optical microscopy modalities were developed for quantitative structural investigations of nano and micro-sized architectures. Non-invasive extraction of crystallographic information in microscopic samples will have a number of potential benefits, for example, in clinical applications, allowing observations of disease states inside tissues without the need for biopsy. Industrial nanotechnology will benefit from fast determination of nanostructures with nonlinear microscopy that will improve quality of nanodevices.

Nous avons découvert une méthode originale pour produire une transformation de phase dans les nanofils de Ge et Si(de structure cubique diamant 3C).Sous l’action d’une contrainte externe à chaud, des nanodomaines de structure hexagonale diamant 2H se forment de manière quasi-périodique le long du fil ce qui résulte en un réseau 1D d’hétérostructures 3C/2H.Dans ce contexte,ce projet de thèse vise à mettre en lumière les mécanismes de cette transformation de phase et à caractériser les propriétés physiques de la phase 2H.Nous avons mis en place des analyses structurales systématiques dans les nanofils de Ge et Si-3C/2H pour mettre en évidence les paramètres clés de la transformation de phase.Les nanodomaines 2H sont formés dans des bandes de cisaillement de direction e2-5-5e.Une relation d’orientation a été mise en évidence:(1-10)3C//(-2110)2H et (110)3C//(0001)2H et les bandes 2H reposent majoritairement sur les plans d’interface (115)3C.Les études préliminaires montrent que la contrainte de cisaillement et le budget thermique sont nécessaires à la transformation avec une température seuil minimale de 350°C et 500°C pour le Ge et le Si respectivement,ces conditions sont caractéristiques d’une transformation martensitique.Les paramètres clés identifiés : l’orientation cristallographique et le diamètre des nanofils.Dans les nanofils de Si, la formation des bandes de cisaillement et donc des domaines 2H est induite par la composante de contrainte de cisaillement dans la direction de glissement du plan interfacial 3C/2H. D’après ces résultats, la transformation de phase serait compatible avec un mécanisme de relaxation plastique via la formation des bandes de cisaillement (5-5-2)(1-15)3C.Nous avons réalisé des mesures Raman spatialement résolues sur nanofil unique de Ge- et Si-3C/2H afin de mettre en évidence les modes de phonons optiques. Dans le Ge, nous avons détecté deux pics Raman à 288 cm−1 et 301 cm−1 attribués aux modes E2g et E1g + A1g + F2g. Dans le Si, nous avons observé trois pics Raman à 498, 515 et 520 cm−1 respectivement associés aux modes E2g, A1g et F2g. Ces valeurs coïncident avec les calculs reportés.Nous avons également mesuré les largeurs de bandes interdites dans les nanofils de Ge-3C/2H par spectroscopie infrarouge à transformée de Fourier:nous avons obtenu un gap direct à 0,58 eV attribué à la phase 2H et un gap indirect à 0,72 eV qui proviendrait vraisemblablement de la phase 3C.Ces valeurs constituent les premières mesures expérimentales du gap de la phaseGe-2H et vont dans le sens des calculs théoriques qui prédisent un gap étroit et direct. La phase 2H peut également être obtenue dans le massif de Si et Ge après décompression dans une cellule à enclumes de diamant menant à la phase BC8 qui se convertit à température ambiante(dans le Ge) ou à chaud(dans le Si) en phase 2H. Afin de comparer les propriétés du massif, nous avons réalisé des mesures in-situ par spectroscopie Raman et par diffraction des rayons X dans le massif en étudiant différents chemins de décompression. A température ambiante,nous obtenons soit la phase Ge-ST12, soit un mélange des phases Ge-ST12 et Ge-BC8 en fonction de la vitesse de décompression.La nucléation de la phase 2H est donc complexe car elle dépend fortement du chemin de décompression et des conditions hydrostatiques dans la cellule. Ces études révèlent de plus un effet de taille. Dans les nanofils de Ge,nous observons après décompression un retour vers la phase 3C avec une composante amorphe.Les mesures in-situ du gap dans le Ge massif et les nanofils de Ge en fonction de la pression confirment cet effet de taille. Après décompression dans le Ge massif, nous obtenons un gap direct égal à 0,53 eV et un gap indirect valant 0,73 eV. Ces valeurs sont liées à la structure de bandes de la phase Ge-ST12 et s’accordent avec les récents résultats reportés.La mesure dans les nanofils de Ge présente un comportement d’hystérésis avec le retour vers le gap initial après décompression. / We have demonstrated an original way to induce a phase transformation in Si and Ge nanowires under external shear-stress. The transformation results in an unprecedented heterostructure with quasiperiodic embedded Ge-2H nanodomains distributed all along the nanowire. My thesisproject aims at understanding the mechanisms of this phase transformation and at characterizing the physical properties of the heterostructures 2H/3C in Si and Ge nanowires.We have carried out systematic structural analysis in Si- and Ge-2H/3C nanowires to evidence the key parameters of this phase transformation.The phase transformation occurs in shear bands localized along the (2-5-5) direction.The heterostructured nanowires are defined by a specific orientation relationship between the 3C and the 2H bands (both in Si and Ge nanowires)given by(1-10)3C//(-2110)2H and (110)3C//(0001)2H with the 2H bands lying mainly on (115)3C planes.The preliminary studies showed that shear-stress and the thermal budget above a threshold temperature of 350°C in Ge and 500°C in Si are mandatory for this transformation. These conditions meet the common criteria of a martensitic phase transformation. We have identified two key intrinsic parameters:the temperature and the nanowires crystallographic axis.In Si nanowires, we found that the formation of the shear bands i.e. the 2H nanodomains is related to the component of the shear-stress along the glide direction of the 3C/2H interface plane.Based on these results,the transformation could be consistent with a stress relief mechanism through the formation of (5-5-2)(1-15)3C shear bands.We have performed spatially resolved Raman measurements on single Si and Ge heterostructured nanowires to characterize their optical phonon modes.In Ge,we have detected 2 Raman bands at 288 cm⁻ ᴵ and 301 cm⁻ ᴵ attributed to the E2g and E1g + A1g + F2g modes.In Si, we have observed 3 Raman bands at 498, 515 and 520 cm⁻ ᴵ that are associated respectively to the E2g, A1g and F2g modes.Those values agree well with the literature.Moreover, we have performed Fourier Transform Infrared spectroscopy on transformed Ge nanowires to measure the optical band gap of the 2H phase.We have obtained a direct band gap of 0,58 eV attributed to the 2H phase and an indirect bandgap of 0,72 eV that might stem from the 3C phase. Those results are the first experimental data of the Ge-2H band gap.The values align well with the simulations that predict a narrow direct band gap for this structure.The 2H structure can also be achieved in bulk Si and Ge after unloading of the BC8 phase in a diamond anvil cell.The BC8 phase is unstable and convertsinto the 2H phase at room temperature in Ge or by thermal annealing in Si.In order to compare the bulk properties of the 2H phase, we have performedin-situ Raman and X-ray diffraction experiments in bulk samples by studyingvarious unloading pathways. In particular, unloading at room temperature ledto the formation of the ST12 phase or a mixture of the BC8 and ST12 phasesdepending on the unloading rate.The formation of the 2H phase is thuscomplex given its dependency on the unloading conditions and the hydrostaticconditions within the cell that are difficult to garanty. Our studies also reveala size effect. After unloading of Ge-3C nanowires, the nanostructures revertback to the 3C phase with an amorphous component detected.In addition, we have carried out in-situ band gap measurements in bulk Ge and Ge nanowires as a function of pressure.After unloading, we havemeasured optical gap values that are related to the band structure of theGe-ST12 allotrope with a direct bandgap of 0,53 eV and an indirect bandgapof 0,73 eV.Those results are consistent with the experimental values reported.The experiments on Ge nanowires showed an hysteresis behavior with theinitial value of the band gap measured after unloading.Those results clearly evidenced novel relaxation mechanisms at the nanoscale that need to be investigated.

No description available.

Ce travail de thèse porte sur l’étude des propriétés optiques de nanofils InP et d’hétérostructures nanofils InAs/InP épitaxiés sur substrat silicium. Ce travail de thèse a été réalisé principalement dans le cadre du projet ANR «INSCOOP». / This thesis is focused upon the experimental investigation of optical properties of InAs/InP NW heterostructures by means of photoluminescence (PL) spectroscopy. First, it was demonstrated that the host-substrate may have significant impacts on the optical properties of pure InP NWs, as due to the strain, created by the difference in the LTECs of the NWs and the host-substrate, as due to some other surface effects. Next, the optical properties of such nanowire heterostructures as quantum rod (QRod) and radial quantum well (QWell) NWs were investigated. The features of obtained spectra were explained using theoretical simulation of similar NW heterostructures. The polarization properties of single InP NWs, InAs/InP QWell-NWs, InAs/InP QRod-NWs and ensemble of the InAs well ordered NWs were studied at different temperatures. Further, we report on the evidences of the strain-induced piezoelectric field in WZ InAs/InP QRod-NWs. Finally, PL QE of NW heterostructures and their planar analogues are measured by means of a PL setup coupled to an integrating sphere. In general, the obtained knowledge of the optical and mechanical properties of pure InP NWs and InAs/InP NW heterostructures will improve understanding of the electrical and mechanical processes taking place in semiconductor NW heterostructures and will serve for the fabrication of future nanodevice applications.

Im Rahmen der vorliegenden Arbeit wurden planare und drahtförmige Heterostrukturen (HS) mit ZnO- und ZnCdO-Quantengräben bezüglich ihrer Lumineszenz untersucht. Die Proben wurden mit der gepulsten Laserabscheidung (PLD) hergestellt. Bei ZnO-basierten drahtförmigen HS mit Durchmessern im Mikro- und Nanometer-Bereich handelt es sich um vielversprechende Kandidaten für miniaturisierte optoelektronische Bauelemente. Da es für viele Anwendungen notwendig ist, dass die Emission des Quantengrabens (QW) in einem breiten Spektralbereich eingestellt werden kann, muss die ZnO-Bandlücke möglichst stark verändert werden können. Durch ZnCdO und MgZnO ist dies möglich. Durch eine Optimierung der Abscheideparameter wurde der für PLD erreichte maximale Cd-Gehalt signifikant auf 0,25 erhöht. Große Mg-Gehalte konnten schon vor der Forschung zur vorliegenden Arbeit mit der PLD realisiert werden. Die planaren HS mit ZnO-Quantengräben wurden vorrangig bezüglich Ihrer Lumines-zenzeigenschaften untersucht. Aufgrund der Orientierung der QW sollten diese zusätzlich zum Quantum-Confinement Effekt den Quantum-Confined Stark Effect (QCSE) zeigen. Der QCSE wurde durch zeitabhängige und anregungsabhängige Lumineszenzmessungen nachgewiesen. In den Mikrodraht (µW)- bzw. Nanodraht (NW)-HS mit ZnO-QW wurde die Emission zwischen 3,4 eV und 3,6 eV bzw. 3,4 eV und 3,7 eV eingestellt. Um HS mit ZnCdO-QW herstellen zu können, war es notwendig, die strukturellen und optischen Eigenschaften sowie die elektronische Struktur von ZnCdO-Dünnfilmen zu untersuchen. Durch einen hohen Cd-Gehalt von 0,25 war es möglich, die Bandlücken-energie um 0,8 eV zu verringern. In planaren HS wurde ZnO bzw. MgZnO als Barriere verwendet und die QW-Emission zwischen 2,5 eV und 3,1 eV bzw. 2,5 eV und 3,65 eV eingestellt. Es wurde untersucht, ob für HS mit ZnCdO-QW ein QCSE auftritt. Die experimentellen Energien wurden dazu mit berechneten Werten verglichen, die mithilfe einer Effektiv-Masse-Näherung und dem Modell eines endlich tiefen Potentialtopfes bestimmt wurden. In entsprechenden µW- bzw. NW-HS wurde die QW-Emission infolge des Quantum-Confinement Effektes zwischen 2,7 eV und 3,1 eV bzw. 2,5 eV und 3,4 eV variiert. Da es für die Anwendung von µW- und NW-HS wichtig ist, dass diese eine homogene QW-Emission zeigen, wurde deren spektrale Position entlang der Struktur und für die verschiedenen Facetten der hexagonalen Drähte untersucht. Die Homogenität der Emission ist für die µW-HS kleiner als für die NW-HS.:I Einleitung 1 II Grundlagen 5 1 Kristall- und Bandstruktur der verwendeten Materialien 7 1.1 Kristallstruktur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.2 Bandstruktur und effektive Massen . . . . . . . . . . . . . . . . . . . . . 9 1.3 ZnO-basierte Mikro- und Nanostrukturen . . . . . . . . . . . . . . . . . 14 2 Lumineszenz 17 2.1 Band-Band-Übergänge . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.2 Exzitonen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.3 Exziton-Polaritonen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.4 Lumineszenz von ZnO-Dünnfilmen und -Einkristallen . . . . . . . . . . . 21 2.5 Lumineszenz von ZnO-Mikro- und ZnO-Nanostrukturen . . . . . . . . . 25 2.6 Lumineszenz von ternären Halbleitern . . . . . . . . . . . . . . . . . . . 27 3 Quantengrabenstrukturen 29 3.1 Energieniveaus im Quantengraben . . . . . . . . . . . . . . . . . . . . . 30 3.2 Exzitonenbindungsenergie . . . . . . . . . . . . . . . . . . . . . . . . . . 33 3.3 Quantum-Confined Stark Effect . . . . . . . . . . . . . . . . . . . . . . . 35 4 Hexagonale Resonatoren 43 4.1 Fabry-Pérot- und WGM-Resonatoren . . . . . . . . . . . . . . . . . . . . 43 4.2 Brechungsindex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 III Experimentelle Methoden 51 5 Proben 53 5.1 Herstellungsmethoden . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 5.2 Probenherstellung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 6 Untersuchungsmethoden 61 6.1 Strukturelle Charakterisierung . . . . . . . . . . . . . . . . . . . . . . . . 61 6.2 Optische Charakterisierung und Charakterisierung der elektronischen Struktur . . . . . . . 65 IV Ergebnisse und Diskussion 69 7 Heterostrukturen mit ZnO-Quantengräben 71 7.1 Planare Heterostrukturen . . . . . . . . . . . . . . . . . . . . . . . . . . 71 7.2 Mikrodraht-Heterostrukturen . . . . . . . . . . . . . . . . . . . . . . . . 85 7.3 Nanodraht-Heterostrukturen . . . . . . . . . . . . . . . . . . . . . . . . . 93 8 ZnCdO/ZnO-Doppelheterostrukturen 103 8.1 Lumineszenzeigenschaften . . . . . . . . . . . . . . . . . . . . . . . . . . 103 8.2 Tempern und thermische Stabilität . . . . . . . . . . . . . . . . . . . . . 115 9 Heterostrukturen mit ZnCdO-Quantengräben 123 9.1 ZnCdO-Dünnfilme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 9.2 Planare ZnCdO/ZnO-Multiquantengrabenstrukturen . . . . . . . . . . . 133 9.3 Planare ZnCdO/MgZnO-Quantengrabenstrukturen . . . . . . . . . . . . 151 9.4 Mikrodraht-Heterostrukturen . . . . . . . . . . . . . . . . . . . . . . . . 163 9.5 Nanodraht-Heterostrukturen . . . . . . . . . . . . . . . . . . . . . . . . . 169 Zusammenfassung und Ausblick 179 V Anhang 185 Ausheizen eines Niedrigtemperatur-ZnO-Dünnfilmes 187 Abkürzungsverzeichnis 191 Eigene Veröffentlichungen 193 Eigene Tagungsbeiträge 195 Literaturverzeichnis 197 Danksagung 210 Selbstständigkeitserklärung 211 Lebenslauf 213

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.

Made available in DSpace on 2016-06-02T20:15:31Z (GMT). No. of bitstreams: 1 5844.pdf: 11430873 bytes, checksum: b80a5790a9ebf6ae63ff48e52968ae60 (MD5) Previous issue date: 2014-02-21 / Universidade Federal de Sao Carlos / O crescimento e caracterização de sistemas de heteroestruturas semicondutoras quasi-unidimensionais têm atraído grande interesse devido à sua potencial de aplicação tecnológica, como foto-detectores, dispositivos opto-eletrônicos assim como seu para o processamento de informação quântica e aplicações em fotônica. O objetivo desta tese é o estudo das propriedades de transporte eletrônico e de spin em sistemas semicondutores quasi-unidimensionais, especificamente trataremos de nanofios (NWs) homogêneos, NWs acoplados, NWs do tipo plano-geminado (TP), diodos de tunelamento ressonante (ETD) e cadeias de pontos quânticos (QDCS). Escolhemos o método k-p, particularmente o Hamiltoniano de Luttinger, para descrever os efeitos de confinamento e tensão biaxial. Este sugeriu uma modulação do caráter do estado fundamental que, complementada com a dinâmica fônons fornecidas pelas simulações da Dinâmica Molecular (MD), permitiu a descrição da modulação da mobilidade de buracos por emissão ou absorção de fônons. Em relação ao sistema de NWs acoplado,estudamos, através do método da matriz de transferência (TMM), as propriedades de transporte de elétrons e spin sob a interação de spin-órbita (SOI) de Eashba, localizada na região de acoplamento entre fios. Foram consideradas várias configurações de tensões de gate (Vg) aplicadas nos fios. Desse modo, compreendemos a modulação do transporte de spin quando esse é projetado no direção-z através da combinação do SOI e das dimensionalidades do sistema. Da mesma forma, a combinação de SOI e da Vg aplicada deu origem a modulação da polarização, quando o spin medido é projetado na mesma direção em que o SOI de Eashba atua, a direção y. Usando o TMM, exploramos as propriedades de transporte de um DBS e o efeito de uma resistência em série com o intuito de provar a natureza da biestabilidade das curvas características I V bem como o aumento de sua área com temperatura, resultados fornecidos por experimentos. O modelo indicou que aumentando da resistência pela diminuição sa temperatura aumenta a área biestável. A presença de uma hetero-junção adicional ao sistema induz uma densidade de carga nas suas interfaces. De acordo com esta configuração, a queda de tensão total do ETDS muda, podendo ser confirmada experimentalmente. A formação dos peculiares campos de deformação e sua influência sobre a estrutura eletrônicas e propriedades de transporte em superredes de TP foi estudada sistematicamente. Assim, as propriedades de transporte, de ambos os elétrons e buracos, pode ser sintonizada eficientemente, mesmo no caso de elétrons r em sistemas de blenda de zinco, contrastando com a prevista transparência de elétrons r em superredes de semicondutores III-V heteroestruturados. Além disso, constatamos que a probabilidade de transmissão para buracos da banda de valência também poderia ser efetivamente modificada através de uma tensão externa.Por fim, colaboradores sintetizaram com sucesso sistemas de QDCs de InGaAs através da epitaxia de feixe molecular e engenharia de tensão. Um comportamento anisotrópico da condutância com a temperatura foi observado em QDCs com diferentes concentrações de dopagem, medida realizada ao longo e entre os QDCs. O modelo teórico 1D de hoppíng desenvolvido mostrou que a presença de estados OD modela a resposta anisotrópica da condutância neste sistemas. / The growth and characterization of semiconductor quasi-one-dimensional heterostructure systems have attracted increasing interest due to their potential technological application, like photo-detectors, optoelectronic devices and their promising features for quantum information processing and photonic applications. The goal of this thesis is the study of electronic and spin transport properties on quasi-one-dimensional semiconductor systems; specifically, homogenous nanowires (NWs), coupled NW s, twin-plane (TP) NWs, resonant tunneling diodes (RTDs), and quantum dot chains (QDCs). The k-p method, in particular the Luttinger Hamiltonian, was chosen to describe the effects of biaxial confinement and strain. This suggested a modulation of the ground state character that, complemented with the phonon dynamics provided by Molecular Dynamics (MD) simulations, allowed the description of the hole mobility modulation by either phonon emission or absorption. Regarding the coupled NW s system, the electron and spin transport properties affected by a Rashba spin-orbit interaction (SOI) at the joined region were unveiled through the Transfer Matrix Method (TMM). Various configurations of gate voltages (Vg), applied on the wire structure, were considered. We were able to understand the modulation of the spin transport projected in the z-direction trough the combination of the SOI and the system dimensionalities. Likewise, the combination of SOI and applied Vg gave rise to a modulation of the polarization, when the measured spin is projected in the same direction where the Rashba SOI acts, the y-direction. The transport properties of a DBS and the effect of a resistance in series was explored within the TMM to prove the nature of a bistability of the I V characteristics and its enhanced area with temperature provided by the experiment. The model indicates that increasing the resistente by decreasing the temperature, the bistable area enhances. The presence of an additional heterojunction induces a sheet charge at its interfaces. Under this configuration, the total voltage drop of the RTD changes and can be confirmed experimentally.The formation of the peculiar strain fields and their influence on the electronic structure and transport properties of a TP superlattice was systematically studied. Hence, the transport properties of both electrons and holes could be effectively tuned even in the case of T-electrons of zincblende systems, contrasting to the predicted transparency of T-electrons in heterolayered III-V semiconductor superlattices. Also, the transmission probability for holes at valence band could also be effectively modified by applying an external stress. Finally, using molecular-beam-epitaxy and skillful strain engineering, systems of In-GaAs QDCs were successfully synthesized by collaborators. The QDCs with different doping concentrations showed an anisotropic behavior of the conductance, measured along and across the QDCs, with temperature. The theoretical ID hopping model developed found that the presence of OD states shapes the anisotropic response of the conductance in this system.