abstract: Complex dynamical systems consisting interacting dynamical units are ubiquitous in nature and society. Predicting and reconstructing nonlinear dynamics of units and the complex interacting networks among them serves the base for the understanding of a variety of collective dynamical phenomena. I present a general method to address the two outstanding problems as a whole based solely on time-series measurements. The method is implemented by incorporating compressive sensing approach that enables an accurate reconstruction of complex dynamical systems in terms of both nodal equations that determines the self-dynamics of units and detailed coupling patterns among units. The representative advantages of the approach are (i) the sparse data requirement which allows for a successful reconstruction from limited measurements, and (ii) general applicability to identical and nonidentical nodal dynamics, and to networks with arbitrary interacting structure, strength and sizes. Another two challenging problem of significant interest in nonlinear dynamics: (i) predicting catastrophes in nonlinear dynamical systems in advance of their occurrences and (ii) predicting the future state for time-varying nonlinear dynamical systems, can be formulated and solved in the framework of compressive sensing using only limited measurements. Once the network structure can be inferred, the dynamics behavior on them can be investigated, for example optimize information spreading dynamics, suppress cascading dynamics and traffic congestion, enhance synchronization, game dynamics, etc. The results can yield insights to control strategies design in the real-world social and natural systems. Since 2004, there has been a tremendous amount of interest in graphene. The most amazing feature of graphene is that there exists linear energy-momentum relationship when energy is low. The quasi-particles inside the system can be treated as chiral, massless Dirac fermions obeying relativistic quantum mechanics. Therefore, the graphene provides one perfect test bed to investigate relativistic quantum phenomena, such as relativistic quantum chaotic scattering and abnormal electron paths induced by klein tunneling. This phenomenon has profound implications to the development of graphene based devices that require stable electronic properties. / Dissertation/Thesis / Ph.D. Electrical Engineering 2012

This dissertation presents results of a project bringing Scanning Tunneling Microscope (STM) into a regime of unlimited operational time at cryogenic conditions. Freedom from liquid helium consumption was achieved and technical characteristics of the instrument are reported, including record low noise for a scanning probe instrument coupled to a close-cycle cryostat, which allows for atomically resolved imaging, and record low thermal drift. Subsequent studies showed that the new STM opened new prospects in nanoscience research by enabling Scanning Tunneling Spectroscopic (STS) spatial mapping to reveal details of the electronic structure in real space for molecules and low-dimensional nanomaterials, for which this depth of investigation was previously prohibitively expensive. Quantum-confined electronic states were studied in single-walled carbon nanotubes (SWCNTs) deposited on the Au(111) surface. Localization on the nanometer-scale was discovered to produce a local vibronic manifold resulting from the localization-enhanced electron-vibrational coupling. STS showed the vibrational overtones, identified as D-band Kekulé vibrational modes and K-point transverse out-of plane phonons. This study experimentally connected the properties of well-defined localized electronic states to the properties of associated vibronic states. Electronic structures of alkyl-substituted oligothiophenes with different backbone lengths were studied and correlated with torsional conformations assumed on the Au(111) surface. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans- mutual orientations and at higher coverage self-assembled into ordered structures, binding to each other via interdigitated alkyl ligands. STS maps visualized, in real space, particle-in-a-box-like molecular orbitals. Shorter quaterthiophenes have substantially varying orbital energies because of local variations in surface reactivity. Different conformers of longer oligothiophenes with significant geometrical distortions of the oligothiophene backbones surprisingly exhibited similar electronic structures, indicating insensitivity of interaction with the surface to molecular conformation. Electronic states for annealed ligand-free lead sulfide nanocrystals were investigated, as well as hydrogen-passivated silicon nanocrystals, supported on the Au(111) surface. Delocalized quantum-confined states and localized defect-related states were identified, for the first time, via STS spatial mapping. Physical mechanisms, involving surface reconstruction or single-atom defects, were proposed for surface state formation to explain the observed spatial behavior of the electronic density of states. This dissertation includes previously published co-authored material.

MELO, Heitor Alves de. Propriedades eletrônicas de pontos quânticos contendo muitos elétrons. 2010. 75 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2010. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-05-04T17:47:42Z No. of bitstreams: 1 2010_dis_hamelo.pdf: 2475149 bytes, checksum: f2b733568c55c95683fc14e493c5ab31 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-05-07T14:29:38Z (GMT) No. of bitstreams: 1 2010_dis_hamelo.pdf: 2475149 bytes, checksum: f2b733568c55c95683fc14e493c5ab31 (MD5) / Made available in DSpace on 2015-05-07T14:29:38Z (GMT). No. of bitstreams: 1 2010_dis_hamelo.pdf: 2475149 bytes, checksum: f2b733568c55c95683fc14e493c5ab31 (MD5) Previous issue date: 2010 / This work investigates the electronic properties of semiconductor quantum dots in which there are many electrons confined. In particular, we study Si and Ge quantum dots embedded in dielectric matrices (SiO2 e HfO2). The theoretical method used to calculate the total energy of N electrons confined in quantum dots is based on a simplified version of the Hartree-Fock method. In this model, the total energy is obtained from single-particle wavefunctions and eigen-energies. The obtained results show that the total energy in Ge quantum dots are always larger than in Si ones. The reason is the smaller electron e effective mass in Ge, which raises the energies of the confined states. As for the role of the dielectric matrix, the total energy is always larger for SiO2 than for HfO2. Physically, this e effect is caused by the fact that SiO2 has larger confinement barriers (3.2 eV) than HfO2(1.5 eV). Smaller barriers favor larger spatial extent of the wavefunctions, decreasing the repulsion energy of the confined electrons. The chemical potential and additional energy was also calculated as function of the number of confined electrons. It was observed that the chemical potential of Ge quantum dots are always larger than Si ones, but the role of the dielectric matrix is inverted. The chemical potential for HfO2 is larger than for SiO2. With respect to the additional energy, we observed that this quantity strongly oscillates within the range 0 to 0.4 eV for cases. If one takes into account that the Coulomb blockade phenomena is only observed for additional energies much larger the thermal energy (of the order of 3/2kBT), this phenomena can only be observed for the case where there are only a few electrons confined in the quantum dots. / Este trabalho dedica-se ao estudo das propriedades eletrônicas de pontos quânticos semicondutores contendo muitos elétrons confinados. Em particular, serão investigados semicondutores contendo muitos elétrons confinados. Em particular, serão investigados pontos quânticos de Si e Ge imersos em matrizes dielétricas (SiO2 e HfO2). O método teórico utilizado para calcular a energia total de um sistema de N elétrons confinados baseia-se numa versão simplificada do método de Hartree-Fock. Neste modelo a energia total e calculada a partir das funções de onda e estados de energia de uma única partícula Os resultados obtidos mostram que a energia total em pontos quânticos de Ge são em geral maiores que em pontos quânticos de Si, independentemente do número de elétrons confinados. Isto acontece devido a massa efetiva menor dos elétrons no Ge que aumentam as energia de confinamento. Em relação ao papel das barreiras dielétricas, a energia total é sempre maior nos casos em que o ponto quântico está envolvido por SiO2. Fisicamente, isto se deve ao fato de que a barreira de confinamento do SiO2 (3.2 eV) é maior que a do HfO2 (1.5 eV). Barreiras mais baixas favorecem o aumento da extensão espacial das funções de onda, reduzindo a repulsão coulombiana dos elétrons confinados. Calculou se também o potencial químico dos pontos quânticos em função do número de elétrons confinados, e a energia adicional necessária para aprisionar mais um elétron nos pontos quânticos. Verificou-se que o potencial químico dos pontos quânticos de Ge são sempre maiores que nos de Si, por em o potencial químico para pontos quânticos envoltos em HfO2 são sempre maiores que no caso do SiO2. Em relação a energia adicional, observa-se que esta quantidade apresenta fortes oscilações e que varia entre 0 e 0.4 eV para todos os casos estudados. Se levarmos em conta que o fenômeno conhecido como bloqueio de Coulomb acontece quando a energia adicional é muito maior que a energia térmica (da ordem de 3=2kBT), este fenômeno são será observado quando houver poucos elétrons confinados nos pontos quânticos.

Making use of the non-covalent bond to make materials is of great interest in many fields of research. This PhD thesis describes a variety of highly interdisciplinary research undertaken at the interface between chemistry, materials science, physics and engineering. Chapter 1 is an introductory chapter into the core concepts underlying this thesis. Supramolecular chemistry as a broad research field is briefly reviewed, followed by a focus on host-guest chemistry. The macrocyclic cucurbit[n]urils (CB[n]s) in particular are highlighted with a discussion on their recent applications since their discovery. Emulsions and their controlled generation with microfluidic techniques are then reviewed, as they have been used as templates for self-assembly processes throughout this thesis. A study into the synthesis of extended polymer networks composed entirely from small molecules held together by non-covalent interactions is described in Chapter 2. These highly dynamic and responsive supramolecular polymer networks have not yet been constructed with CB[n] host-guest chemistry. The ability of the larger CB[8] macrocycle to encapsulate multiple guest molecules in a stepwise fashion was taken advantage on in designing the synthesis of branching monomers. The monomers had two (A$_2$) or three (B$_3$) terminal guest moieties for CB[8], which upon combination formed branching supramolecular polymers that were multi-stimuli responsive. However, the polymers precipitated from solution at high concentrations rather than form a cross-linked network, due to competing intra-chain cyclisation and the limited water solubility of CB[8]. By confining these polymers to microfluidic droplets, directed assembly to the liquid-liquid interface could drive polymerisation to form an interfacial cross-linked gel that was both elastic and self-healing. Chapter 3 follows on from these results, describing attempts into constructing hyperbranched supramolecular polymers from an AB$_2$ guest molecule and CB[8] that would form globular polymers. Intramolecular complexation dominated with the guest molecules synthesised (A and B complexing within the molecule), evidenced by a variety of characterisation. Compared to previous works that relied on linear molecules to form a folded conformation for intramolecular complexes, these molecules were pre-organised with a unique cooperative complexation pathway. The stimuli-responsiveness of the complexes was probed, and the formation of self-sorting mixtures was demonstrated with multiple CB[n] and additional guest molecules. Controlling the self-assembly of semi-conducting nanocrystals with CB[7] is detailed in Chapter 4, a process that typically requires harsh conditions or extensive time-scales. Semi-conducting nanocrystals could be assembled instantaneously from water into extended networks that were highly porous with excess CB[7], retaining their nanoscale properties. Limiting quantities of CB[7] could then form nanoscale aggregates that remained in solution. Confinement of these assemblies within microfluidic droplets allowed the synthesis of dense microparticles, that retained their shape after re-dispersal in water. By simply including metallic nanocrystals as a minor component, mixed aggregates could be synthesised analogously. Finally, Chapter 5 draws overall conclusions from the results of this thesis, looking broadly at the potential for future prospects in these areas of research.

abstract: The work contained in this dissertation is focused on the structural and optical properties of III-V semiconductor structures for solar cell applications. By using transmission electron microscopy, many of their structural properties have been investigated, including morphology, defects, and strain relaxation. The optical properties of the semiconductor structures have been studied by photoluminescence and cathodoluminescence. Part of this work is focused on InAs quantum dots (QDs) embedded in AlGaAs matrices. This QD system is important for the realization of intermediate-band solar cells, which has three light absorption paths for high efficiency photovoltaics. The suppression of plastic strain relaxation in the QDs shows a significant improvement of the optoelectronic properties. A partial capping followed by a thermal annealing step is used to achieve spool-shaped QDs with a uniform height following the thickness of the capping layer. This step keeps the height of the QDs below a critical value that is required for plastic relaxation. The spool-shaped QDs exhibit two photoluminescence peaks that are attributed to ground and excited state transitions. The luminescence peak width is associated with the QD diameter distribution. An InAs cover layer formed during annealing is found responsible for the loss of the confinement of the excited states in smaller QDs. The second part of this work is focused on the investigation of the InxGa1-xN thin films having different bandgaps for double-junction solar cells. InxGa1-xN films with x ≤ 0.15 were grown by metal organic chemical vapor deposition. The defects in films with different indium contents have been studied. Their effect on the optical properties of the film have been investigated by cathodoluminescence. InxGa1-xN films with indium contents higher than 20% were grown by molecular beam epitaxy. The strain relaxation in the films has been measured from electron diffraction patterns taken in cross-sectional TEM specimens. Moiré fringes in some of the films reveal interfacial strain relaxation that is explained by a critical thickness model. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

Nous avons étudié la dynamique de spin d'un atome de Mn inséré dans une boite quantique CdTe. Nos résultats montrent que la relaxation de spin du Mn est plus rapide lorsque la boite quantique contient un exciton. Ceci peut permettre une orientation optique du spin du Mn. Le mélange de bande de valence est le paramètre essentiel permettant la relaxation rapide du spin du Mn dans le champ d'échange de l'exciton. Ce mélange de bande de valence est controlé par la forme et les contraintes dans la boite quantique. L'influence de ces paramètres sur la dynamique du pompage optique a été analysée en détail. Nos simulations du pompage optique sont en bon accord avec les expériences. La dynamique cohérente d'un Mn individuel a aussi été étudiée. L'influence sur le pompage optique de la dynamique cohérente du spin électronique et nucléaire est discutée. Nous avons montré que le couplage entre spin électronique et nucléaire peut être contrôlé optiquement permettant une manipulation du spin du Mn. Nous avons finalement montré que la combinaison d'une excitation résonante optique et micro-onde peut être utilisée pour détecter optiquement la résonance magnétique d'un Mn dans une boite quantique CdTe. / We have studied the spin dynamics of an individual Mn atom embedded a CdTe quantum dot. Our results show that the Mn spin relaxation is faster when the quantum dot contains an exciton. This can result in an optical orientation of the Mn spin. The valence band mixing is the critical parameter for the fast relaxation rates of the Mn spin in the exchange field of the exciton. This valence band mixing is controlled by the shape and strain of the quantum dot. The influence of these parameters on the optical pumping dynamics were analyzed in detail. Our simulation of optical pumping are in good agreement with experiments. The coherent dynamics of an individual Mn spin was also investigated. We discussed the influence of the coherent dynamics of the coupled electronic and nuclear spins on the optical pumping. We have shown that optically controlled coupling between electronic and nuclear spins could be used for Mn spin switching. We finally demonstrated that the combination of resonant laser and microwave fields can be used to optically detect the magnetic resonance of a Mn spin in a CdTe quantum dot.

A Terapia Fotodinâmica (TFD) é um método de tratamento do câncer e de outras doenças baseado no efeito conjunto de um composto fotoativo, luz da região visível ou infravermelho próximo e oxigênio molecular. O diagnóstico por fluorescência (DF) é uma técnica para o diagnóstico precoce de diversas doenças que consiste em utilizar algum composto fluorescente para distinguir tecido tumoral de tecido saudável. As porfirinas são amplamente utilizadas como fotossensibilizadores (FS) na TFD e como fluoróforos (FF) no DF. Os pontos quânticos (PQ) são novas nanoestruturas que possuem intenso e largo espectro de absorção na região espectral UV e visível, espectro de luminescência muito intenso e estreito e são fotoestáveis. Isso os torna promissores para o uso em TFD ou em DF, competindo com FS e FF orgânicos. A interação entre PQ e FS orgânicos pode aumentar a eficiência de ambos, devido aos processos de transferência de energia e/ou de carga. Durante o fototratamento os FS podem sofrer fototransformações, perdendo sua fotoatividade e formando produtos estáveis tóxicos. Isso torna importante o estudo da fototransformação dos FS. Neste trabalho, estudou-se, através da espectroscopia de absorção óptica, da fluorescência com resolução temporal e de flash-fotólise, a interação das porfirinas meso-tetrametil piridil (TMPyP) e meso-tetrasulfonatofenil (TPPS4) com o PQ de Telureto de Cádmio (CdTe) encapsulado com ácido 3-mercaptopropiônico (MPA) e sua fotólise individual e em conjunto. Os experimentos entre a TMPyP e o PQ mostraram que existe a formação de um complexo de transferência de carga entre a porfirina e o PQ. Verificou-se que a formação do complexo TMPyP-PQ aumenta a eficiência do processo de fotólise. A interação entre a p TPPS4 e o PQ em pH 4,0 (TPPS4 biprotonada) induz a transferência dos prótons para o PQ. A porfirina TPPS4 em pH 7,0 com adição de PQ não apresentou mudanças espectrais. Entretanto, em ambos os pHs, o PQ causava o aumento da velocidade de fotólise da TPPS4, sendo que o efeito do PQ foi maior em pH 4,0. Os resultados obtidos mostraram a importância da carga dos componentes, tanto na sua interação, como na eficiência de fotólise, devido à sua interação eletrostática. Também foi observado um aumento da intensidade da fluorescência de sistemas porfirina-PQ durante a fotólise. Esse efeito pode ser explicado pela redução da supressão da fluorescência devido à diminuição das concentrações dos componentes durante a fotólise. / The Photodynamic Therapy (PDT) is a method of treatment of cancer and other diseases based on combined effects of a photoactive compound, visible or near infrared light and molecular oxygen. The diagnosis by fluorescence (DF) is a technique for diagnostics of disease that consists in utilizing fluorescence compound to discern tumor tissue from a healthy one. Porphyrins are widely used as photosensitizer (PS) in PDT and as fluorophore (FP) in DF. Quantum dots (QD) are new nanostructures, which have intense and broad absorption spectrum in the UV and visible light region, intense and narrow luminescence spectrum and possess high photostability. They are considered promising for clinical application in PDT and/or DF, competing with organic PS and FP. Interaction between QD and organic PS can increase the efficiencies of both, due to the energy and/or charge transfer processes. The PS phototransformation during phototreatment may lead to loss of the PS photoactivity and formation of toxic products, that is important to study the processes of the PS phototransformation. In this work, with the support of absorption spectroscopy, steady state and time resolved fluorescence and flash-photolysis, we study interaction of meso-tetramethyl pyridyl (TMPyP) and meso-tetrakis sulfonatofenyl (TPPS4) porphyrins with CdTe QD functionalized with 3-mercaptopropionic acid (MPA) and their photolysis individual and in mutual. Experiments with TMPyP and QD demonstrate formation of a charge transfer complex between the porphyrin and the QD. We have verified that TMPyP-QD complex increases the efficiency of the porphyrin photolysis. The photolysis of the proper complex has been observed, as well. The interaction between TPPS4 and QD at pH 4.0 (biprotonated TPPS4) provokes deprotonation of the porphyrin via the proton transfer to QD. At pH 7.0 (deprotonated TPPS4) interaction of the porphyrin with the QD does not change TPPS4 spectral characteristics. Nevertheless, at both pHs QD cause increase in the TPPS4 photolysis rate, the effect being higher at pH 4.0. The observed results demonstrate the importance of the component charges both at their interaction and in photolysis efficiency, associated with their electrostatic interaction. The fluorescence intensity of the porphyrin-QD systems is enhanced during photolysis. This effect may be explained as the fluorescence quenching reduction due to decrease of the compound concentrations in the photolysis process.

Estudamos transporte quântico dependente de spin em sistemas de ponto e de poço quântico acoplados a contatos magnéticos. O primeiro passo do nosso estudo foi a dedução de fórmulas originais para a corrente e para o ruído em sistemas com tunelamento dependente de spin, através do formalismo de funções de Green de mão equilíbrio. As equações deduzidas reproduzem casos limites da literatura - em particular as fórmulas de Landauer-Buttiker. Posteriormente aplicamos essas fórmulas para estudar três sistemas distintos: (1) ponto quântico acoplado a contatos ferromagnéticos, (2) um ponto quântico acoplado a múltiplos terminais ferromagnéticos, e (3) um poço quântico acoplado a terminais de semicondutor magnético diluído (DMS). No sistema (1) consideramos os alinhamentos paralelo (P) e anti-paralelo (AP) entre as magnetizações dos terminais. Nesse sistema levamos em conta interação de Coulomb e espalhamento de spin no ponto quântico. Com as fórmulas para corrente e ruído deduzidas aqui, encontramos, por exemplo, que a interação de Coulomb, combinada com o magnetismo dos eletrodos, leva a um bloqueio de Coulomb dependente de spin. Esse efeito por sua vez leva a uma polarização da corrente que pode ser modulada (intensidade e sinal) através de uma tens~ao externa. Também encontramos que o espalhamento de spin leva a comportamentos contrastantes entre corrente e ruído. Enquanto a corrente na configuração AP aumenta com a taxa de espalhamento de spin R, o ruído nessa mesma configuração é suprimido para uma certa faixa de valores de R. Um outro efeito interessante que observamos foi a possibilidade de se suprimir o ruído térmico através de uma tensão de porta. Para o sistema (2) mostramos que é possível injetar corrente &#8593-polarizada no ponto quântico e coletar simultaneamente correntes &#8593 e &#8595 polarizadas em terminais diferentes. Além disso, a corrente ao passar do reservatório emissor para um dos reservatórios coletores tem a sua polarização intensificada. Portanto esse sistema pode operar como inversor e amplificador de polarização de corrente. Por último, analisamos os efeitos de terminais DMS e quantização de Landau (na presença de um campo magnético externo) sobre a corrente e o ruído no sistema (3). Encontramos que o efeito Zeeman gigante nos terminais DMS, gerado pela interação de troca s-d, leva a uma polarização da corrente. Em particular, para uma certa faixa de tensão o efeito Zeeman gigante resulta na completa supressão de uma dada componente de spin no transporte. Com isso é possível controlar a polarização da corrente através de uma tensão externa. Também observamos oscilações na corrente, no ruído e no fator de Fano como função do campo magnético. / We study spin dependent quantum transport in quantum dots and quantum well devices attached to magnetic leads. We first derive general formulas, including electron-electron interaction and spin flip, for both current and noise, using the no equilibrium Green function technique (Keldysh). From our equations we regain limiting cases in the literature - in particular the Landauer-Buttiker formula when we neglect electron-electron interaction. We apply these formulas to study three distinct systems: (1) a quantum dot attached to two ferromagnetic leads, (2) a quantum dot linked to many ferromagnetic leads, and (3) a quantum well coupled to dilute magnetic semiconductor (DMS) terminals. In the first system we consider both parallel (P) and anti-parallel (AP) ferromagnetic alignments of the leads. Coulomb interaction and spin flip scattering are also taken into account. With the formulas for the current and the noise derived here, we find, for instance, that the Coulomb interaction, combined with the magnetism of the electrodes, gives rise to a spin-dependent Coulomb blockade. This effect allows the control (intensity and sign) of the current polarization via the bias voltage. We also observe that spin flip scattering yields contrasting behavior between current and shot noise. While the current in the AP configuration increases with the spin flip, the shot noise becomes suppressed for a range of spin flip rates. Another interesting finding is the possibility to suppress the thermal noise via a gate voltage. For the dot coupled to three magnetic leads, we show that it is possible to inject current &#8593-polarized into the dot from the FM emitter, detect simultaneously &#8593 and &#8595 - polarized currents at distinct collectors. In addition, we find that the current has its polarization amplified when going from the emitter to one of the collectors. Therefore we have a device that operates as both as current polarization inverter and amplifier. Finally, we analyze the effects of DMS leads and Landau quantization on the current and noise of system (3). We and that the giant Zeeman effect in the DMS leads, due to the it s-d exchange interaction, gives rise to a spin polarized current, and for a particular bias voltage range, full suppression of one spin component. This gives rise to the possibility of tuning the current polarization via the bias voltage. We also observe oscillations in the current, the noise and the Fano factor as a function of the magnetic field.

Les boîtes quantiques semiconductrices, confiné dans les trois directions de l’espace, ont une structure électronique proche de celle d’un atome. Une excitation lumineuse y crée des états hors équilibre entraînant l’émission des différents états de charge. Ce travail porte sur l’étude de boîtes quantiques GaAs/AlGaAs produites par une méthode d’épitaxie par jet moléculaire modifiée sur un substrat de GaAs (111) insérées dans une structure de type diode. La première partie porte sur la séparation des différents états de charge dans une boîte unique par la tension appliquée puis leur identification compte tenu de l’échange coulombien et de leurs propriétés magnéto-optiques. Une deuxième partie porte sur l’interaction hyperfine des trous avec le champ nucléaire. Un modèle d’Hamiltonien effectif est proposé pour cette interaction. Des phénomènes de bistabilité, en champ magnétique, de la polarisation des spins nucléaire et électronique sont mis en évidence. / The electronic structure of a semiconductor quantum dot, with 3D carrier confinement on the nano-scale, is close to an atom with discrete state. Above-gap laser excitation creates different exciton state that show very rich emission patterns. This work studies GaAs/AlGaAs quantum dots grown droplet epitaxy on (111)A GaAs substrate embedded in a diode structure. The first part of this thesis presents the spectral separation of exciton complexes due to the bias applied to the sample; the different charge states are identified by analyzing the Coulomb exchange interaction and magneto-optics behavior. The second part studies the hyperfine interaction of the hole spin confined to a dot with the nuclear spins of the atoms that form the dot. An effective Hamiltonian model is proposed for this interaction. Bistable nuclear and also carrier spin polarization states are uncovered in magnetic field dependent measurements.

The study of photovoltaic materials is important so as to develop new solar energy technologies: in particular, quantum-confined semiconductors could offer increased quantum efficiencies at a much lower manufacture cost. This thesis contains results from a number of pump-probe experiments designed to probe the carrier dynamics in bulk and quantum-confined photovoltaics. A THz time-domain spectrometer was designed, built and commissioned. The THz refractive indices and absorption coefficients of toluene and hexane were determined, and the spectrometer was benchmarked using a photoexcited GaAs wafer. Results are presented of time-resolved THz spectroscopy of photoexcited bulk InP as a function of laser excitation wavelength. These data were used to extract the quantum efficiency of bulk InP in order to compare with recent results for InP quantum dots. The quantum efficiency in quantum dots increases when the incident photon energy is at least twice the band gap energy, whereasthe efficiency of the bulk material is found to decrease. This is because of surface recombination, and these measurements therefore verify the potential superiority of quantum dot materials over bulk materials for use in solar energy applications. Initial measurements of quantum dots using THz spectroscopy highlighted the various experimental challenges involved and the upgrades required to study such samples in the future.The time-dependence of the photoinduced surface photovoltage (SPV) in Si was studied on nanosecond timescales by synchronizing an ultrafast laser system to a synchrotron radiation source (the SRS at Daresbury, UK), and measuring the resulting shift in the photoelectron spectrum. The equilibrium band bending was determined, and the decay of the SPV was attributed to the recombination of charge carriers across the band gap. Results are presented for the SPV in bulk ZnO and for PbS quantum dot chemically attached to ZnO. The fact that the PbS quantum dots were chemically attached to the surface without becoming oxidized was verified using X-ray photoelectron spectroscopy (XPS). The changes caused by photoexcitation occur on much longer timescales in ZnO than Si (sub-milliseconds rather than nanoseconds), and these timescales were conveniently accessed using the time-resolved XPS facility at the TEMPO beamline at Synchrotron SOLEIL (Paris, France). This is due to oxygen adsorption and desorption processes at the ZnO surface affectingthe transfer of charge carriers. The addition of PbS quantum dots to the ZnO surface was found to increase the speed of this charge transfer due to injection of carriers directly from the PbS quantum dot to the bulk ZnO conduction band.