This thesis details the development of a novel photovoltaic device based on organometal halide perovskites. The initial focus of this thesis begins with the study of lighttrapping strategies in solid-state dye-sensitised solar cells (detailed in chapter 3). While I report enhancement in device performance through the application of near and far-field light-trapping techniques, I find that improvements remain step-wise due to fundamental limitations currently employed in dye-sensitised solar cell technology— notably, the available light-sensitising materials. I found a promising yet under researched family of materials in the methyl ammonium tri-halide plumbate perovskite (detailed in chapter 4). The perovskite light-sensitiser was applied to the traditional mesoscopic sensitised solar cell device architecture as a replacement to conventional dye yielding world-record breaking photo-conversion e!ciencies for solid-state sensitised solar cells as high as 8.5%. The system was further developed leading to the conception of a novel device architecture, termed the mesoporous superstructured solar cell (MSSC), this new architecture replaces the conventional mesoporous titanium dioxide semiconductor with a porous insulating oxide in aluminium oxide, resulting in very low fundamental losses evidenced through high photo-generated open-circuit voltages of over 1.1 V. This development has delivered striking photo-conversion ef- ficiencies of 10.9% (detailed in chapter 6).

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.

Quasi-one-dimensional quantum models are ideal for theoretically exploring the physical phenomena associated with strong correlations. In this thesis we study three examples where strong correlations play an important role in the static or dynamic properties of the system. Firstly, we examine the behaviour of a doped fermionic two-leg ladder in which umklapp interactions are present. Such interactions arise at special band fillings and can be induced by the formation of charge density wave order in an array of two-leg ladders with long-range (three-dimensional) interactions. For the umklapp which arises from the half-filling of one of the bands, we show that the low-energy theory has a number of phases, including a strong coupling regime in which the dominant fluctuations are superconducting in nature. These superconducting fluctuations carry a finite wave vector – they are the one-dimensional analogue of Fulde-Ferrell-Larkin-Ovchinnikov superconductivity. In a second example, we consider a quantum spin model which captures the essential one-dimensional physics of CoNb₂O₆, a quasi-one-dimensional Ising ferromagnet. Motivated by high-resolution inelastic neutron scattering experiments, we calculate the dynamical structure in the paramagnetic phase and show that a small misalignment of the transverse field can lead to quasi-particle breakdown – a surprising broadening in the single particle mode observed in experiment. Finally, we study the out-of-equilibrium dynamics of a model with tuneable integrability breaking. When integrability is broken by the presence of weak interactions, we show that the system relaxes to a non-thermal state on intermediate time scales, the so-called “prethermalization plateau”. We describe the approximately stationary behaviour in this regime by constructing a generalised Gibbs ensemble with charges deformed to leading order in perturbation theory. Expectation values of these charges are time-independent, but interestingly the charges do not commute with the Hamiltonian to leading order in perturbation theory. Increasing the strength of the integrability breaking interactions leads to behaviour compatible with thermalisation. In each case we use a combination of perturbative analytical calculations and non-perturbative numerical computations to study the problem at hand.

Transition metal oxides (TMO) have proven to exhibit novel properties such as high temperature superconductivity, magnetic ordering, charge and spin density waves, metal to insulator transitions and colossal magnetoresistance. Among these are a spin-orbit coupling (SOC) induced Mott insulator Sr2IrO4. The electric transport properties of this material remain finite even at cryogenic temperatures enabling its complex electronic structure to be investigated by a scanning tunneling microscope. At T = 77 K, we observed two features which represent the Mott gap with a value of 2D ~ 615 meV. Additionally an inelastic loss feature was observed inside this gap due to a single magnon excitation at an energy of ~ 125 meV. These features are consistent with similar measurements with other probes. In addition to these features, at T = 4.2 K lower energy features appear which are believed to be due to additional magnetic ordering. Another material that exhibits a unique physical behavior is the sliding charge density wave (CDW) material TaS3. It is a quasi-one dimensional material that forms long narrow ribbon shaped crystals. It exhibits anomalies including non-ohmic conductivity, a decrease in the Young’s modulus, a decrease in the shear modulus and voltage induced changes in the crystal’s overall length. In addition, we have observed the torsional piezo-like response, voltage induced torsional strain (VITS), in TaS3 which was first discovered by Pokrovskii et. al. in 2007. Our measurements were conducted with a helical resonator. The VITS response has a huge effective piezoelectric coefficient of ~ 104 cm/V. In addition we have concluded that the VITS is a very slow response with time constants of ~ 1 s near the CDW depinning threshold, that these time constants are dependent on the CDW current, and we suggest that the VITS is due to residual twists being initially present in the crystal.

<p>In this work, we study two important themes in the physics of the interacting one-dimensional (1D) electron gas: the transition from one-dimensional to higher dimensional behavior, and the role of inhomogeneity. The interplay between interactions, reduced dimensionality, and inhomogeneity drives a rich variety of phenomena in mesoscopic physics. In 1D, interactions fundamentally alter the nature of the electron gas, and the homogeneous 1D electron gas is described by Luttinger Liquid theory. We use Quantum Monte Carlo methods to study two situations that are beyond Luttinger Liquid theory --- the quantum phase transition from a linear 1D electron system to a quasi-1D zigzag arrangement, and electron localization in quantum point contacts. </p><p>Since the interacting electron gas has fundamentally different behavior in one dimension than in higher dimensions, the transition from 1D to higher dimensional behavior is of both practical and theoretical interest. We study the first stage in such a transition; the quantum phase transition from a 1D linear arrangement of electrons in a quantum wire to a quasi-1D zigzag configuration, and then to a liquid-like phase at higher densities. As the density increases from its lowest values, first, the electrons form a linear Wigner crystal; then, the symmetry about the axis of the wire is broken as the electrons order in a quasi-1D zigzag phase; and, finally, the electrons form a disordered liquid-like phase. We show that the linear to zigzag phase transition occurs even in narrow wires with strong quantum fluctuations, and that it has characteristics which are qualitatively different from the classical transition.</p><p>Experiments in quantum point contacts (QPC's) show an unexplained feature in the conductance known as the ``0.7 Effect''. The presence of the 0.7 effect is an indication of the rich physics present in inhomogeneous systems, and we study electron localization in quantum point contacts to evaluate several different proposed mechanisms for the 0.7 effect. We show that electrons form a Wigner crystal in a 1D constriction; for sharp constriction potentials the localized electrons are separated from the leads by a gap in the density, while for smoother potentials, the Wigner crystal is smoothly connected to the leads. Isolated bound states can also form in smooth constrictions if they are sufficiently long. We thus show that localization can occur in QPC's for a variety of potential shapes and at a variety of electron densities. These results are consistent with the idea that the 0.7 effect and bound states observed in quantum point contacts are two distinct phenomena.</p> / Dissertation

This thesis reports studies done on single-walled carbon nanotubes (SWNTs) using optical spectroscopy as the primary investigative technique. It focuses on advances in sample preparation which have been made possible through improvements to the method of photo-luminescence excitation (PLE) mapping of nanotubes. An introduction to the field and some theoretical models are presented initially to provide a background to the experimental chapters which follow. A description of the standard procedure for sample preparation in aqueous surfactants is then followed by a detailed introduction to PLE mapping, including modeling of SWNT spectra. The next chapter discusses improvements to the sample preparation method by using organic polymer solutions instead of aqueous surfactants for suspending the nanotubes. The results show reductions in the distribution of SWNT species which are solubilised, leading to significant improvements in the resolution of the optical absorbance spectra and an increased photoluminescence yield. Two experiments which were performed on the novel polymer-SWNT systems are then described. The first shows (via PLE mapping) that energy is transfered to the SWNTs when the polymer is photo-excited. The possible mechanisms behind this, as well as the implications for using carbon nanotubes as an additive in polymer photovoltaics, are discussed. The second experiment details a recent magneto-PL study of SWNTs embedded in films produced from the polymer solutions. Here, the improved optical signatures and absence of strain at low temperatures have revealed a previously unseen high field intensity dependence. The behavior has been explained by the magnetic field induced mixing of the excitonic states.

This thesis forms part of an ongoing project in the DNA Group to build and operate a synthetic ribosome. We present two synthetic ribosome designs that can be combined with DNA-templated chemistry to generate libraries of functional synthetic small molecules. In Chapter 2 we use the DNA strand displacement technique to construct a mechanism that is capable of moving along a DNA track. We explore ways to control the speed and the driving force of the mechanism, and present a mathematical model of the system. We discuss the ability of the design to incorporate chemically-functionalised DNA strands. In Chapter 3 we use a 2D DNA origami tile as the basis of the synthetic ribosome mechanism. Functionalised DNA strands are arranged on the surface of the tile, and we demonstrate the ability to template reactions between the strands, and discuss the possibility of creating a library of distinct chemical products from a single origami tile.

This thesis describes studies on nanohybrid systems consisting of single-walled carbon nanotubes (SWNTs) with monolayer coatings of semiconducting polymers. Steady-state and time-resolved optical and high-resolution microscopy experiments were used to investigate the blends. These materials show promise for use in organic photovoltaics (OPVs) owing to the high carrier mobilities and large aspect ratios of SWNTs, the controllable solubilisation of tubes with various polymers and the broad light-harvesting abilities of organic polymers. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising carbon nanotubes in OPV devices, revealing poor performances to date. The experimental methods used during the thesis are detailed in Chapter 3 and the solution processing techniques used to prepare the polymer–nanotube blend samples are described in Chapter 4. Chapter 5 describes a study on a nanotube blend with a thiophene polymer, a system previously unsuccessfully implemented into OPV devices. Ultrafast spectroscopic measurements showed that electrons can transfer on a 400 fs time scale from the polymer to nanotubes and the conditions to allow long-lived free charges to be produced were found. The study is extended in Chapter 6 to show that nanostructures consisting of a nanotube coated in one polymer can then be coated by a second polymer and that these nano-engineered structures could be implemented into OPV devices. The use of a competition binding process to isolate purely semiconducting nanotubes dispersed with any desired polymer is then described in Chapter 7. Finally, Chapter 8 introduces systems consisting of chains of porphyrin units, nature’s light-harvesting systems, bound to nanotubes and the blends were found to exhibit the required electronic alignment for use in OPVs. The work described in this thesis provides an explanation for the poor device behaviour of nanotube–polymer blends to date and, in particular, demonstrates several nanohybrid systems that show particular promise for improved OPV applications.

This thesis describes my investigations into the principles underlying self-assembly of DNA origami nanostructures and discusses how these principles may be applied. To study the origami folding process I designed, synthesized and characterized a polymorphic tile, which could adopt various shapes. The distribution of tile shapes provided new insights into assembly. The origami tiles I studied were based on scaffolds derived from customized plasmids, which I prepared using recombinant DNA technology. I developed a technique to monitor incorporation of individual staples in real time using fluorescence, measuring small differences in staple binding temperatures (~0.5-5 °C). I examined the tiles using Atomic Force Microscopy and I found that a remarkably high proportion of polymorphic tiles folded well, which suggests that there are assembly <b>pathways</b>, arising from strong cooperation between staples. In order to analyse the tile shapes quantitatively, I developed a specialized image processing technique. For validation of the method, I generated and analysed simulated data, and the results confirmed that I could measure individual tile parameters with sub-pixel resolution. I studied eleven variants of the polymorphic tile, and I proved that minor staple modifications can be used to change the folding pathway dramatically. The strength of cooperation between staples affects their behaviour, which is also influenced by their length and base sequences. Paired staples are particularly significant in assembly, and there are clear parallels with protein folding. I describe in an Appendix how I applied origami assembly principles in the development of my concept for an autonomous rotary nanomotor utilizing the sequential opening of DNA hairpins (already used for linear motors). This device represents an advance over non-autonomous rotary motors and I have simulated its performance. In this thesis I have answered important questions about DNA origami assembly, and my findings could enable the development of more sophisticated DNA nanostructures for specific purposes.

Research on inherently nanolaminated transition metal carbides is inspired by their unique properties combining metals and ceramics, such as higher damage tolerance, better machinability and lower brittleness compared to the binary counterparts, yet retaining the metallic conductivity. The interesting properties are related to their laminated structure, composed of transition-metalcarbide layers interleaved by non-transition-metal (carbide) layers. These materials in thin-film form are particularly interesting for potential applications such as protective coatings and electrical contacts. The goal of this work is to explore nanolaminated transition metal carbides from the aspects of phase formation and crystal growth during thin-film synthesis. This was realized by studying phases in select material systems synthesized from two major approaches, namely, fromdirect-deposition and post-deposition treatment. The first approach was used in studies on the Mo-Ga-C and Zr-Al-C systems. In the former system, intriguing properties have been predicted for the 3D phases and their 2D derivatives (socalled MXenes), while in the latter system, the phases are interesting for nuclear applications. In this work, the discovery of a new Mo-based nanolaminated ternary carbide, Mo2Ga2C, is evidenced from thin-film and bulk processes. Its structure was determined using theoretical and experimental techniques, showing that Mo2Ga2C has Ga double-layers in simple hexagonal stacking between adjacent Mo2C layers, and therefore is structurally very similar to Mo2GaC, except for the additional Ga layers. For the Zr-Al-C system, the optimization of phase composition and structure of Zr2Al3C4 in a thin-film deposition process was studied by evaluating the effect of deposition parameters. I concluded that the formation of Zr2Al3C4 is favored with a plasma flux overstoichiometric in Al, and with a minimum lattice-mismatch to the substrates. Consequently, epitaxial Zr2Al3C4 thin film of high quality were deposited on 4H-SiC(001) substrates at 800 °C. With the approach of post-deposition treatment, the studies were focused on a new method of thermally-induced selective substitution reaction of Au for the non-transition-metal layers in nanolaminated carbides. Here, the reaction mechanism has been explored in Al-containing (Ti2AlC and Ti3AlC2) and Ga-containing (Mo2GaC and Mo2Ga2C) phases. The Al and Ga in these phases were selectively replaced by Au while the carbide layers remained intact, resulting in the formation of new layered phases, Ti2Au2C, Ti3Au2C2, Mo2AuC, and Mo2(Au1-xGax)2C, respectively. The substitution reaction was explained by fast outward diffusion of the Al or Ga being attracted to the surface Au, in combination with back-filling of Au, which is chemically inert to the carbide layers,to the vacancies. The substitution reaction was further applied to Ga-containing nanolaminated carbides, (Cr0.5Mn0.5)2GaC and Mo2GaC, motivated by development of novel magnetic nanolaminates. The former experiment resulted in the formation of (Cr0.5Mn0.5)2AuC, where the retained (Cr0.5Mn0.5)2C layers allowed a comparative study on the magnetic properties under the exchange of Ga for Au. After Au substitution, reduction in the Curie temperature and the saturation magnetization were observed, showing a weakened magnetic exchange interaction of the magnetic (Cr0.5Mn0.5)2 Clayers across the Au. In the Mo2GaC case, an Fe-containing MAX phase, Mo2AC with 50 at.% of Fe on the A site, was synthesized through selective substitution of Au-Fe alloy for the Ga layers, showing the first direct evidence for Fe in the MAX-phase structure. The substitution of Fe did not take place on another Mo2GaC sample tested for Fe exchange only, indicating the essential role of Au in catalyzing the Fe-substitution reaction. The knowledge gained from this thesis work contributes to improved approaches for attaining thin films of nanolaminated transition metal carbides with desired phase composition and crystal quality. The reports on the new nanolaminated phases through exchange interactions are likely to expand the family of nanolaminated carbides and advance their properties, and trigger more studies on related (quasi-) 2D materials.