(Quantum-) critical dynamics of magnetoelectric materials

In this thesis the critical dynamics of several magnetoelectric compounds at their phase transition were examined. Mostly measurements of the dielectric properties in the frequency range of below 1 Hz up to 5 GHz were employed to evaluate the critical exponents for both magnetic field and temperature-dependent measurements. Most of the materials that are part of this work show anomalous behavior, especially at very low temperatures where quantum fluctuations are of the order of or even dominate those induced thermally. This anomalous behavior manifests in different forms. In Dy2Ti2O7 we demonstrate the existence of electric dipoles on magnetic monopoles. Here the dynamics at the critical endpoint located at 0.36K and in a magnetic field of 1T parallel to the [111] direction are of special interest. At this critical endpoint the expected critical slowing down of the dynamics could not only not be observed but instead the opposite, critical speeding-up by several orders of magnitude, could be demonstrated. Furthermore, we show that the phase diagram of Dy2Ti2O7 in this field direction can be reproduced solely from the dynamical properties, for example the resonance frequency of the observed relaxation that is connected to the monopole movement. Away from this point of the phase diagram the dynamics are slowing-down with reduction of temperature as one would expect. Additional measurements on Y2Ti2O7, a structurally identical but non-magnetic material, show only slowing down with reduction of temperature and no additional features. A possible explanation for the observed critical speeding-up is a coherent movement of magnetic monopoles close to the critical field that increases the resonance frequency by reducing the damping of the process. LiCuVO4 on the other hand behaves normally at its phase transition as long as the temperature is higher than 0.4 K. In this temperature regime the dynamics show critical slowing-down analogous to classical ferroelectric materials. This analogy extends also towards higher frequencies where the permittivity displays a ‘dispersion’ minimum that is temperature-dependent but of the order of 2 GHz. Below 0.4K the observed behavior changes drastically. Here we found no longer relaxational behavior but instead an excitation with very low energy. This low energy excitation was predicted by theory and is caused by nearly gapless soliton excitations within the 1D Cu2+ chains of LiCuVO4. Finally, in TbMnO3 the dynamics of the phase transition into the multiferroic phase was observed at roughly 27 K, a much higher temperature compared to the other materials. Here the expected critical slowing-down was observed, even though in low-frequency measurements this transition into the ferroelectric phase is overshadowed by the so-called c-axis relaxation. Therefore, only frequencies above 1MHz could be used to determine the critical exponents for both temperatureand magnetic-field-dependent measurements. This was done for both the peak frequency as well as the relaxation strength. In TbMnO3 an electromagnetic soft-mode with small optical weight causes the observed fluctuations, similar to the case of multiferroic MnWO4.

Fluctuations in and out of equilibrium: Thermalization, quantum measurements and Coulomb disorder

This purely theoretical thesis covers aspects of two contemporary research fields: the non-equilibrium dynamics in quantum systems and the electronic properties of three-dimensional topological insulators. In the first part we investigate the non-equilibrium dynamics in closed quantum systems. Thanks to recent technologies, especially from the field of ultracold quantum gases, it is possible to realize such systems in the laboratory. The focus is on the influence of hydrodynamic slow modes on the thermalization process. Generic systems in equilibrium, either classical or quantum, in equilibrium are described by thermodynamics. This is characterized by an ensemble of maximal entropy, but constrained by macroscopically conserved quantities. We will show that these conservation laws slow down thermalization and the final equilibrium state can be approached only algebraically in time. When the conservation laws are violated thermalization takes place exponential in time. In a different study we calculate probability distributions of projective quantum measurements. Newly developed quantum microscopes provide the opportunity to realize new measurement protocols which go far beyond the conventional measurements of correlation functions. The second part of this thesis is dedicated to a new class of materials known as three-dimensional topological insulators. Also here new experimental techniques have made it possible to fabricate these materials to a high enough quality that their topological nature is revealed. However, their transport properties are not fully understood yet. Motivated by unusual experimental results in the optical conductivity we have investigated the formation and thermal destruction of spatially localized electron- and hole-doped regions. These are caused by charged impurities which are introduced into the material in order to make the bulk insulating. Our theoretical results are in agreement with the experiment and can explain the results semi-quantitatively. Furthermore, we study emergent lengthscales in the bulk as well as close to the conducting surface.

Self-Assembled InAs/GaAs Quantum Dot Solar Cells

Our work focuses on experimental and theoretical studies aimed at establishing a fundamental understanding of the principal electrical and optical processes governing the operation of quantum dot solar cells (QDSC) and their feasibility for the realization of intermediate band solar cell (IBSC). Uniform performance QD solar cells with high conversion efficiency have been fabricated using carefully calibrated process recipes as the basis of all reliable experimental characterization. The origin for the enhancement of the short circuit current density (Jsc) in QD solar cells was carefully investigated. External quantum efficiency (EQE) measurements were performed as a measure of the below bandgap distribution of transition states. In this work, we found that the incorporation of self-assembled quantum dots (QDs) interrupts the lattice periodicity and introduce a greatly broadened tailing density of states extending from the bandedge towards mid-gap. A below-bandgap density of states (DOS) model with an extended Urbach tail has been developed. In particular, the below-bandgap photocurrent generation has been attributed to transitions via confined energy states and background continuum tailing states. Photoluminescence measurement is used to measure the energy level of the lowest available state and the coupling effect between QD states and background tailing states because it results from a non-equilibrium process. A basic I-V measurement reveals a degradation of the open circuit voltage (Voc) of QD solar cells, which is related to a one sub-bandgap photon absorption process followed by a direct collection of the generated carriers by the external circuit. We have proposed a modified Shockley-Queisser (SQ) model that predicts the degradation of Voc compared with a reference bulk device. Whenever an energy state within the forbidden gap can facilitate additional absorption, it can facilitate recombination as well. If the recombination is non-radiative, it is detrimental to solar cell performance. We have also investigated the QD trapping effects as deep level energy states. Without an efficient carrier extraction pathway, the QDs can indeed function as mobile carriers traps. Since hole energy levels are mostly connected with hole collection under room temperature, the trapping effect is more severe for electrons. We have tried to electron-dope the QDs to exert a repulsive Coulomb force to help improve the carrier collection efficiency. We have experimentally observed a 30% improvement of Jsc for 4e/dot devices compared with 0e/dot devices. Electron-doping helps with better carrier collection efficiency, however, we have also measured a smaller transition probability from valance band to QD states as a direct manifestation of the Pauli Exclusion Principle. The non-linear performance is of particular interest. With the availability of laser with on-resonance and off-resonance excitation energy, we have explored the photocurrent enhancement by a sequential two-photon absorption (2PA) process via the intermediate states. For the first time, we are able to distinguish the nonlinearity effect by 1PA and 2PA process. The observed 2PA current under off-resonant and on-resonant excitation comes from a two-step transition via the tailing states instead of the QD states. However, given the existence of an extended Urbach tail and the small number of photons available for the intermediate states to conduction band transition, the experimental results suggest that with the current material system, the intensity requirement for an observable enhancement of photocurrent via a 2PA process is much higher than what is available from concentrated sun light. In order to realize the IBSC model, a matching transition strength needs to be achieved between valance band to QD states and QD states to conduction band. However, we have experimentally shown that only a negligible amount of signal can be observed at cryogenic temperature via the transition from QD states to conduction band under a broadband IR source excitation. Based on the understanding we have achieved, we found that the existence of the extended tailing density of states together with the large mismatch of the transition strength from VB to QD and from QD to CB, has systematically put into question the feasibility of the IBSC model with QDs.

Phase Transitions in Engineered Ultracold Quantum Systems

The study of quantum degenerate gases has many applications in topics such as condensed matter dynamics, precision measurements and quantum phase transitions. We built an apparatus to create 87Rb Bose-Einstein condensates (BECs) and generated, via optical and magnetic interactions, novel quantum systems in which we studied the contained phase transitions. For our first experiment we quenched multi-spin component BECs from a miscible to dynamically unstable immiscible state. The transition rapidly drives any spin fluctuations with a coherent growth process driving the formation of numerous spin polarized domains. At much longer times these domains coarsen as the system approaches equilibrium. For our second experiment we explored the magnetic phases present in a spin-1 spin-orbit coupled BEC and the contained quantum phase transitions. We observed ferromagnetic and unpolarized phases which are stabilized by the spin-orbit coupling’s explicit locking between spin and motion. These two phases are separated by a critical curve containing both first-order and second-order transitions joined at a critical point. The narrow first-order transition gives rise to long-lived metastable states. For our third experiment we prepared independent BECs in a double-well potential, with an artificial magnetic field between the BECs. We transitioned to a single BEC by lowering the barrier while expanding the region of artificial field to cover the resulting single BEC. We compared the vortex distribution nucleated via conventional dynamics to those produced by our procedure, showing our dynamical process populates vortices much more rapidly and in larger number than conventional nucleation.

Interaction-free measurements by quantum Zeno stabilization of ultracold atoms

Quantum mechanics predicts that our physical reality is influenced by events that can potentially happen but factually do not occur. Interaction-free measurements (IFMs) exploit this counterintuitive influence to detect the presence of an object without requiring any interaction with it. Here we propose and realize an IFM concept based on an unstable many-particle system. In our experiments, we employ an ultracold gas in an unstable spin configuration, which can undergo a rapid decay. The object-realized by a laser beam-prevents this decay because of the indirect quantum Zeno effect and thus, its presence can be detected without interacting with a single atom. Contrary to existing proposals, our IFM does not require single-particle sources and is only weakly affected by losses and decoherence. We demonstrate confidence levels of 90%, well beyond previous optical experiments.

Implementation of continuous-variable quantum key distribution with composable and one-sided-device-independent security against coherent attacks

Secret communication over public channels is one of the central pillars of a modern information society. Using quantum key distribution this is achieved without relying on the hardness of mathematical problems, which might be compromised by improved algorithms or by future quantum computers. State-of-the-art quantum key distribution requires composable security against coherent attacks for a finite number of distributed quantum states as well as robustness against implementation side channels. Here we present an implementation of continuous-variable quantum key distribution satisfying these requirements. Our implementation is based on the distribution of continuous-variable Einstein–Podolsky–Rosen entangled light. It is one-sided device independent, which means the security of the generated key is independent of any memoryfree attacks on the remote detector. Since continuous-variable encoding is compatible with conventional optical communication technology, our work is a step towards practical implementations of quantum key distribution with state-of-the-art security based solely on telecom components.

Probing the interactions between ionic liquids and water: experimental and quantum chemical approach

For an adequate choice or design of ionic liquids, the knowledge of their interaction with other solutes and solvents is an essential feature for predicting the reactivity and selectivity of systems involving these compounds. In this work, the activity coefficient of water in several imidazolium-based ionic liquids with the common cation 1-butyl-3-methylimidazolium was measured at 298.2 K. To contribute to a deeper insight into the interaction between ionic liquids and water, COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies. The results showed good agreement between experimental and predicted activity coefficient of water in ionic liquids and that the interaction of water and ionic liquids was strongly influenced by the hydrogen bonding of the anion with water. Accordingly, the intensity of interaction of the anions with water can be ranked as the following: [CF3SO3](-) < [SCN](-) < [TFA](-) < Br(-) < [TOS](-) < Cl(-) < [CH3SO3](-) [DMP](-) < [Ac](-). In addition, fluorination and aromatization of anions are shown to reduce their interaction with water. The effect of temperature on the activity coefficient of water at infinite dilution was measured by inverse gas chromatography and predicted by COSMO-RS. Further analysis based on COSMO-RS provided information on the nature of hydrogen bonding between water and anion as well as the possibility of anion-water complex formation.

Shortcuts to adiabaticity in the double well

123 p.

Stranski-Krastanov InN/InGaN quantum dots grown directly on Si(111)

The authors discuss and demonstrate the growth of InN surface quantum dots on a high-In-content In0.73Ga0.27N layer, directly on a Si(111) substrate by plasma-assisted molecular beam epitaxy. Atomic force microscopy and transmission electron microscopy reveal uniformly distributed quantum dots with diameters of 10–40 nm, heights of 2–4 nm, and a relatively low density of ∼7 × 109 cm−2. A thin InN wetting layer below the quantum dots proves the Stranski-Krastanov growth mode. Near-field scanning optical microscopy shows distinct and spatially well localized near-infrared emission from single surface quantum dots. This holds promise for future telecommunication and sensing devices.

Quantum of Vision

Visual inputs to artificial and biological visual systems are often quantized: cameras accumulate photons from the visual world, and the brain receives action potentials from visual sensory neurons. Collecting more information quanta leads to a longer acquisition time and better performance. In many visual tasks, collecting a small number of quanta is sufficient to solve the task well. The ability to determine the right number of quanta is pivotal in situations where visual information is costly to obtain, such as photon-starved or time-critical environments. In these situations, conventional vision systems that always collect a fixed and large amount of information are infeasible. I develop a framework that judiciously determines the number of information quanta to observe based on the cost of observation and the requirement for accuracy. The framework implements the optimal speed versus accuracy tradeoff when two assumptions are met, namely that the task is fully specified probabilistically and constant over time. I also extend the framework to address scenarios that violate the assumptions. I deploy the framework to three recognition tasks: visual search (where both assumptions are satisfied), scotopic visual recognition (where the model is not specified), and visual discrimination with unknown stimulus onset (where the model is dynamic over time). Scotopic classification experiments suggest that the framework leads to dramatic improvement in photon-efficiency compared to conventional computer vision algorithms. Human psychophysics experiments confirmed that the framework provides a parsimonious and versatile explanation for human behavior under time pressure in both static and dynamic environments.

Synthesis and electronic properties of luminescent silicon nanocrystals and copper indium sulphide quantum dots

In the last decades, nanomaterials, and in particular semiconducting nanoparticles (or quantum dots), have gained increasing attention due to their controllable optical properties and potential applications. Silicon nanoparticles (also called silicon nanocrystals, SiNCs) have been extensively studied in the last years, due to their physical and chemical properties which render them a valid alternative to conventional quantum dots. During my PhD studies I have planned new synthetical routes to obtain SiNCs functionalised with molecules which could ameliorate the properties of the nanoparticle. However, this was certainly challenging, because SiNCs are very susceptible to many reagents and conditions that are often used in organic synthesis. They can be irreversibly quenched in the presence of alkalis, they can be damaged in the presence of oxidants, they can modify their optical properties in the presence of many nitrogen-containing compounds, metal complexes or simple organic molecules. If their surface is not well-passivated, the oxygen can introduce defect states, or they can aggregate and precipitate in several solvents. Therefore, I was able to functionalise SiNCs with different ligands: chromophores, amines, carboxylic acids, poly(ethylene)glycol, even ameliorating functionalisation strategies that already existed. This thesis will collect the experimental procedures used to synthesize silicon nanocrystals, the strategies adopted to functionalise effectively the nanoparticle with different types of organic molecules, and the characterisation of their surface, physical properties and luminescence (mostly photogenerated, but also electrochemigenerated). I also spent a period of 7 months in Leeds (UK), where I managed to learn how to synthesize other cadmium-free quantum dots made of copper, indium and sulphur (CIS QDs). During my last year of PhD, I focused on their functionalisation by ligand exchange techniques, yielding the first example of light-harvesting antenna based on those quantum dots. Part of this thesis is dedicated to them.

Investigating the learning potential of the Second Quantum Revolution: development of an approach for secondary school students

In recent years we have witnessed important changes: the Second Quantum Revolution is in the spotlight of many countries, and it is creating a new generation of technologies. To unlock the potential of the Second Quantum Revolution, several countries have launched strategic plans and research programs that finance and set the pace of research and development of these new technologies (like the Quantum Flagship, the National Quantum Initiative Act and so on). The increasing pace of technological changes is also challenging science education and institutional systems, requiring them to help to prepare new generations of experts. This work is placed within physics education research and contributes to the challenge by developing an approach and a course about the Second Quantum Revolution. The aims are to promote quantum literacy and, in particular, to value from a cultural and educational perspective the Second Revolution. The dissertation is articulated in two parts. In the first, we unpack the Second Quantum Revolution from a cultural perspective and shed light on the main revolutionary aspects that are elevated to the rank of principles implemented in the design of a course for secondary school students, prospective and in-service teachers. The design process and the educational reconstruction of the activities are presented as well as the results of a pilot study conducted to investigate the impact of the approach on students' understanding and to gather feedback to refine and improve the instructional materials. The second part consists of the exploration of the Second Quantum Revolution as a context to introduce some basic concepts of quantum physics. We present the results of an implementation with secondary school students to investigate if and to what extent external representations could play any role to promote students’ understanding and acceptance of quantum physics as a personal reliable description of the world.

Quantum Dots As Biophotonics Tools.

This chapter provides a short review of quantum dots (QDs) physics, applications, and perspectives. The main advantage of QDs over bulk semiconductors is the fact that the size became a control parameter to tailor the optical properties of new materials. Size changes the confinement energy which alters the optical properties of the material, such as absorption, refractive index, and emission bands. Therefore, by using QDs one can make several kinds of optical devices. One of these devices transforms electrons into photons to apply them as active optical components in illumination and displays. Other devices enable the transformation of photons into electrons to produce QDs solar cells or photodetectors. At the biomedical interface, the application of QDs, which is the most important aspect in this book, is based on fluorescence, which essentially transforms photons into photons of different wavelengths. This chapter introduces important parameters for QDs' biophotonic applications such as photostability, excitation and emission profiles, and quantum efficiency. We also present the perspectives for the use of QDs in fluorescence lifetime imaging (FLIM) and Förster resonance energy transfer (FRET), so useful in modern microscopy, and how to take advantage of the usually unwanted blinking effect to perform super-resolution microscopy.

Measuring The Hydrodynamic Radius Of Quantum Dots By Fluorescence Correlation Spectroscopy.

Fluorescence Correlation Spectroscopy (FCS) is an optical technique that allows the measurement of the diffusion coefficient of molecules in a diluted sample. From the diffusion coefficient it is possible to calculate the hydrodynamic radius of the molecules. For colloidal quantum dots (QDs) the hydrodynamic radius is valuable information to study interactions with other molecules or other QDs. In this chapter we describe the main aspects of the technique and how to use it to calculate the hydrodynamic radius of quantum dots (QDs).

Atomic Charge Transfer-counter Polarization Effects Determine Infrared Ch Intensities Of Hydrocarbons: A Quantum Theory Of Atoms In Molecules Model.

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.