Les matériaux quantiques ont récemment introduit en physique de la matière condensée pour unifier tous les matériaux dans lesquels les fortes corrélations électroniques gouvernent les propriétés physiques du système (e.g. les isolants de Mott) et les matériaux dont les propriétés électroniques sont déterminées par la géométrie de la fonction d’onde (e.g. matériaux de Dirac). Ces matériaux montrent des propriétés émergentes résultantes de l’intrication de différents degrés de libertés : la charge, le spin et le moment orbital, donnant lieu aux propriétés topologiques des électrons. L’étude de ces interactions et des compétitions entre les degrés de liberté pertinents nécessite l’utilisation de techniques pompe-sonde ultra-rapides. Particulièrement, les pulses laser femtosecondes interagissent uniquement avec les électrons pour les placer dans un état hors-équilibre décrit par des distributions de type non Fermi-Dirac. La dynamique subséquente implique de nombreux processus, avec un temps de relaxation relié aux constantes de couplage. De plus, dans les techniques résolues en temps, la lumière peut agir comme un paramètre externe, différent des paramètres thermodynamiques, pour explorer le diagramme de phase. Cela nous donne l’opportunité de stabiliser de nouveaux états inaccessibles par des chemins thermiques quasi-adiabatiques ou de manipuler les propriétés physiques des systèmes.Dans cette thèse, nous avons réalisé différentes expériences dans le but d’étudier les propriétés à l’équilibre et hors équilibre de deux matériaux corrélés: BaCo₁₋ₓNiₓS₂ et (V₁₋ₓMₓ)₂O₃.La première partie de ce projet a été dédiée principalement à l’étude de BaNiS₂, le précurseur métallique de la transition de Mott dans BaCo₁₋ₓNiₓS₂ . En utilisant l’ARPES, nous avons étudié la structure de bandes électroniques de BaNiS₂ dans toute la zone de Brillouin. L’expérience, combinée avec des calculs théoriques, révèle un nouveau type de cône de Dirac bidimensionel à caractère orbitalaire d et induit par les corrélations. Le croisement des bandes est protégé par les symétries particulières de la structure cristalline. Nous avons aussi mesuré la structure de bandes de l’isolant de Mott BaCoS₂ dans ses phases magnétique et non magnétiques.Dans la seconde partie, nous avons étudié la dynamique électronique hors équilibre de BaNiS₂ et (V₁₋ₓMx)₂O₃. Grâce à des mesures tr-ARPES et tr-Réflectivité, nous avons observé une renormalisation non thermique et ultra-rapide du cône de Dirac dans BaNiS₂. Ce phénomène est purement provoqué par les excitations électroniques et est stabilisé par l’intéraction entre les électrons et les phonons. De plus, en utilisant différentes techniques pompe-sonde (tr-XRD basé sur XFEL et tr-Réflectivité) nous avons aussi exploré des phases hors-équilibre du matériau prototype de Mott-Hubbard (V₁₋ₓMx)₂O₃ appartenant à différentes parties de son diagramme de phase. Nos résultats montrent une phase transitoire non thermique se développant immédiatement après la photoexcitation ultra-rapide et durant quelques picosecondes dans les phases métallique et isolantes. Cette phase transitoire est accompagné par une distorsion structural qui correspond à un durcissement du réseau et est marqué par un “blue shift” du mode phononique A₁g. Nos résultats soulignent l’importance du remplissage des orbitales aussi bien que des effets important des forts couplages électron-réseau sélectifs dans les matériaux fortement corrélés. / Quantum materials is a new term in condensed matter physics that unifies all materials in which strong electronic correlation governs physical properties of the system (e.g. Mott insulators) and materials whose electronic properties are determined by the geometry of the electronic wave function (e.g. Dirac materials). These materials show emergent properties– that is, properties that only appear by intricate interactions among many degrees of freedom, such as charge, spin and orbital, giving rise to topological properties of electrons. The study of these interactions and competitions between the relevant degrees of freedom demands applying ultrafast pump-probe techniques. Particularly, femtosecond laser pulses act only on the electrons and set them to an out-of-equilibrium state inexplicable by the Fermi-Dirac distribution. The ensuing dynamics involves various processes and the rate at which the relaxation occurs is related to the coupling constants. Moreover, in time-resolved pump-probe techniques light can act as an additional external parameter to change of the phase diagram – different from thermodynamic parameters. It gives us the opportunity of stabilizing new states inaccessible by quasi-adiabatic thermal pathways or eventually manipulating the physical properties of the systems.In this thesis, we performed different experiments in order to study the equilibrium and out-of-equilibrium properties of two correlated compounds: BaCo₁₋ₓNiₓS₂ and (V₁₋ₓMₓ)₂O₃.The first part of the project was mainly devoted to the study of BaNiS₂ that is the metallic precursor of the Mott transition in BaCo₁₋ₓNiₓS₂. By applying ARPES, we studied the electronic band structure of BaNiS₂ in its entire Brillouin zone. These results combined with some theoretical calculations give evidence of a novel correlation-induced and two-dimensional Dirac cone with d-orbital character. The band crossing is protected by the specific symmetries of the crystal structure. We also investigated the electronic band structure of the Mott insulator BaCoS₂ in its magnetic and nonmagnetic phases.In the second part, we studied the out-of-equilibrium electron dynamics of BaNiS₂ and (V₁₋ₓMx)₂O₃. By means of tr-ARPES and tr-reflectivity measurements, we observed an ultrafast and non-thermal renormalization of the Dirac cone in BaNiS₂ . This phenomenon is purely provoked by the electronic excitation and is stabilized by the interplay between the electrons and phonons. Moreover, by applying various pump-probe techniques (XFEL-based tr-XRD and tr-Reflectivity) we also explored the out-of-equilibrium phases of the prototype Mott-Hubbard material (V₁₋ₓMx)₂O₃ in different parts of its phase diagram. Our results show a transient non-thermal phase developing immediately after ultrafast photoexcitation and lasting few picoseconds in both metallic and insulating phases. This transient phase is followed by a structural distortion that corresponds to a lattice hardening and is marked by a “blue shift” of the A₁g phonon mode. These results underline the importance of the orbital filling as well as the strong effect of the selective electron-lattice coupling in the strongly correlated materials.

Continuing advances in laser and photonic technology has seen the development of lasers with increasing power and increasingly short pulsewidths, which have become available over an increasing range of wavelengths. As the availability of laser sources grow, so do their applications. To make better use of this improving technology, understanding and controlling laser propagation in free space is critical, as is understanding the interaction between laser light and matter. The need to better control the light obtained from increasingly advanced laser sources leads to the emergence of beam engineering, the systematic understanding and control of light through refractive media and free space. Beam engineering enables control over the beam shape, energy and spectral composition during propagation, which can be achieved through a variety of means. In this dissertation, several methods of beam engineering are investigated. These methods enable improved control over the shape and propagation of laser light. Laser-matter interaction is also investigated, as it provides both a means to control the propagation of pulsed laser light through the atmosphere, and provides a means to generation remote sources of radiation.

No description available.

Doctor of Philosophy / Department of Physics / Kristan L. Corwin / We have made significant accomplishments in the development of portable frequency standard inside hollow optical fibers. Such standards will improve portable optical frequency references available to the telecommunications industry. Our approach relies on the development of a stabilized Cr:forsterite laser to generate the frequency comb in the near-IR region. This laser is self referenced and locked to a CW laser which in turn is stabilized to a sub-Doppler feature of a molecular transition. The molecular transition is realized using a hollow core fiber filled with acetylene gas. We finally measured the absolute frequency of these molecular transitions to characterize the references. In this thesis, the major ideas, techniques and experimental results for the development and absolute frequency measurement of the portable frequency references are presented. A prism-based Cr:forsterite frequency comb is stabilized. We have effectively used the prism modulation along with power modulation inside the cavity in order to actively stabilize the frequency comb. We have also studied the carrier-envelope-offset frequency (f0) dynamics of the laser and its effect on laser stabilization. A reduction of f0 linewidth from [similar to]2 MHz to [similar to]20 kHz has also been observed. Both our in-loop and out-of-loop measurements of the comb stability showed that the comb is stable within a part in 10^11 at 1-s gate time and is currently limited by our reference signal. In order to develop this portable frequency standard, saturated absorption spectroscopy is performed on the acetylene v1+v3 band near 1532 nm inside different kinds of hollow optical fibers. The observed linewidths are a factor 2 narrower in the 20 um fiber as compared to 10 um fiber, and vary from 20-40 MHz depending on pressure and power. The 70 um kagome fiber shows a further reduction in linewidth to less than 10 MHz. In order to seal the gas inside the hollow optical fiber, we have also developed a technique of splicing the hollow fiber to solid fiber in a standard commercial arc splicer, rather than the more expensive filament splicer, and achieved comparable splice loss. We locked a CW laser to the saturated absorption feature using a Frequency Modulation technique and then compared to an optical frequency comb. The stabilized frequency comb, providing a dense grid of reference frequencies in near-infrared region is used to characterize and measure the absolute frequency reference based on these hollow optical fibers.

This thesis is concerned with measuring ultrafast electron dynamics taking place in dye-sensitized mesoporous semiconductor films employed as working electrodes in dye-sensitized solar cells (DSCs). An understanding of these ultrafast charge transfer mechanisms is essential for designing efficient photovoltaic (PV) devices with high photon-to-current conversion efficiency. Optical-pump terahertz-probe (OPTP) spectroscopy is a sub-picosecond resolution, non-contact, photoconductivity measurement technique which can be used to directly measure charge carrier dynamics within nanostructured materials without the need for invoking complex modelling schemes. A combination of OPTP and photovoltaic measurements on mesoporous TiO2 films show an early-time intra-particle electron mobility of 0.1 cm2/(Vs). This value is an order of magnitude lower than that measured in bulk TiO2 and can be partly explained by the restricted electron movement because of geometrical constraints and increased trap sites in the nanostructured material. In addition, the mesoporous film behaves like a nanostructured composite material, with the TiO2 nanoparticles embedded in a low dielectric medium (air or vacuum), leading to lower apparent electron mobility. THz mobility measured in similar mesoporous ZnO and SnO2 films sensitized with the same dye is calculated to be 0.17 cm2/(Vs) for ZnO and 1.01 cm2/(Vs) for SnO2. Possible reasons for the deviation from mobilities reported in literature for the respective bulk materials have been discussed. The conclusion of this study is that while electron mobility values for nanoporous TiO2 films are approaching theoretical maximum values, both intra- and inter-particle electron mobility in mesoporous ZnO and SnO2 films offer considerable scope for improvement. OPTP has also been used to measure electron injection rates in dye-sensitized TiO2, ZnO and SnO2 nanostructured films. They are seen to proceed in the order TiO2 >SnO2 >ZnO. While the process is complete within a few picoseconds in TiO2/Z907, it is seen to extend beyond a nanosecond in case of ZnO. These measurements correlate well with injection efficiencies determined from DSCs fabricated from identical mesoporous films, suggesting that the slow injection components limit the overall solar cell photocurrent. The reasons for this observed difference in charge injection rates have been explored within. It is now fairly common practice in the photovoltaic community to apply a coating of a wide band-gap material over the metal-oxide nanoparticles in DSCs to improve device performance. However, the underlying reasons for the improvement are not fully understood. With this motivation, OPTP spectroscopy has been used to study how the conformal coating affects early-time mechanisms, such as electron injection, trapping or diffusion length. The electron injection process is unaffected in case of TiCl4-treated TiO2 and MgO-treated ZnO, while it becomes much slower in case of MgO-treated SnO2. Finally, a light-soaking effect observed in SnO2-based solid-state DSCs has been examined in detail using THz spectroscopy and transient PV measurement techniques. It is concluded that continued exposure to light results in a rearrangement of charged species at the metal-oxide surface. This leads to an increase in the density of acceptor states or a lowering of the SnO2 conduction band edge with respect to the dye excited state energy level, ultimately leading to faster electron transport and higher device photocurrents.

Thesis (MSc)--University of Stellenbosch, 2011. / Please refer to full text to view abstract.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The demand for renewable energy sources has grown out of the humanity’s increasing need for electricity as well as depleting fossil fuel reserves. Organic-dye sensitised solar cells were developed as a green, cost-effective alternative to the market-dominating silicon solar cell technology. The field of photovoltaic devices and organic-DSSCs is interesting because we want to develop better, more efficient cells at lower costs using environmentally friendly materials. By studying the fundamental physics and chemistry processes occurring during and after the interaction of light with these devices, we create a window into the mechanism of photosynthesis. Our DSSCs were prepared by sensitisation of highly porous ZnO with different indoline dyes containing the same chromophore, but different alkyl chain lengths bonded to one of two carboxyl anchors as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). The role of the dye molecules is to absorb photons and donate electrons to the ZnO which acts as the charge acceptor, at the dye|ZnO interface. Through photoelectrochemical characterisation it was found that the structure of the dyes has an effect on the maximum current (JSC) produced by the cells: the shorter the alkyl chain, the higher the JSC. This macroscopic investigation was complimented by microscopic measurements in the form of transient absorption spectroscopy. This allows us to follow, in real time, the photoinduced oxidation of the dye and its regeneration occurring through desired and undesired pathways. It was found that the injection efficiencies of the dye molecules were directly responsible for the trend in the short circuit currents. / AFRIKAANSE OPSOMMING: Die aanvraag na die ontwikkeling van herwinbare energie bronne spruit voort uit die voorsienbare uitputting van fossiel brandstof bronne sowel as die groeiende behoefte om aan die mensdom se elektrisiteit behoeftes te voldoen. Kleurstof gesensitiseerde sonselle is ontwikkel as ’n groen, koste-effektiewe alternatief tot die silikon sonsel tegnologie wat die mark domineer. Die fotovoltaïse toestel veld, spesifiek organiese kleurstof gesensitiseerde sonselle is interessant omdat daar ruimte bestaan vir die ontwikkeling van beter meer effektiewe selle in terme van vervaardigings koste en prosesse wat omgewingsvriendelik is. Deur die fundamentele fisika en chemiese prosesse wat plaas vind tydens en na lig interaksie met hierdie selle te bestudeer gee dit insig oor die werkingsmeganisme van fotosintese. Ons kleurstof gesensitiseerde sonselle is voorberei deur sensitasie van hoogs poreuse ZnO met verskillende indolien kleurstowwe wat dieselfde kromofoor bevat wat met verskillende alkiel ketting lengtes verbind is aan een van twee karboksiel ankers as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). Die rol van die kleurstof molekules is om fotone te absorbeer en elektrone te doneer aan die ZnO wat as die lading akseptor dien by die kleurstof|ZnO intervlak. Deur fotoelektrochemiese karakterisasie is bevind dat die struktuur van die kleurstof ’n effek het op die maksimum stroom (JSC) wat die selle produseer: hoe korter die die akiel ketting, hoe hoër die JSC. Hierdie makroskopiese ondersoek is voltooi deur mikroskopiese metings in die vorm van tydopgelosde absorpsiespektroskopie. Dit laat ons toe om die fotogeinduseerde oksidasie asook regenerasie van die kleurstof te volg soos wat dit plaas vind deur gewenste sowel as ongewenste roetes. Dit is bevind dat die inspuitings effektiwiteit van die kleurstof molekules direk verantwoordelik is vir die waarneembare trajek in die kortsluitings stroom.

No description available.

Thesis (PhD (Physics))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Ultrafast Electron Diffraction (UED) is a rapidly maturing field which allows investigation of the evolution of atomic arrangement in solids on timescales comparable to the vibrational period of their constituent atoms (~10-13 s). The technique is an amalgamation of conventional high energy electron diffraction methods and pump-probe spectroscopy with femtosecond (1 fs = 10-15 s) laser pulses. Ultrafast pulsed electron sources generally suffer from limitations on the attainable electron number per pulse (brightness) due to Coulomb repulsion among the electrons. In this dissertation, the design and construction of a compact UED source capable of delivering sub-300 fs electron pulses suitable for diffraction experiments and containing about 5000 electrons per shot is described. The setup has been characterised by measurement of the transverse beam size and angular spread, and through recording and analyzing an electron diffraction pattern from a titanium foil. Measurement of the temporal duration of fs electron pulses is not trivial, and a specialised compact streak camera operating in accumulation mode has been developed as part of this study. A sub-200 fs temporal resolution has been achieved, and the dependence of temporal duration on electron number per pulse was investigated for the current UED source. The observed trends correlate well with detailed electron bunch simulations. In order to investigate ultrafast processes on samples that cannot be probed repeatedly, it becomes necessary to significantly increase the brightness of current state of the art compact sources such as the one constructed in the present study. UED sources employing electron pulse compression techniques offer this possibility. Traditional pulse compression schemes based on RF cavities, while simple in principle, pose significant technical challenges in their realisation. The current thesis describes two novel UED pulse compression methods developed by the author: achromatic reflectron compression and pulsed cavity compression. Both concepts are expected to be easier to realise than conventional RF compression. Detailed simulations predict that such sources can attain a brightness improvement of more than one order of magnitude over compact sources that do not employ compression techniques. In addition, such sources show much promise for the attainment of pulse durations in the sub-100 fs range. / AFRIKAANSE OPSOMMING: Ultra vinnige elektron diffraksie is ‘n meettegniek wat tans in die proses is om vinnige ontwikkeling te ondergaan. Die tegniek het ten doel om strukturele omsettingsprosesse op ‘n lengteskaal van atoombindings en ‘n tydskaal van die vibrasie periode van atome in materie, ongeveer 10-13 s, te ondersoek. Dit word bewerkstellig deur die spasieresolusievermoë van gewone hoë energie elektron diffraksie met die tydresolusievermoë van femtosekonde (1 fs = 10-15 s) laserspektroskopie te kombineer. Die aantal elektrone per puls (intensiteit) van ultravinnige gepulsde elektronbronne word beperk deur die Coulomb afstootingskragte tussen die elektrone. Hierdie dissertasie beskryf die ontwerp en konstruksie van ‘n kompakte ultravinnige elektron bron. Die elektronpulse wat geproduseer word bevat tot 5000 elektrone per puls met ‘n tyd durasie van minder as 300 fs, en is geskik vir diffraksie eksperimente. Die aparaat is gekarakteriseer deur die volgende metings: elektronpulsdiameter, straaldivergensie, en ‘n titaan foelie se statiese diffraksie patroon. Dit is nie triviaal om die durasie van femtosekonde elektronpulse te meet nie, en n spesiale kompakte akkumulerende “streak camera” is vir die doeleindes van hierdie projek onwikkel. Die tydresolusie van hierdie “streak camera” is beter as 200 fs, en die afhanklikheid van die pulsdurasie wat deur die ultravinnige elektron bron geproduseer word as n funksie van die elektrongetal per puls is met behulp van hierdie toestel bepaal. Die resultate klop redelik goed met gedetaileerde simulasies van die elektron puls dinamika. Die karakterisasie van monsters wat nie herhaaldelik gemeet kan word nie vereis verkieslik ‘n nog hoër pulsintensiteit as wat met huidige bronne bereik kan word. ‘N verdere doelstelling is dus om ultravinnige elektron bronne te ontwikkel wat pulse met meer elektrone per puls kan genereer. Dit kan bewerkstellig word deur bronne wat van elektron puls kompressie tegnieke gebruik maak. Die tradisionele manier waarop dít gedoen word is deur middel van n kontinu gedrewe radio frekwensie holte. Hierdie metode gaan egter gepaard met aanmerklik hoë tegniese uitdagings. Om hierdie rede het die outeur twee alternatiewe puls kompressie konsepte ontwikkel: akromatiese reflektron kompressie and gepulsde holte kompressie. Albei konsepte sal waarskeinlik makliker wees om te realiseer as die tradisionele radio frekwensie kompressie, en is deur middel van gedetaileerde simulasies geverifiseer. Hierdie simulasies voorspel dat die intensiteit van genoemde bronne met ten minste n grooteorde meer kan wees as wat tans met kompakte ultravinnige elektron bronne moontlik is. Verder blyk dit dat sulke bronne n pulsdurasie van minder as 100 fs kan bereik.

No description available.