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National Science Foundation (U.S.) (CA No. EEC-1041895)

High-temperature annealing, known as Tabula Rasa (TR), proves to be an effective method for dissolving oxygen precipitate nuclei in n-Cz silicon and makes this material resistant to temperature-induced and process-induced lifetime degradation. Tabula Rasa is especially effective in n-Cz wafers with oxygen concentration >15 ppma. Vacancies, self-interstitials, and their aggregates result from TR as a metastable side effect. Temperature-dependent lifetime spectroscopy reveals that these metastable defects have shallow energy levels ~0.12 eV. Their concentrations strongly depend on the ambient gases during TR because of an offset of the thermal equilibrium between vacancies and self-interstitials. However, these metastable defects anneal out at typical cell processing temperatures ≥850°C and have little effect on the bulk lifetime of the processed cell structures. Without dissolving built-in oxygen precipitate nuclei, high-temperature solar cell processing severely degrades the minority carrier lifetimes to below 0.1 millisecond, while TR-treated n-Cz wafers after the cell processing steps exhibit carrier lifetimes above 2.2 milliseconds.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2018., Cataloged from PDF version of thesis., Includes bibliographical references (pages 135-145)., To meet climate targets by 2030, manufacturing capacity for photovoltaic (PV) modules must be scaled at 22-25% annual growth rate while maintaining high performance and low selling price. The most suitable material substrate to enable this scale-up is cast multicrystalline silicon (mc-Si) due to its low operating cost and capital requirements compared to other technologies. However, a new form of light-induced degradation was discovered when transitioning mc-Si to the latest high efficiency device architecture. Light- and elevated temperature-induced degradation (LeTID) causes performance to decrease by about 10% (relative) under field-relevant conditions within only four months. In this work, the root cause of LeTID is investigated in three parts: (1) Candidate hypotheses are developed for LeTID; (2) Targeted experiments are carried out toward developing a defect-based description of LeTID; and (3) The basis for a predictive model of LeTID is proposed. Techniques including minority carrier lifetime spectroscopy, synchrotron-based X-ray fluorescence, intentional contamination, and process simulation are employed to probe the defect causing LeTID. The results indicate that LeTID is caused by at least two reactants-hydrogen and one or more reactants that can be modified by high-temperature processing-and that the defect at the point of maximum degradation has recombination characteristics similar to a deep-level donor in silicon. By providing the basis for a predictive model, this work enables both identification of the root cause of LeTID and de-risking of novel solar cell architectures based on mc-Si, allowing assessment of the impact of LeTID on the future of the PV industry. This work also enables development of mitigating strategies for LeTID., Funding from the National Science Foundation Graduate Research Fellowship Program and grants from the National Science Foundation and the U.S. Department of Energy, by Mallory Ann Jensen., Ph. D.

The primary problem with the explosion of biomedical datasets is not the data, not computational resources, and not the required storage space, but the general lack of trained and skilled researchers to manipulate and analyze these data. Eliminating this problem requires development of comprehensive educational resources. Here we present a community-driven framework that enables modern, interactive teaching of data analytics in life sciences and facilitates the development of training materials. The key feature of our system is that it is not a static but a continuously improved collection of tutorials. By coupling tutorials with a web-based analysis framework, biomedical researchers can learn by performing computation themselves through a web browser without the need to install software or search for example datasets. Our ultimate goal is to expand the breadth of training materials to include fundamental statistical and data science topics and to precipitate a complete re-engineering of undergraduate and graduate curricula in life sciences. This project is accessible at https://training.galaxyproject.org. We developed an infrastructure that facilitates data analysis training in life sciences. It is an interactive learning platform tuned for current types of data and research problems. Importantly, it provides a means for community-wide content creation and maintenance and, finally, enables trainers and trainees to use the tutorials in a variety of situations, such as those where reliable Internet access is unavailable.

We investigate the microscopic distributions of sub-band-gap luminescence emission (the so-called D-lines D1/D2/D3/D4) and the band-to-band luminescence intensity, near recombination-active subgrain boundaries in multicrystalline silicon wafers for solar cells. We find that the sub-band-gap luminescence from decorating defects/impurities (D1/D2) and from intrinsic dislocations (D3/D4) has distinctly different spatial distributions, and is asymmetric across the subgrain boundaries. The presence of D1/D2 is correlated with a strong reduction in the band-to-band luminescence, indicating a higher recombination activity. In contrast, D3/D4 emissions are not strongly correlated with the band-to-band intensity. Based on spatially resolved, synchrotron-based micro-X-ray fluorescence measurements of metal impurities, we confirm that high densities of metal impurities are present at locations with strong D1/D2 emission but low D3/D4 emission. Finally, we show that the observed asymmetry of the sub-band-gap luminescence across the subgrain boundaries is due to its inclination below the wafer surface. Based on the luminescence asymmetries, the subgrain boundaries are shown to share a common inclination locally, rather than being orientated randomly., Australian Research Council, Australian Renewable Energy Agency (gramt RND009), National Science Foundation (U.S.). Graduate Research Fellowship (Grant No.1122374), United States. Department of Energy. Office of Science (Contract No. DE-AC02-06CH11357)

The presence of metal impurities and their interactions with structural defects (e.g., dislocations) are deleterious to the performance of Si-based solar cell devices. To achieve higher minority carrier lifetimes that translate into higher solar cell efficiencies, novel growth methods with low dislocation densities and reduced metal impurity concentrations have recently been developed. These methods simultaneously aim to achieve low capital expense (capex), necessary to ensure rapid industry scaling. Monocrystalline Si grown by the non-contact crucible method (NOC-Si) has the potential to achieve high bulk minority carrier lifetimes and high efficiencies at low cost given its low structural defect density. Growth in large-diameter crucibles ensures high throughput consistent with low capex. However, high temperatures, coupled with conditions during Si growth (e.g., crucible and ambient gas) can lead to the in-diffusion of impurities, compromising the potential to achieve high efficiency solar cell devices. Herein, we report high minority-carrier lifetimes exceeding 3 milliseconds (ms) in n-type NOC-Si material, achieved through a strict impurity-control procedure at the growth stage that prevents in-diffusion of impurities to the melt, coupled with a tailored defect-engineering process via optimized phosphorus gettering. Keywords: defects; impurities; minority-carrier lifetime; non-contact crucible; top-seeded solution growth; silicon; solar cells, National Science Foundation (U.S.) (Grant 1122374), National Science Foundation (U.S.) (Contract EEC-1041895), United States. Department of Energy (Contract EEC-1041895)

In recent years, high-performance multicrystalline silicon (HPMC-Si) has emerged as an attractive alternative to traditional ingot-based multicrystalline silicon (mc-Si), with a similar cost structure but improved cell performance. Herein, we evaluate the gettering response of traditional mc-Si and HPMC-Si. Microanalytical techniques demonstrate that HPMC-Si and mc-Si share similar lifetime-limiting defect types but have different relative concentrations and distributions. HPMC-Si shows a substantial lifetime improvement after P-gettering compared with mc-Si, chiefly because of lower area fraction of dislocation-rich clusters. In both materials, the dislocation clusters and grain boundaries were associated with relatively higher interstitial iron point-defect concentrations after diffusion, which is suggestive of dissolving metal-impurity precipitates. The relatively fewer dislocation clusters in HPMC-Si are shown to exhibit similar characteristics to those found in mc-Si. Given similar governing principles, a proxy to determine relative recombination activity of dislocation clusters developed for mc-Si is successfully transferred to HPMC-Si. The lifetime in the remainder of HPMC-Si material is found to be limited by grain-boundary recombination. To reduce the recombination activity of grain boundaries in HPMC-Si, coordinated impurity control during growth, gettering, and passivation must be developed. Keywords: Defects; dislocation recombination activity; dislocations; eccentricity variation; high-performance multicrystalline silicon (HPMC-Si); minority-carrier lifetime; photovoltaics; recombination; synchrotron, United States. Department of Energy (Contract EEC-1041895), National Science Foundation (U.S.) (Contract EEC-1041895)

The bulk minority-carrier lifetime in p-And n-type kerfless epitaxial (epi) crystalline silicon wafers is shown to increase >500× during phosphorus gettering. We employ kinetic defect simulations and microstructural characterization techniques to elucidate the root cause of this exceptional gettering response. Simulations and deep-level transient spectroscopy (DLTS) indicate that a high concentration of point defects (likely Pt) is "locked in" during fast (60 °C/min) cooling during epi wafer growth. The fine dispersion of moderately fast-diffusing recombination-active point defects limits as-grown lifetime but can also be removed during gettering, confirmed by DLTS measurements. Synchrotron-based X-ray fluorescence microscopy indicates metal agglomerates at structural defects, yet the structural defect density is sufficiently low to enable high lifetimes. Consequently, after phosphorus diffusion gettering, epi silicon exhibits a higher lifetime than materials with similar bulk impurity contents but higher densities of structural defects, including multicrystalline ingot and ribbon silicon materials. Device simulations suggest a solar-cell efficiency potential of this material >23%., United States. Department of Energy (Contract DE-EE0005314), United States. Department of Energy (Contract EEC-1041895), National Science Foundation (U.S.) (Contract EEC-1041895)

Chromium (Cr) can degrade silicon wafer-based solar cell efficiencies at concentrations as low as 10¹⁰cm⁻³. In this contribution, we employ synchrotron-based X-ray fluorescence microscopy to study chromium distributions in multicrystalline silicon in as-grown material and after phosphorous diffusion. We complement quantified precipitate size and spatial distribution with interstitial Cr concentration and minority carrier lifetime measurements to provide insight into chromium gettering kinetics and offer suggestions for minimizing the device impacts of chromium. We observe that Cr-rich precipitates in as-grown material are generally smaller than iron-rich precipitates and that Cr[subscript i] point defects account for only one-half of the total Cr in the as-grown material. This observation is consistent with previous hypotheses that Cr transport and CrSi₂ growth are more strongly diffusion-limited during ingot cooling. We apply two phosphorous diffusion gettering profiles that both increase minority carrier lifetime by two orders of magnitude and reduce [Cr[subscript i]] by three orders of magnitude to 10¹⁰cm⁻³. Some Cr-rich precipitates persist after both processes, and locally high [Cr[subscript i]] after the high-temperature process indicates that further optimization of the chromium gettering profile is possible., United States. Department of Energy (Contract DE-EE0005314), National Science Foundation (U.S.) (Contract EEC-1041895), United States. Department of Energy (Contract EEC-1041895), National Science Foundation (U.S.) (Grant 1122374)

Impurity contamination in thin-film solar cells remains an uncertain risk due to the little-known impact of impurities on recombination. Building upon previous work, in which we intentionally contaminated lead halide perovskite (LHP) solar cells with iron, we further examine the distribution and charge state of iron-induced defects in LHP films using synchrotron-based X-ray techniques. X-ray absorption measurements suggest that iron-rich regions, which form among iron feedstock concentrations that exceed 100 ppm, most closely resemble the chemistry of Fe2O3. Iron distributed within the bulk may form a mix of Fe2+and Fe3+, the latter of which is not expected to be recombination active, potentially allowing LHPs to incorporate more iron than traditional semiconductors. X-ray beam induced current measurements show little correlation between the presence of iron-rich regions and charge collection, which further suggests low recombination activity at these sites. These results further elucidate the recombination behavior caused by iron incorporation in LHP films, revealing insight into how inhomogeneous incorporation of impurities may mitigate photovoltaic performance degradation., National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (award number DMR-1419807), United States. Department of Energy. Office of Science User Facility (Contract No. DE-AC02-06CH11357), National Science Foundation (U.S.) (NSF EECS Award No. 1541959), Martin Family Society of Fellows for Sustainability, National Science Foundation (U.S.). Graduate Research Fellowship (Grant No. 1122374), National Science Foundation (U.S.). (CA No. EEC-1041895)

Dairy cows are at greatest risk of infectious and metabolic disease during the periparturient period. This period of three weeks either side of calving is also known as the transition period due to the transition into lactation. This thesis had several aims; one was to characterise innate immune function during the transition period in grazing dairy cows by investigating molecular changes in circulating neutrophils and to assess if common on-farm management strategies (pre-calving feeding level and body condition at calving) were able to influence these molecular changes. Next, metabolic stress on neutrophil function was assessed by establishing a model of cows divergent in metabolic health status. This model was further utilised with the aim to investigate nanoparticles (exosomes), which are regulators of innate immune function and indicators of disease state. To address these aims blood was collected from pasture-fed transition dairy cows. Cellular and molecular methods used included cell and exosome isolation, reverse transcriptase (RT)-quantitative PCR, RNA sequencing, cell culture, and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results indicated that grazing dairy cows experience a change in innate immune function during the transition period, reflective of reduced functional capacity of the immune system to overcome infectious agents. This altered function was similar to that experienced by housed cows fed a total mixed ration, which adds evidence to support that the dysfunction is a natural part of the transition into lactation at calving. These results also indicated that the functional changes could be influenced by nutrition status, feeding level, and metabolic stress. Analysis of exosomes isolated from the blood of transition cows indicated that these particles carried cargo indicative of metabolic state during the transition period and that they had the ability to alter target cell processes (gene expression, protein expression, and c

Thesis: S.M., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2015., Cataloged from PDF version of thesis., Includes bibliographical references (pages 61-67)., Photovoltaic (PV) modules provide a source of renewable electricity by harnessing solar energy. Currently, crystalline silicon dominates the PV market with an approximate market share of 90% and record solar cell efficiencies greater than 20%. However, the PV market must decrease the cost to the consumer to maintain growth and meet global electricity demands. Increasing the solar-to-electricity conversion efficiency is one of the most significant cost levers. Transition metal impurities can degrade silicon wafer-based solar cell efficiencies at concentrations as low as 1010 cm3 . By removing interstitial metals from the bulk and/or collecting interstitial metals at heterogeneous nucleation sites, phosphorous diffusion gettering renders them less detrimental in the final solar cell. While they exist for iron, kinetics process simulation tools do not yet exist for chromium, which has higher capture cross-sections for minority carriers and is therefore more detrimental in both p- and n-type materials. In this thesis, I employ synchrotron-based X-ray fluorescence microscopy to study chromium (Cr) distributions in multicrystalline silicon in as-grown material and after two phosphorous diffusion profiles. I complement quantified precipitate size and spatial distribution with interstitial Cr concentration and minority carrier lifetime measurements to provide insight into chromium gettering kinetics and offer suggestions for minimizing the device impacts of chromium. The data presented in this thesis can be used in development of kinetics process simulation tools for chromium gettering. Finally, I describe a new technique for detecting low concentrations of impurities in n- and p-type silicon. The development of high-performance silicon materials, including n-type, necessitates more sensitive impurity detection techniques, capable of measuring interstitial contaminations below 1010 cm-3. I propose the development of a free-carrier absorption-based technique that incorporate, by Mallory Ann Jensen., S.M.