Zn-VI/Cu2O Heterojunctions for Earth-Abundant Photovoltaics

The need for sustainable energy production motivates the study of photovoltaic materials, which convert energy from sunlight directly into electricity. This work has focused on the development of Cu₂O as an earth-abundant solar absorber due to the abundance of its constituent elements in the earth's crust, its suitable band gap, and its potential for low cost processing. Crystalline wafers of Cu₂O with minority carrier diffusion lengths on the order of microns can be manufactured in a uniquely simple fashion — directly from copper foils by thermal oxidation. Furthermore, Cu₂O has an optical band gap of 1.9 eV, which gives it a detailed balance energy conversion efficiency of 24.7% and the possibility for an independently connected Si/Cu₂O dual junction with a detailed balance efficiency of 44.3%.

However, the highest energy conversion efficiency achieved in a photovoltaic device with a Cu₂O absorber layer is currently only 5.38% despite the favorable optical and electronic properties listed above. There are several challenges to making a Cu₂O photovoltaic device, including an inability to dope the material, its relatively low chemical stability compared to other oxides, and a lack of suitable heterojunction partners due to an unusually small electron affinity. We have addressed the low chemical stability, namely the fact that Cu₂O is an especially reactive oxide due to its low enthalpy of formation (ΔH_f⁰ = -168.7 kJ/mol), by developing a novel surface preparation technique. We have addressed the lack of suitable heterojunction partners by investigating the heterojunction band alignment of several Zn-VI materials with Cu₂O. Finally, We have addressed the typically high series resistance of Cu₂O wafers by developing methods to make very thin, bulk Cu₂O, including devices on Cu₂O wafers as thin as 20 microns. Using these methods we have been able to achieve photovoltages over 1 V, and have demonstrated the potential of a new heterojunction material, Zn(O,S).

Imaging the earth with ambient noise and earthquakes

In this thesis, I develop the velocity and structure models for the Los Angeles Basin and Southern Peru. The ultimate goal is to better understand the geological processes involved in the basin and subduction zone dynamics. The results are obtained from seismic interferometry using ambient noise and receiver functions using earthquake- generated waves. Some unusual signals specific to the local structures are also studied. The main findings are summarized as follows:

(1) Los Angeles Basin

The shear wave velocities range from 0.5 to 3.0 km/s in the sediments, with lateral gradients at the Newport-Inglewood, Compton-Los Alamitos, and Whittier Faults. The basin is a maximum of 8 km deep along the profile, and the Moho rises to a depth of 17 km under the basin. The basin has a stretch factor of 2.6 in the center decreasing to 1.3 at the edges, and is in approximate isostatic equilibrium. This "high-density" (~1 km spacing) "short-duration" (~1.5 month) experiment may serve as a prototype experiment that will allow basins to be covered by this type of low-cost survey.

(2) Peruvian subduction zone

Two prominent mid-crust structures are revealed in the 70 km thick crust under the Central Andes: a low-velocity zone interpreted as partially molten rocks beneath the Western Cordillera – Altiplano Plateau, and the underthrusting Brazilian Shield beneath the Eastern Cordillera. The low-velocity zone is oblique to the present trench, and possibly indicates the location of the volcanic arcs formed during the steepening of the Oligocene flat slab beneath the Altiplano Plateau.

The Nazca slab changes from normal dipping (~25 degrees) subduction in the southeast to flat subduction in the northwest of the study area. In the flat subduction regime, the slab subducts to ~100 km depth and then remains flat for ~300 km distance before it resumes a normal dipping geometry. The flat part closely follows the topography of the continental Moho above, indicating a strong suction force between the slab and the overriding plate. A high-velocity mantle wedge exists above the western half of the flat slab, which indicates the lack of melting and thus explains the cessation of the volcanism above. The velocity turns to normal values before the slab steepens again, indicating possible resumption of dehydration and ecologitization.

(3) Some unusual signals

Strong higher-mode Rayleigh waves due to the basin structure are observed in the periods less than 5 s. The particle motions provide a good test for distinguishing between the fundamental and higher mode. The precursor and coda waves relative to the interstation Rayleigh waves are observed, and modeled with a strong scatterer located in the active volcanic area in Southern Peru. In contrast with the usual receiver function analysis, multiples are extensively involved in this thesis. In the LA Basin, a good image is only from PpPs multiples, while in Peru, PpPp multiples contribute significantly to the final results.

Studies of noble gases in meteorites and in the earth

The isotopic and elemental abundances of noble gases in the solar system are investigated, using simple mixing models and mass-spectrometric measurements of the noble gases in meteorites and terrestrial rocks and minerals.

Primordial neon is modeled by two isotopically distinct components from the interstellar gas and dust. Neon from the gas dominates solar neon, which contains about ten times more ²⁰Ne than ²²Ne. Neon from the dust is represented in meteorites by neon-E, with ²⁰Ne/²²Ne less than 0.6. Isotopic variations in meteorites require neon from both dust and gas to be present. Mixing dust and gas without neon loss generates linear correlation lines on three-isotope and composition-concentration diagrams. A model for solar wind implantation predicts small deviations from linear mixing, due to preferential sputtering of the lighter neon isotopes.

Neon in meteorites consists of galactic cosmic ray spallation neon and at least two primordial components, neon-E and neon-S. Neon was measured in several meteorites to investigate these end- members. Cosmogenic neon produced from sodium is found to be strongly enriched in ²²Ne. Neon measurements on sodium-rich samples must be interpreted with care so not to confuse this source of ²²Ne with neon-E, which is also rich in ²²Ne.

Neon data for the carbonaceous chondrite Mokoia show that the end member composition of neon-Si in meteorites is ²⁰Ne/²²Ne = 13.7, the same as the present solar wind. The solar wind composition evidently has remained constant since before the compaction of Mokoia.

Ca, Al-rich inclusions from the Allende meteorite were examined for correlation between neon-E and oxygen or magnesium isotopic anomalies. ²²Ne and ³⁶Ar enrichments found in some inclusions are attributed to cosmic- ray-induced reactions on Na and Cl, not to a primordial component. Neon-E is not detectably enriched in Allende.

Measurements were made to determine the noble gas contents of various terrestrial rocks and minerals, and to investigate the cycling of noble gases between different terrestrial reservoirs. Beryl crystals contain a characteristic suite of magmatic gases including nucleogenic ²¹Ne and ²²Ne from (α,n) reactions, radiogenic ⁴⁰Ar, and fissiogenic ^131-136Xe from the decay of K and U in the continental crust. Significant concentrations of atmospheric noble gases are also present in beryl.

Both juvenile and atmospheric noble gases are found in rocks from the Skaergaard intrusion. The ratio ⁴⁰Ar/³⁶Ar (corrected for in situ decay of ⁴⁰K) correlates with δ¹⁸O in plagioclase. Atmospheric argon has been introduced into samples that have experienced oxygen-isotope exchange with circulating meteoric hydrothermal fluids. Unexchanged samples contain juvenile argon with ⁴⁰Ar/³⁶Ar greater than 6000 that was trapped from the Skaergaard magma.

Juvenile and atmospheric gases have been measured in the glassy rims of mid-ocean ridge (MOR) pillow basalts. Evidence is presented that three samples contain excess radiogenic ¹²⁹Xe and fission xenon, in addition to the excess radiogenic ⁴⁰Ar found in all samples. These juvenile gases are being outgassed from the upper-mantle source region of the MOR magma. No isotopic evidence has been found here for juvenile primordial noble gases accompanying the juvenile radiogenic gases in the MOR glasses. Large argon isotopic variations in a single specimen provide a clear indication of the late-stage addition of atmospheric argon, probably from seawater.

The Skaergaard data demonstrate that atmospheric noble gases dissolved in ground water can be transferred into crustal rocks. Subduction of oceanic crust altered by seawater can transport atmospheric noble gases into the upper mantle. A substantial portion of the noble gases in mantle derived rocks may represent subducted gases, not a primordial component as is often assumed.

Dynamical models for the Earth's geoid

The Earth's largest geoid anomalies occur at the lowest spherical harmonic degrees, or longest wavelengths, and are primarily the result of mantle convection. Thermal density contrasts due to convection are partially compensated by boundary deformations due to viscous flow whose effects must be included in order to obtain a dynamically consistent model for the geoid. These deformations occur rapidly with respect to the timescale for convection, and we have analytically calculated geoid response kernels for steady-state, viscous, incompressible, self-gravitating, layered Earth models which include the deformation of boundaries due to internal loads. Both the sign and magnitude of geoid anomalies depend strongly upon the viscosity structure of the mantle as well as the possible presence of chemical layering.

Correlations of various global geophysical data sets with the observed geoid can be used to construct theoretical geoid models which constrain the dynamics of mantle convection. Surface features such as topography and plate velocities are not obviously related to the low-degree geoid, with the exception of subduction zones which are characterized by geoid highs (degrees 4-9). Recent models for seismic heterogeneity in the mantle provide additional constraints, and much of the low-degree (2-3) geoid can be attributed to seismically inferred density anomalies in the lower mantle. The Earth's largest geoid highs are underlain by low density material in the lower mantle, thus requiring compensating deformations of the Earth's surface. A dynamical model for whole mantle convection with a low viscosity upper mantle can explain these observations and successfully predicts more than 80% of the observed geoid variance.

Temperature variations associated with density anomalies in the man tie cause lateral viscosity variations whose effects are not included in the analytical models. However, perturbation theory and numerical tests show that broad-scale lateral viscosity variations are much less important than radial variations; in this respect, geoid models, which depend upon steady-state surface deformations, may provide more reliable constraints on mantle structure than inferences from transient phenomena such as postglacial rebound. Stronger, smaller-scale viscosity variations associated with mantle plumes and subducting slabs may be more important. On the basis of numerical modelling of low viscosity plumes, we conclude that the global association of geoid highs (after slab effects are removed) with hotspots and, perhaps, mantle plumes, is the result of hot, upwelling material in the lower mantle; this conclusion does not depend strongly upon plume rheology. The global distribution of hotspots and the dominant, low-degree geoid highs may correspond to a dominant mode of convection stabilized by the ancient Pangean continental assemblage.

High frequency wave propagation in the earth: theory and observation

The wave-theoretical analysis of acoustic and elastic waves refracted by a spherical boundary across which both velocity and density increase abruptly and thence either increase or decrease continuously with depth is formulated in terms of the general problem of waves generated at a steady point source and scattered by a radially heterogeneous spherical body. A displacement potential representation is used for the elastic problem that results in high frequency decoupling of P-SV motion in a spherically symmetric, radially heterogeneous medium. Through the application of an earth-flattening transformation on the radial solution and the Watson transform on the sum over eigenfunctions, the solution to the spherical problem for high frequencies is expressed as a Weyl integral for the corresponding half-space problem in which the effect of boundary curvature maps into an effective positive velocity gradient. The results of both analytical and numerical evaluation of this integral can be summarized as follows for body waves in the crust and upper mantle:

1) In the special case of a critical velocity gradient (a gradient equal and opposite to the effective curvature gradient), the critically refracted wave reduces to the classical head wave for flat, homogeneous layers.

2) For gradients more negative than critical, the amplitude of the critically refracted wave decays more rapidly with distance than the classical head wave.

3) For positive, null, and gradients less negative than critical, the amplitude of the critically refracted wave decays less rapidly with distance than the classical head wave, and at sufficiently large distances, the refracted wave can be adequately described in terms of ray-theoretical diving waves. At intermediate distances from the critical point, the spectral amplitude of the refracted wave is scalloped due to multiple diving wave interference.

These theoretical results applied to published amplitude data for P-waves refracted by the major crustal and upper mantle horizons (the Pg, P*, and Pn travel-time branches) suggest that the 'granitic' upper crust, the 'basaltic' lower crust, and the mantle lid all have negative or near-critical velocity gradients in the tectonically active western United States. On the other hand, the corresponding horizons in the stable eastern United States appear to have null or slightly positive velocity gradients. The distribution of negative and positive velocity gradients correlates closely with high heat flow in tectonic regions and normal heat flow in stable regions. The velocity gradients inferred from the amplitude data are generally consistent with those inferred from ultrasonic measurements of the effects of temperature and pressure on crustal and mantle rocks and probable geothermal gradients. A notable exception is the strong positive velocity gradient in the mantle lid beneath the eastern United States (2 x 10^-3 sec^-1), which appears to require a compositional gradient to counter the effect of even a small geothermal gradient.

New seismic-refraction data were recorded along a 800 km profile extending due south from the Canadian border across the Columbia Plateau into eastern Oregon. The source for the seismic waves was a series of 20 high-energy chemical explosions detonated by the Canadian government in Greenbush Lake, British Columbia. The first arrivals recorded along this profile are on the Pn travel-time branch. In northern Washington and central Oregon their travel time is described by T = Δ/8.0 + 7.7 sec, but in the Columbia Plateau the Pn arrivals are as much as 0.9 sec early with respect to this line. An interpretation of these Pn arrivals together with later crustal arrivals suggest that the crust under the Columbia Plateau is thinner by about 10 km and has a higher average P-wave velocity than the 35-km-thick, 62-km/sec crust under the granitic-metamorphic terrain of northern Washington. A tentative interpretation of later arrivals recorded beyond 500 km from the shots suggests that a thin 8.4-km/sec horizon may be present in the upper mantle beneath the Columbia Plateau and that this horizon may form the lid to a pronounced low-velocity zone extending to a depth of about 140 km.

Using Earth Deformation Caused by Surface Mass Loading to Constrain the Elastic Structure of the Crust and Mantle

Surface mass loads come in many different varieties, including the oceans, atmosphere, rivers, lakes, glaciers, ice caps, and snow fields. The loads migrate over Earth's surface on time scales that range from less than a day to many thousand years. The weights of the shifting loads exert normal forces on Earth's surface. Since the Earth is not perfectly rigid, the applied pressure deforms the shape of the solid Earth in a manner controlled by the material properties of Earth's interior. One of the most prominent types of surface mass loading, ocean tidal loading (OTL), comes from the periodic rise and fall in sea-surface height due to the gravitational influence of celestial objects, such as the moon and sun. Depending on geographic location, the surface displacements induced by OTL typically range from millimeters to several centimeters in amplitude, which may be inferred from Global Navigation and Satellite System (GNSS) measurements with sub-millimeter precision. Spatiotemporal characteristics of observed OTL-induced surface displacements may therefore be exploited to probe Earth structure. In this thesis, I present descriptions of contemporary observational and modeling techniques used to explore Earth's deformation response to OTL and other varieties of surface mass loading. With the aim to extract information about Earth's density and elastic structure from observations of the response to OTL, I investigate the sensitivity of OTL-induced surface displacements to perturbations in the material structure. As a case study, I compute and compare the observed and predicted OTL-induced surface displacements for a network of GNSS receivers across South America. The residuals in three distinct and dominant tidal bands are sub-millimeter in amplitude, indicating that modern ocean-tide and elastic-Earth models well predict the observed displacement response in that region. Nevertheless, the sub-millimeter residuals exhibit regional spatial coherency that cannot be explained entirely by random observational uncertainties and that suggests deficiencies in the forward-model assumptions. In particular, the discrepancies may reveal sensitivities to deviations from spherically symmetric, non-rotating, elastic, and isotropic (SNREI) Earth structure due to the presence of the South American craton.

Rare earth doped beta-diketone complexes as promising high-density optical recording materials for blue optoelectronics

Some kinds of rare earth beta-diketone complexes with blue-violet light absorption edge were synthesized using the ligands of thenoyltrifluoroacctone (HTTA), 2, 2'-dipyridyl (BIPY) and different metal ions (Gd3+, Sm3+ and La3+). Their contents, structures and optoelectronic parameters were monitored by elemental analysis, MS, IR and UV spectra. The solubility of rare earth beta-diketone complexes in 2, 2, 3, 3-tetrafluoro-1-propanol (TFP) and absorption properties of their films in the region 300-800 nm were measured. The influence on the difference of absorption maximum from rare earth beta-diketone complexes to beta-diketone ligand by different metal ions was studied. In addition, the thermal stability of rare earth beta-diketone complexes was also reported. (C) 2005 Elsevier B.V. All rights reserved.

Rare earth dibenzoylmethane complexes for potential application as high-density recordable optical recording materials

Three kinds of rare earth complexes derived from dibenzoylmethane (DBM) ligand were synthesized by reacting free ligand and different rare earth ions(La (3+), Sm3+ and Gd3+). Their contents and structures were postulated based on elemental analysis, LDI-TOF-MS, FT-IR spectra and UV-Vis spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption and reflection properties of thin film and thermal stability of these complexes were evaluated. These complexes would be a promising recording material for high-density digital versatile disc-recordable (HD-DVD-R) system. (c) 2007 Elsevier B.V. All rights reserved.

Effect of alkaline-earth metal composition on spectroscopic properties of Er3+ in fluorophosphate glasses

Optical spectroscopic properties of Er3+-doped alkaline-earth metal modified fluoropho sphate glasses have been investigated experimentally for developing broadband fiber and planar amplifiers. The results show a strong correlation between the alkaline-earth metal content and the spectroscopic parameters such as absorption and emission cross sections, full widths at half-maximum and Judd-Ofelt intensity parameters. It is found that strontium ions could have more influences on the Judd-Ofelt intensity parameters and the absorption and emission cross sections than other alkaline-earth metal ions such as Mg2+, Ca2+, Ba2+. The sample containing 23 mol% strontium fluoride exhibits the maximum emission cross section of 7.58 x 10(-21) cm(2), the broadest full width at half-maximum of 65 nm and the longer lifetime of 8.6 ms among the alkaline-earth metal modified fluorophosphates glasses studied. The Judd-Ofelt intensity parameter Omega(6)s, the emission cross sections and the full widths at half-maximum in the Er3+-doped fluorophosphate glasses studied are larger than in the silicate and phosphate glasses.

Ultrabroad infrared luminescences from Bi-doped alkaline earth metal germanate glasses

We report on ultrabroad infrared (IR) luminescences covering the 1000-1700-nm wavelength region, from Bi-doped 75GeO(2) 20RO-5Al(2)O(3) 1B(2)O(3) (R = Sr, Ca, and Mg) glasses. The full width at half-maximum of the IR luminescences excited at 980 nm increases (315 -> 440 -> 510 nm) with the change of alkaline earth metal (Mg2+ -> Ca2+ -> Sr2+). The fluorescence lifetime of the glass samples is 1725, 157, and 264 mu s when R is Sr, Ca, and Mg, respectively. These materials may be promising candidates for broad-band fiber amplifiers and tunable laser resources.

Effect of alkali and alkaline earth fluoride introduction on thermal stability and structure of fluorophosphate glasses

The thermal stability and structure of RF-RF2-AIF(3)-Al(PO3)(3) fluorophosphate glasses were investigated. Analyses of infrared absorbance spectra and Raman spectra reveal that with increasing number of alkali and alkaline earth fluoride components, the sum of P-O-P bond and O-P-O bond increases and glass network is strengthened. Consequently, the inhibition to nucleation and crystallization processes is improved, which is proved by the increment of thermal stability factors AT and S determined by differential scanning calorimetry. In addition, it was found that LiF has poor ability to form glass in univalent alkali fluorides and MgF2 has comparative strong ability to form glass in bivalent alkaline earth fluorides. (c) 2006 Published by Elsevier B.V.

Effect of various alkaline-earth metal oxides on the broadband infrared luminescence from bismuth-doped silicate glasses

We report on the effect of various alkaline-earth metal oxides on the broadband infrared luminescence covering 1000-1600 nm wavelength region from bismuth-doped silicate glasses. The full width at half maximum (FWHM) of the infrared luminescence and the fluorescent lifetime is more than 200 nm and 400 mu s, respectively. The fluorescent intensity decreases with increasing basicity of host glasses. Besides the broadband infrared luminescence, luminescence centered at 640 nm was also observed, which should be ascribed to Bi2+ rather than to the familiar Bi3+. We suggest that the infrared luminescence should be assigned to the X-2 (2)Pi (3/2) -> X-1 (2)Pi(1/2) transition of BiO molecules dispersed in the host glasses. (c) 2006 Elsevier Ltd. All rights reserved.