Superconductivity, spin-glass properties, and ferromagnetism in amorphous La-Gd-Au alloys

The superconducting and magnetic properties of splat cooled amorphous alloys of composition (La_100-xGd_x)₈₀Au₂₀ (0 ≤ x ≤ 100) have been studied. The La₈₀Au₂₀ alloys are ideal type II super-conductors (critical temperature T_c = 3.5° K ). The concentration range (x less than 1) where superconductivity and spin-glass freezing n1ight coexist has been studied in detail. The spin-glass alloys (0 less than x less than 70) exhibit susceptibility maxima and thermomagnetic history effects. In the absence of complications due to crystal field and enhanced matrix effects, a phenomenological model is proposed in which the magnetic clusters are treated as single spin entities interacting via random forces using the molecular field approach. The fundamental parameters (such as the strength of the forces and the size of clusters) can be deduced from magnetization measurements. The remanent magnetization is shown to arise from an interplay of the RKKY and dipolar forces. Magnetoresistivity results are found to be consistent with the aforementioned picture. The nature of magnetic interactions in an amorphous matrix is also discussed. The moment per Gd atom (7µ_B) is found to be constant and close to that of the crystalline value throughout the concentration range investigated. Finally, a detail study is made of the critical phenomena and magnetic properties of the amorphous ferromagnet: Gd₈₀Au₂₀. The results are compared with recent theories on amorphous magnetism.

OBSERVATION OF CAVITY QUANTUM-ELECTRODYNAMIC EFFECTS IN A ND-GLASS MICROSPHERE

In a Nd:glass microspherical cavity the enhancement and inhibition of spontaneous-emission processes that are due to cavity QED effects have been observed. The rates of the enhanced spontaneous emission are location dependent and reach a maximum value of more than 10(3) times the free-space value. The large enhancement strongly modifies the decay processes of Nd ions in glass, and the radiative properties of Nd:glass have been changed. As a result a new spectrum including new lasing wavelengths in the Nd:glass sphere has been observed.

Existence of the transverse relaxation time in optically excited bulk semiconductors

Two basic types of depolarization mechanisms, carrier-carrier (CC) and carrier-phonon (CP) scattering, are investigated in optically excited bulk semiconductors (3D), in which the existence of the transverse relaxation time is proven based on the vector property of the interband transition matrix elements. The dephasing rates for both CC and CP scattering are determined to be equal to one half of the total scattering-rate-integrals weighted by the factors (1 - cos chi), where chi are the scattering angles. Analytical expressions of the polarization dephasing due to CC scattering are established by using an uncertainty broadening approach, and analytical ones due to both the polar optical-phonon and non-polar deformation potential scattering (including inter-valley scattering) are also presented by using the sharp spectral functions in the dephasing rate calculations. These formulas, which reveal the trivial role of the Coulomb screening effect in the depolarization processes, are used to explain the experimental results at hand and provide a clear physical picture that is difficult to extract from numerical treatments.

Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

Nanophotonic Light Trapping In Thin Solar Cells

Over the last several decades there have been significant advances in the study and understanding of light behavior in nanoscale geometries. Entire fields such as those based on photonic crystals, plasmonics and metamaterials have been developed, accelerating the growth of knowledge related to nanoscale light manipulation. Coupled with recent interest in cheap, reliable renewable energy, a new field has blossomed, that of nanophotonic solar cells.

In this thesis, we examine important properties of thin-film solar cells from a nanophotonics perspective. We identify key differences between nanophotonic devices and traditional, thick solar cells. We propose a new way of understanding and describing limits to light trapping and show that certain nanophotonic solar cell designs can have light trapping limits above the so called ray-optic or ergodic limit. We propose that a necessary requisite to exceed the traditional light trapping limit is that the active region of the solar cell must possess a local density of optical states (LDOS) higher than that of the corresponding, bulk material. Additionally, we show that in addition to having an increased density of states, the absorber must have an appropriate incoupling mechanism to transfer light from free space into the optical modes of the device. We outline a portfolio of new solar cell designs that have potential to exceed the traditional light trapping limit and numerically validate our predictions for select cases.

We emphasize the importance of thinking about light trapping in terms of maximizing the optical modes of the device and efficiently coupling light into them from free space. To further explore these two concepts, we optimize patterns of superlattices of air holes in thin slabs of Si and show that by adding a roughened incoupling layer the total absorbed current can be increased synergistically. We suggest that the addition of a random scattering surface to a periodic patterning can increase incoupling by lifting the constraint of selective mode occupation associated with periodic systems.

Lastly, through experiment and simulation, we investigate a potential high efficiency solar cell architecture that can be improved with the nanophotonic light trapping concepts described in this thesis. Optically thin GaAs solar cells are prepared by the epitaxial liftoff process by removal from their growth substrate and addition of a metallic back reflector. A process of depositing large area nano patterns on the surface of the cells is developed using nano imprint lithography and implemented on the thin GaAs cells.

Signatures of Topological Superconductors

Topological superconductors are particularly interesting in light of the active ongoing experimental efforts for realizing exotic physics such as Majorana zero modes. These systems have excitations with non-Abelian exchange statistics, which provides a path towards topological quantum information processing. Intrinsic topological superconductors are quite rare in nature. However, one can engineer topological superconductivity by inducing effective p-wave pairing in materials which can be grown in the laboratory. One possibility is to induce the proximity effect in topological insulators; another is to use hybrid structures of superconductors and semiconductors.

The proposal of interfacing s-wave superconductors with quantum spin Hall systems provides a promising route to engineered topological superconductivity. Given the exciting recent progress on the fabrication side, identifying experiments that definitively expose the topological superconducting phase (and clearly distinguish it from a trivial state) raises an increasingly important problem. With this goal in mind, we proposed a detection scheme to get an unambiguous signature of topological superconductivity, even in the presence of ordinarily detrimental effects such as thermal fluctuations and quasiparticle poisoning. We considered a Josephson junction built on top of a quantum spin Hall material. This system allows the proximity effect to turn edge states in effective topological superconductors. Such a setup is promising because experimentalists have demonstrated that supercurrents indeed flow through quantum spin Hall edges. To demonstrate the topological nature of the superconducting quantum spin Hall edges, theorists have proposed examining the periodicity of Josephson currents respect to the phase across a Josephson junction. The periodicity of tunneling currents of ground states in a topological superconductor Josephson junction is double that of a conventional Josephson junction. In practice, this modification of periodicity is extremely difficult to observe because noise sources, such as quasiparticle poisoning, wash out the signature of topological superconductors. For this reason, We propose a new, relatively simple DC measurement that can compellingly reveal topological superconductivity in such quantum spin Hall/superconductor heterostructures. More specifically, We develop a general framework for capturing the junction's current-voltage characteristics as a function of applied magnetic flux. Our analysis reveals sharp signatures of topological superconductivity in the field-dependent critical current. These signatures include the presence of multiple critical currents and a non-vanishing critical current for all magnetic field strengths as a reliable identification scheme for topological superconductivity.

This system becomes more interesting as interactions between electrons are involved. By modeling edge states as a Luttinger liquid, we find conductance provides universal signatures to distinguish between normal and topological superconductors. More specifically, we use renormalization group methods to extract universal transport characteristics of superconductor/quantum spin Hall heterostructures where the native edge states serve as a lead. Interestingly, arbitrarily weak interactions induce qualitative changes in the behavior relative to the free-fermion limit, leading to a sharp dichotomy in conductance for the trivial (narrow superconductor) and topological (wide superconductor) cases. Furthermore, we find that strong interactions can in principle induce parafermion excitations at a superconductor/quantum spin Hall junction.

As we identify the existence of topological superconductor, we can take a step further. One can use topological superconductor for realizing Majorana modes by breaking time reversal symmetry. An advantage of 2D topological insulator is that networks required for braiding Majoranas along the edge channels can be obtained by adjoining 2D topological insulator to form corner junctions. Physically cutting quantum wells for this purpose, however, presents technical challenges. For this reason, I propose a more accessible means of forming networks that rely on dynamically manipulating the location of edge states inside of a single 2D topological insulator sheet. In particular, I show that edge states can effectively be dragged into the system's interior by gating a region near the edge into a metallic regime and then removing the resulting gapless carriers via proximity-induced superconductivity. This method allows one to construct rather general quasi-1D networks along which Majorana modes can be exchanged by electrostatic means.

Apart from 2D topological insulators, Majorana fermions can also be generated in other more accessible materials such as semiconductors. Following up on a suggestion by experimentalist Charlie Marcus, I proposed a novel geometry to create Majorana fermions by placing a 2D electron gas in proximity to an interdigitated superconductor-ferromagnet structure. This architecture evades several manufacturing challenges by allowing single-side fabrication and widening the class of 2D electron gas that may be used, such as the surface states of bulk semiconductors. Furthermore, it naturally allows one to trap and manipulate Majorana fermions through the application of currents. Thus, this structure may lead to the development of a circuit that enables fully electrical manipulation of topologically-protected quantum memory. To reveal these exotic Majorana zero modes, I also proposed an interference scheme to detect Majorana fermions that is broadly applicable to any 2D topological superconductor platform.

Ab initio study of anharmonicity in high pressure Cmca-4 metallic hydrogen

Hydrogen is the only atom for which the Schr odinger equation is solvable. Consisting only of a proton and an electron, hydrogen is the lightest element and, nevertheless, is far from being simple. Under ambient conditions, it forms diatomic molecules H2 in gas phase, but di erent temperature and pressures lead to a complex phase diagram, which is not completely known yet. Solid hydrogen was rst documented in 1899 [1] and was found to be isolating. At higher pressures, however, hydrogen can be metallized. In 1935 Wigner and Huntington predicted that the metallization pressure would be 25 GPa [2], where molecules would disociate to form a monoatomic metal, as alkali metals that lie below hydrogen in the periodic table. The prediction of the metallization pressure turned out to be wrong: metallic hydrogen has not been found yet, even under a pressure as high as 320 GPa. Nevertheless, extrapolations based on optical measurements suggest that a metallic phase may be attained at 450 GPa [3]. The interest of material scientist in metallic hydrogen can be attributed, at least to a great extent, to Ashcroft, who in 1968 suggested that such a system could be a hightemperature superconductor [4]. The temperature at which this material would exhibit a transition from a superconducting to a non-superconducting state (Tc) was estimated to be around room temperature. The implications of such a statement are very interesting in the eld of astrophysics: in planets that contain a big quantity of hydrogen and whose temperature is below Tc, superconducting hydrogen may be found, specially at the center, where the gravitational pressure is high. This might be the case of Jupiter, whose proportion of hydrogen is about 90%. There are also speculations suggesting that the high magnetic eld of Jupiter is due to persistent currents related to the superconducting phase [5]. Metallization and superconductivity of hydrogen has puzzled scientists for decades, and the community is trying to answer several questions. For instance, what is the structure of hydrogen at very high pressures? Or a more general one: what is the maximum Tc a phonon-mediated superconductor can have [6]? A great experimental e ort has been carried out pursuing metallic hydrogen and trying to answer the questions above; however, the characterization of solid phases of hydrogen is a hard task. Achieving the high pressures needed to get the sought phases requires advanced technologies. Diamond anvil cells (DAC) are commonly used devices. These devices consist of two diamonds with a tip of small area; for this reason, when a force is applied, the pressure exerted is very big. This pressure is uniaxial, but it can be turned into hydrostatic pressure using transmitting media. Nowadays, this method makes it possible to reach pressures higher than 300 GPa, but even at this pressure hydrogen does not show metallic properties. A recently developed technique that is an improvement of DAC can reach pressures as high as 600 GPa [7], so it is a promising step forward in high pressure physics. Another drawback is that the electronic density of the structures is so low that X-ray di raction patterns have low resolution. For these reasons, ab initio studies are an important source of knowledge in this eld, within their limitations. When treating hydrogen, there are many subtleties in the calculations: as the atoms are so light, the ions forming the crystalline lattice have signi cant displacements even when temperatures are very low, and even at T=0 K, due to Heisenberg's uncertainty principle. Thus, the energy corresponding to this zero-point (ZP) motion is signi cant and has to be included in an accurate determination of the most stable phase. This has been done including ZP vibrational energies within the harmonic approximation for a range of pressures and at T=0 K, giving rise to a series of structures that are stable in their respective pressure ranges [8]. Very recently, a treatment of the phases of hydrogen that includes anharmonicity in ZP energies has suggested that relative stability of the phases may change with respect to the calculations within the harmonic approximation [9]. Many of the proposed structures for solid hydrogen have been investigated. Particularly, the Cmca-4 structure, which was found to be the stable one from 385-490 GPa [8], is metallic. Calculations for this structure, within the harmonic approximation for the ionic motion, predict a Tc up to 242 K at 450 GPa [10]. Nonetheless, due to the big ionic displacements, the harmonic approximation may not su ce to describe correctly the system. The aim of this work is to apply a recently developed method to treat anharmonicity, the stochastic self-consistent harmonic approximation (SSCHA) [11], to Cmca-4 metallic hydrogen. This way, we will be able to study the e ects of anharmonicity in the phonon spectrum and to try to understand the changes it may provoque in the value of Tc. The work is structured as follows. First we present the theoretical basis of the calculations: Density Functional Theory (DFT) for the electronic calculations, phonons in the harmonic approximation and the SSCHA. Then we apply these methods to Cmca-4 hydrogen and we discuss the results obtained. In the last chapter we draw some conclusions and propose possible future work.

Composition and bulk properties of Dorset river gravels

Considerable interest has been expressed in the composition of the stream gravels, the movement of bed materials and the relationship of sediment composition, packing and siltation of void space to invertebrate ecology. In the autumn of 1982, freeze-samples of gravel were obtained in Dorset streams. Data were required on the depth of salmonid egg pocke and were part of a broader investigation of regional variation in the independent variables of salmonid fish length, gravel size, current velocity and the resultant dependent variable ~egg burial depth. The Dorset river gravels examined are bimodal. The grain size distribution may be resolved into two near-normal frequency distributions interpreted as representing a primary framework or lattice of gravel particles into which a secondary matrix population of sand particles has penetrated.

Microwave dynamics of quasiparticles and critical fields in superconducting films

The microwave response of the superconducting state in equilibrium and non-equilibrium configurations was examined experimentally and analytically. Thin film superconductors were mostly studied in order to explore spatial effects. The response parameter measured was the surface impedance.

For small microwave intensity the surface impedance at 10 GHz was measured for a variety of samples (mostly Sn) over a wide range of sample thickness and temperature. A detailed analysis based on the BCS theory was developed for calculating the surface impedance for general thickness and other experimental parameters. Experiment and theory agreed with each other to within the experimental accuracy. Thus it was established that the samples, thin films as well as bulk, were well characterised at low microwave powers (near equilibrium).

Thin films were perturbed by a small dc supercurrent and the effect on the superconducting order parameter and the quasiparticle response determined by measuring changes in the surface resistance (still at low microwave intensity and independent of it) due to the induced current. The use of fully superconducting resonators enabled the measurement of very small changes in the surface resistance (< 10^-9 Ω/sq.). These experiments yield information regarding the dynamics of the order parameter and quasiparticle systems. For all the films studied the results could be described at temperatures near T_c by the thermodynamic depression of the order parameter due to the static current leading to a quadratic increase of the surface resistance with current.

For the thinnest films the low temperature results were surprising in that the surface resistance decreased with increasing current. An explanation is proposed according to which this decrease occurs due to an additional high frequency quasiparticle current caused by the combined presence of both static and high frequency fields. For frequencies larger than the inverse of the quasiparticle relaxation time this additional current is out of phase (by π) with the microwave electric field and is observed as a decrease of surface resistance. Calculations agree quantitatively with experimental results. This is the first observation and explanation of this non-equilibrium quasiparticle effect.

For thicker films of Sn, the low temperature surface resistance was found to increase with applied static current. It is proposed that due to the spatial non-uniformity of the induced current distribution across the thicker films, the above purely temporal analysis of the local quasiparticle response needs to be generalised to include space and time non-equilibrium effects.

The nonlinear interaction of microwaves arid superconducting films was also examined in a third set of experiments. The surface impedance of thin films was measured as a function of the incident microwave magnetic field. The experiments exploit the ability to measure the absorbed microwave power and applied microwave magnetic field absolutely. It was found that the applied surface microwave field could not be raised above a certain threshold level at which the absorption increased abruptly. This critical field level represents a dynamic critical field and was found to be associated with the penetration of the app1ied field into the film at values well below the thermodynamic critical field for the configuration of a field applied to one side of the film. The penetration occurs despite the thermal stability of the film which was unequivocally demonstrated by experiment. A new mechanism for such penetration via the formation of a vortex-antivortex pair is proposed. The experimental results for the thinnest films agreed with the calculated values of this pair generation field. The observations of increased transmission at the critical field level and suppression of the process by a metallic ground plane further support the proposed model.