Contactless Spectral-Dependent Measurement of Bulk Lifetime and Surface Recombination Velocity in Silicon Photovoltaic Materials

Charge carrier lifetime measurements in bulk or unfinished photovoltaic (PV) materials allow for a more accurate estimate of power conversion efficiency in completed solar cells. In this work, carrier lifetimes in PV- grade silicon wafers are obtained by way of quasi-steady state photoconductance measurements. These measurements use a contactless RF system coupled with varying narrow spectrum input LEDs, ranging in wavelength from 460 nm to 1030 nm. Spectral dependent lifetime measurements allow for determination of bulk and surface properties of the material, including the intrinsic bulk lifetime and the surface recombination velocity. The effective lifetimes are fit to an analytical physics-based model to determine the desired parameters. Passivated and non-passivated samples are both studied and are shown to have good agreement with the theoretical model.

RELATIONSHIP BETWEEN COLUMN DENSITY AND SURFACE MIXING RATIO FOR O3 AND NO2: IMPLICATIONS FOR SATELLITE OBSERVATIONS AND THE IMPACTS OF VERTICAL MIXING

Satellites have great potential for diagnosis of surface air quality conditions, though reduced sensitivity of satellite instrumentation to the lower troposphere currently impedes their applicability. One objective of the NASA DISCOVER-AQ project is to provide information relevant to improving our ability to relate satellite-observed columns to surface conditions for key trace gases and aerosols. In support of DISCOVER-AQ, this dissertation investigates the degree of correlation between O3 and NO2 column abundance and surface mixing ratio during the four DISCOVER-AQ deployments; characterize the variability of the aircraft in situ and model-simulated O3 and NO2 profiles; and use the WRF-Chem model to further investigate the role of boundary layer mixing in the column-surface connection for the Maryland 2011 deployment, and determine which of the available boundary layer schemes best captures the observations. Simple linear regression analyses suggest that O3 partial column observations from future satellite instruments with sufficient sensitivity to the lower troposphere may be most meaningful for surface air quality under the conditions associated with the Maryland 2011 campaign, which included generally deep, convective boundary layers, the least wind shear of all four deployments, and few geographical influences on local meteorology, with exception of bay breezes. Hierarchical clustering analysis of the in situ O3 and NO2 profiles indicate that the degree of vertical mixing (defined by temperature lapse rate) associated with each cluster exerted an important influence on the shapes of the median cluster profiles for O3, as well as impacted the column vs. surface correlations for many clusters for both O3 and NO2. However, comparisons to the CMAQ model suggest that, among other errors, vertical mixing is overestimated, causing too great a column-surface connection within the model. Finally, the WRF-Chem model, a meteorology model with coupled chemistry, is used to further investigate the impact of vertical mixing on the O3 and NO2 column-surface connection, for an ozone pollution event that occurred on July 26-29, 2011. Five PBL schemes were tested, with no one scheme producing a clear, consistent “best” comparison with the observations for PBLH and pollutant profiles; however, despite improvements, the ACM2 scheme continues to overestimate vertical mixing.

SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

The role of the Indian Ocean sector and sea surface salinity for prediction of the coupled Indo-Pacific system

The purpose of this dissertation is to evaluate the potential downstream influence of the Indian Ocean (IO) on El Niño/Southern Oscillation (ENSO) forecasts through the oceanic pathway of the Indonesian Throughflow (ITF), atmospheric teleconnections between the IO and Pacific, and assimilation of IO observations. Also the impact of sea surface salinity (SSS) in the Indo-Pacific region is assessed to try to address known problems with operational coupled model precipitation forecasts. The ITF normally drains warm fresh water from the Pacific reducing the mixed layer depths (MLD). A shallower MLD amplifies large-scale oceanic Kelvin/Rossby waves thus giving ~10% larger response and more realistic ENSO sea surface temperature (SST) variability compared to observed when the ITF is open. In order to isolate the impact of the IO sector atmospheric teleconnections to ENSO, experiments are contrasted that selectively couple/decouple the interannual forcing in the IO. The interannual variability of IO SST forcing is responsible for 3 month lagged widespread downwelling in the Pacific, assisted by off-equatorial curl, leading to warmer NINO3 SST anomaly and improved ENSO validation (significant from 3-9 months). Isolating the impact of observations in the IO sector using regional assimilation identifies large-scale warming in the IO that acts to intensify the easterlies of the Walker circulation and increases pervasive upwelling across the Pacific, cooling the eastern Pacific, and improving ENSO validation (r ~ 0.05, RMS~0.08C). Lastly, the positive impact of more accurate fresh water forcing is demonstrated to address inadequate precipitation forecasts in operational coupled models. Aquarius SSS assimilation improves the mixed layer density and enhances mixing, setting off upwelling that eventually cools the eastern Pacific after 6 months, counteracting the pervasive warming of most coupled models and significantly improving ENSO validation from 5-11 months. In summary, the ITF oceanic pathway, the atmospheric teleconnection, the impact of observations in the IO, and improved Indo-Pacific SSS are all responsible for ENSO forecast improvements, and so each aspect of this study contributes to a better overall understanding of ENSO. Therefore, the upstream influence of the IO should be thought of as integral to the functioning of ENSO phenomenon.