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We present a design strategy for fabricating ultrastable phase-pure films of formamidinium lead iodide (FAPbI3) by lattice templating using specific two-dimensional (2D) perovskites with FA as the cage cation. When a pure FAPbI3 precursor solution is brought in contact with the 2D perovskite, the black phase forms preferentially at 100°C, much lower than the standard FAPbI3 annealing temperature of 150°C. X-ray diffraction and optical spectroscopy suggest that the resulting FAPbI3 film compresses slightly to acquire the (011) interplanar distances of the 2D perovskite seed. The 2D-templated bulk FAPbI3 films exhibited an efficiency of 24.1% in a p-i-n architecture with 0.5-square centimeter active area and an exceptional durability, retaining 97% of their initial efficiency after 1000 hours under 85°C and maximum power point tracking.

With rising atmospheric CO2 levels and a growing demand for sustainable energy, it is imperative to search for a means of a carbon-neutral fuel source that can replace the current global energy infrastructure. Electrochemical and photoelectrochemical CO2 reduction (CO2R) are promising paths towards producing carbon-neutral fuels like methanol. Recently, immobilized molecular catalysts (CoPc) on carbon nanotubes have been growing in interest as they exhibit extraordinary catalytic properties, such as high current density, high product selectivity, long-term stability, high turnover-frequency, low overpotentials, and the ability to operate in aqueous environments. To improve upon these hybrid CO2R systems, it is crucial to understand how the molecular catalyst interacts with the graphitic support to further tailor the catalyst or the local microenvironment. This dissertation will be focusing on discussing the local microenvironments surrounding the catalysts and multiwalled carbon nanotube (MWCNT) support. First, a broad overview of catalyst types in electrochemistry is discussed, which gives context to the current field of immobilized molecular catalysts on graphitic supports for CO2 reduction. The following chapter discusses how the preparation methods of these hybrid catalyst/MWCNT electrodes can affect the surface morphology, electrochemical behavior, and catalysis. Next, in-situ XAS electrochemical measurements were taken of Re(tBu-bpy)(CO)3Cl on MWCNT to study their electronic coupling and molecular interactions. The next chapter discusses how applied bias and mass transport affect the selectivity of immobilized CoPc on MWCNT for selective methanol generation, and the role of CO as a reactive unbound intermediate. This model catalyst layer preparation was integrated onto a 3-terminal tandem device (3TT) for a photoelectrochemical CO2R cascade scheme to generate methanol using light in a near neutral pH aqueous system. The last chapter is focused on providing ide

Functional oxides on silicon have been the subject of in-depth research for more than 20 years. Much of this research has been focused on the quality of the integration of materials due to their intrinsic thermodynamic incompatibility, which has hindered the flourishing of the field of research. Nevertheless, growth of epitaxial transition metal oxides on silicon with a sharp interface has been achieved by elaborated kinetically controlled sequential deposition while the crystalline quality of different functional oxides has been considerably improved. In this Research Update, we focus on three applications in which epitaxial ferroelectric oxides on silicon are at the forefront, and in each of these applications, other aspects of the integration of materials play an important role. These are the fields of piezoelectric microelectromechanical system devices, electro-optical components, and catalysis. The overview is supported by a brief analysis of the synthesis processes that enable epitaxial growth of oxides on silicon. This Research Update concludes with a theoretical description of the interfaces and the possibility of manipulating their electronic structure to achieve the desired coupling between (ferroelectric) oxides and semiconductors, which opens up a remarkable perspective for many advanced applications. © 2021 Author(s).

While halide perovskites attract significant academic attention, examples of at-scale industrial production are still sparse. In this perspective, we review practical challenges hindering the commercialization of halide perovskites, and discuss how machine-learning (ML) tools could help: (1) active-learning algorithms that blend institutional knowledge and human expertise could help stabilize and rapidly update baseline manufacturing processes; (2) ML-powered metrology, including computer imaging, could help narrow the performance gap between large- and small-area devices; and (3) inference methods could help accelerate root-cause analysis by reconciling multiple data streams and simulations, focusing research effort on areas with highest probability for improvement. We conclude that to satisfy many of these challenges, incremental -- not radical -- adaptations of existing ML and statistical methods are needed. We identify resources to help develop in-house data-science talent, and propose how industry-academic partnerships could help adapt "ready-now" ML tools to specific industry needs, further improve process control by revealing underlying mechanisms, and develop "gamechanger" discovery-oriented algorithms to better navigate vast materials combination spaces and the literature., Comment: 21 pages, 2 figures

Copyright © 2020 American Chemical Society. Degradation due to electron beam exposure has posed a challenge in the use of electron microscopy to probe halide perovskite materials and devices. In this study, the interaction between the electron beam and the perovskite across acceleration voltages and at low probe currents is investigated in a scanning electron microscope (SEM) by monitoring the electron-beam-induced current (EBIC) response in perovskite solar cells in a plan-view configuration. SEM probe conditions are identified where dozens of repeated scans over a single region of the perovskite solar cell induce minimal electronic degradation. Overall, the induced current response of the perovskite device is found to strongly depend upon the beam condition: Rapid decay occurs at high beam powers, the current activates at the lowest beam powers, and a newfound quasi-steady response is revealed at intermediate beam conditions. A quantitative window for the successful conduction of e-beam studies with minimal electronic degradation is revealed by evaluating induced current response over a wide range of perovskite devices, which invites broader use of SEM-based characterization techniques, including EBIC, as powerful techniques for correlative microscopy investigations.

Functional oxides on silicon have been the subject of in-depth research for more than 20 years. Much of this research has been focused on the quality of the integration of materials due to their intrinsic thermodynamic incompatibility, which has hindered the flourishing of the field of research. Nevertheless, growth of epitaxial transition metal oxides on silicon with a sharp interface has been achieved by elaborated kinetically controlled sequential deposition while the crystalline quality of different functional oxides has been considerably improved. In this Research Update, we focus on three applications in which epitaxial ferroelectric oxides on silicon are at the forefront, and in each of these applications, other aspects of the integration of materials play an important role. These are the fields of piezoelectric microelectromechanical system devices, electro-optical components, and catalysis. The overview is supported by a brief analysis of the synthesis processes that enable epitaxial growth of oxides on silicon. This Research Update concludes with a theoretical description of the interfaces and the possibility of manipulating their electronic structure to achieve the desired coupling between (ferroelectric) oxides and semiconductors, which opens up a remarkable perspective for many advanced applications. © 2021 Author(s).

Lead halide perovskites are among the most exciting classes of optoelectronic materials due to their unique ability to form high‐quality crystals with tunable bandgaps in the visible and near‐infrared using simple solution precipitation reactions. This facile crystallization is driven by their ionic nature; just as with other salts, it is challenging to form amorphous halide perovskites, particularly in thin‐film form where they can most easily be studied. Here, rapid desolvation promoted by the addition of acetate precursors is shown as a general method for making amorphous lead halide perovskite films with a wide variety of compositions, including those using common organic cations (methylammonium and formamidinium) and anions (bromide and iodide). By controlling the amount of acetate, it is possible to tune from fully crystalline to fully amorphous films, with an interesting intermediate state consisting of crystalline islands embedded in an amorphous matrix. The amorphous lead halide perovskite has a large and tunable optical bandgap. It improves the photoluminescence quantum yield and lifetime of incorporated crystalline perovskite, opening up the intriguing possibility of using amorphous perovskite as a passivating contact, as is currently done in record efficiency silicon solar cells.

Perovskite solar cells have drawn much attention in recent years, owing to its world-record setting photovoltaic performances. Despite its promising use in tandem applications and flexible devices, its practicality is still limited by its structural instability often arising from ion migration and defect formation. While it is generally understood that ion instability is a primary cause for degradation, there is still a lack of direct evidence of structural transformation at the atomistic scale. Such an understanding is crucial to evaluate and pin-point how such instabilities are induced relative to external perturbations such as illumination or electrical bias with time, allowing researchers to devise effective strategies to mitigate them. Here, we designed an in-situ TEM setup to enable real-time observation of amorphization in double cation mixed perovskite materials under electrical biasing at 1 V. It is found that amorphization occurs along the (001) and (002) planes, which represents the observation of in-situ facet-dependent amorphization of a perovskite crystal. To reverse the degradation, the samples were heated at 50 oC and was found to recrystallize, effectively regaining its performance losses. This work is vital toward understanding fundamental ion-migration phenomena and address instability challenges of perovskite optoelectronics.

Though generally reliable, silicon solar modules can be subject to unforeseen degradation, leading to a duty life shorter than the expected 25-year life cycle. Potential-induced degradation (PID) has proven difficult to characterize and study. This dissertation is dedicated to developing a physical model to understand the kinetics of PID of the shunting type, and explain the factors that may lead to the design of PID-robust modules.A bias-temperature stress (BTS) methodology to study ion migration in dielectric films is presented, which accounts for the contribution of bulk traps in the dielectric. Using this method, an Arrhenius relationship for the diffusivity of Na+ in SiNx is determined, for which the prefactor is D0=1.4E-14 cm^2/s, and the activation energy is Ea = 0.14 eV, with a 95% confidence interval of [0.07, 0.21] eV. Based on this result, we bound the transit time of sodium ions through highly resistive SiNx anti-reflective coatings, within 1 h and 2 days, under temperature and electric fields relevant to PV operation.A numerical solution to the coupled Poisson-Nernst-Planck system of equations is presented, based on the finite element method (FEM), that can accurately simulate ionic transport in dielectrics and stacks of materials. The FEM implementation adequately describes the accumulation of charge in the semiconductor interface of metal-insulator-semiconductor capacitors (MIS). Using this model, we evaluate diffusion coefficients of Na+ in SiO2 under BTS conditions. A methodology to simulate PID degradation in PV modules is derived, which uses the result from the ion transport model to simulate the characteristic J-V of the devices. PID is adequately described by the presence of metallic shunt at the p-n junction of the cell, for which, the metal conductivity depends on the sodium concentration. An upper bound for the diffusivity of Na in stacking faults that result in PID is estimated to be 1E-14 cm^2/s, based on comparison of the simulated PID tim

Perovskite solar cells have drawn much attention in recent years, owing to its world-record setting photovoltaic performances. Despite its promising use in tandem applications and flexible devices, its practicality is still limited by its structural instability often arising from ion migration and defect formation. While it is generally understood that ion instability is a primary cause for degradation, there is still a lack of direct evidence of structural transformation at the atomistic scale. Such an understanding is crucial to evaluate and pin-point how such instabilities are induced relative to external perturbations such as illumination or electrical bias with time, allowing researchers to devise effective strategies to mitigate them. Here, we designed an in-situ TEM setup to enable real-time observation of amorphization in double cation mixed perovskite materials under electrical biasing at 1 V. It is found that amorphization occurs along the (001) and (002) planes, which represents the observation of in-situ facet-dependent amorphization of a perovskite crystal. To reverse the degradation, the samples were heated at 50 oC and was found to recrystallize, effectively regaining its performance losses. This work is vital toward understanding fundamental ion-migration phenomena and address instability challenges of perovskite optoelectronics.

Though generally reliable, silicon solar modules can be subject to unforeseen degradation, leading to a duty life shorter than the expected 25-year life cycle. Potential-induced degradation (PID) has proven difficult to characterize and study. This dissertation is dedicated to developing a physical model to understand the kinetics of PID of the shunting type, and explain the factors that may lead to the design of PID-robust modules.A bias-temperature stress (BTS) methodology to study ion migration in dielectric films is presented, which accounts for the contribution of bulk traps in the dielectric. Using this method, an Arrhenius relationship for the diffusivity of Na+ in SiNx is determined, for which the prefactor is D0=1.4E-14 cm^2/s, and the activation energy is Ea = 0.14 eV, with a 95% confidence interval of [0.07, 0.21] eV. Based on this result, we bound the transit time of sodium ions through highly resistive SiNx anti-reflective coatings, within 1 h and 2 days, under temperature and electric fields relevant to PV operation.A numerical solution to the coupled Poisson-Nernst-Planck system of equations is presented, based on the finite element method (FEM), that can accurately simulate ionic transport in dielectrics and stacks of materials. The FEM implementation adequately describes the accumulation of charge in the semiconductor interface of metal-insulator-semiconductor capacitors (MIS). Using this model, we evaluate diffusion coefficients of Na+ in SiO2 under BTS conditions. A methodology to simulate PID degradation in PV modules is derived, which uses the result from the ion transport model to simulate the characteristic J-V of the devices. PID is adequately described by the presence of metallic shunt at the p-n junction of the cell, for which, the metal conductivity depends on the sodium concentration. An upper bound for the diffusivity of Na in stacking faults that result in PID is estimated to be 1E-14 cm^2/s, based on comparison of the simulated PID tim

The role of the alkali metal cations in halide perovskite solar cells is not well understood. Using synchrotron-based nano-x-ray fluorescence and complementary measurements, we found that the halide distribution becomes homogenized upon addition of cesium iodide, either alone or with rubidium iodide, for substoichiometric, stoichiometric, and overstoichiometric preparations, where the lead halide is varied with respect to organic halide precursors. Halide homogenization coincides with long-lived charge carrier decays, spatially homogeneous carrier dynamics (as visualized by ultrafast microscopy), and improved photovoltaic device performance. We found that rubidium and potassium phase-segregate in highly concentrated clusters. Alkali metals are beneficial at low concentrations, where they homogenize the halide distribution, but at higher concentrations, they form recombination-active second-phase clusters.

The role of the alkali metal cations in halide perovskite solar cells is not well understood. Using synchrotron-based nano-x-ray fluorescence and complementary measurements, we found that the halide distribution becomes homogenized upon addition of cesium iodide, either alone or with rubidium iodide, for substoichiometric, stoichiometric, and overstoichiometric preparations, where the lead halide is varied with respect to organic halide precursors. Halide homogenization coincides with long-lived charge carrier decays, spatially homogeneous carrier dynamics (as visualized by ultrafast microscopy), and improved photovoltaic device performance. We found that rubidium and potassium phase-segregate in highly concentrated clusters. Alkali metals are beneficial at low concentrations, where they homogenize the halide distribution, but at higher concentrations, they form recombination-active second-phase clusters.

We demonstrate an oxide-stabilized III-V photoelectrode architecture for solar fuel production from water in neutral pH. For this tunable architecture we demonstrate 100% Faradaic efficiency for hydrogen evolution, and incident photon-to-current efficiencies (IPCE) exceeding 50%. High IPCE for hydrogen evolution is a consequence of the low-loss interface achieved via epitaxial growth of a thin oxide on a GaAs solar cell. Developing optimal energetic alignment across the interfaces of the photoelectrode using well-established III-V technology is key to obtaining high performance. This advance constitutes a critical milestone towards efficient, unassisted fuel production from solar energy., Massachusetts Institute of Technology. Battelle Postdoctoral Program, MIT Energy Initiative, MIT & Masdar Institute Cooperative Program

Perovskite solar cells have shown remarkable efficiencies beyond 22%, through organic and inorganic cation alloying. However, the role of alkali-metal cations is not well-understood. By using synchrotron-based nano-X-ray fluorescence and complementary measurements, we show that when adding RbI and/or CsI the halide distribution becomes homogenous. This homogenization translates into long-lived charge carrier decays, spatially homogenous carrier dynamics visualized by ultrafast microscopy, as well as improved photovoltaic device performance. We find that Rb and K phase-segregate in highly concentrated aggregates. Synchrotron-based X-ray-beam-induced current and electron-beam-induced current of solar cells show that Rb clusters do not contribute to the current and are recombination active. Our findings bring light to the beneficial effects of alkali metal halides in perovskites, and point at areas of weakness in the elemental composition of these complex perovskites, paving the way to improved performance in this rapidly growing family of materials for solar cell applications.

Perovskite solar cells have shown remarkable efficiencies beyond 22%, through organic and inorganic cation alloying. However, the role of alkali-metal cations is not well-understood. By using synchrotron-based nano-X-ray fluorescence and complementary measurements, we show that when adding RbI and/or CsI the halide distribution becomes homogenous. This homogenization translates into long-lived charge carrier decays, spatially homogenous carrier dynamics visualized by ultrafast microscopy, as well as improved photovoltaic device performance. We find that Rb and K phase-segregate in highly concentrated aggregates. Synchrotron-based X-ray-beam-induced current and electron-beam-induced current of solar cells show that Rb clusters do not contribute to the current and are recombination active. Our findings bring light to the beneficial effects of alkali metal halides in perovskites, and point at areas of weakness in the elemental composition of these complex perovskites, paving the way to improved performance in this rapidly growing family of materials for solar cell applications.

The personal ultraviolet (UV) dosimeter is a useful measurement tool to prevent UV induced dermal damages; however, conventional digital dosimeters are either bulky or require external power sources. Here, a wearable, colorimetric UV film dosimeter that provides color transition, from purple to transparent, is reported to indicate the UV dose. The film dosimeter is made of a purple photodegradable dye ((2Z,6Z)-2,6-bis(2-(2,6-diphenyl-4H-thiopyran-4-ylidene)ethylidene)cyclohexanone or DTEC) blended in low density polyethylene film. The DTEC film discolored 3.3 times more under the exposure of UV light (302 nm) than visible light (543 nm), and a UV bandpass filter is developed to increase this selectivity to UV light. The DTEC film completely discolors to transparency in 2 h under an AM 1.5 solar simulator, suggesting the potential as an indicator for individuals with types I-VI skin to predict interventions to avoid sunburn. Finally, the DTEC film is integrated with the UV bandpass filter on a wristband to function as a wearable dosimeter for low cost and convenient monitoring of sunlight exposure.

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)

Control of detrimental metal impurities is crucial to silicon solar cell performance. Traditional silicon solar cell emitters are diffused in an infinite-source regime and are known to cause strong point defect segregation towards the emitter and thus enhance bulk minority carrier diffusion length. With the advent of ion-implantation and chemical vapor deposition (CVD) glasses, finite-source diffused emitters are attracting interest. This contribution aims to increase their adoption by elucidating the dominant gettering mechanisms present in finite-source diffused emitters. Our findings indicate that infinite-source diffusion is critical for effective segregation gettering, but that high enough surface phosphorus concentration can activate segregation gettering via finite-source diffusion as well. In the case of ion-implanted emitters, the traditional segregation gettering may be considerably enhanced by impurity precipitation in the implanted layer., United States. Department of Energy. Office of Basic Energy Sciences (Contract No. DE-AC02-06CH11357), National Science Foundation (U.S.) (CA No. EEC-1041895), Finnish Cultural Foundation, Fulbright-Technology Industries of Finland Grant, University of California, San Diego. Start Up Funds

Understanding reactions at the electrode/electrolyte interface (EEI) is essential to developing strategies to enhance cycle life and safety of lithium batteries. Despite research in the past four decades, there is still limited understanding by what means different components are formed at the EEI and how they influence EEI layer properties. We review findings used to establish the well-known mosaic structure model for the EEI (often referred to as solid electrolyte interphase or SEI) on negative electrodes including lithium, graphite, tin, and silicon. Much less understanding exists for EEI layers for positive electrodes. High-capacity Li-rich layered oxides yLi[subscript 2–x]MnO[subscript 3]·(1–y)Li[subscript 1–x]MO[subscript 2], which can generate highly reactive species toward the electrolyte via oxygen anion redox, highlight the critical need to understand reactions with the electrolyte and EEI layers for advanced positive electrodes. Recent advances in in situ characterization of well-defined electrode surfaces can provide mechanistic insights and strategies to tailor EEI layer composition and properties., BMW Group, MIT/Battelle postdoctoral associate program, Taiwan. Ministry of Science and Technology (02-2917-I-564-006-A1), National Defense Science and Engineering Graduate (NDSEG) Fellowship, United States. Department of Defense (32 CFR 168a DoD), United States. Air Force. Office of Scientific Research, United States. Department of Energy. Office of Science (Contract No. DE-AC02-05CH11231)

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2013., Cataloged from PDF version of thesis., Includes bibliographical references (pages 175-203)., Efficiency is a major lever for cost reduction in crystalline silicon solar cells, which dominate the photovoltaics market but cannot yet compete subsidy-free in most areas. Iron impurities are a key performance-limiting defect present in commercial and precommercial silicon solar cell materials, affecting devices at concentrations below even one part per billion. The lack of process simulation tools that account for the behavior of such impurities hinders efforts at increasing efficiency in commercial materials and slows the time-to-market for novel materials. To address the need for predictive process modeling focused on the impact of impurities, the Impurity-to-Efficiency kinetics simulation tool is developed to predict solar cell efficiency from initial iron contamination levels. The modeling effort focuses on iron because it is known to limit most industrial solar cells. The simulation models phosphorus diffusion, the coupled diffusion and segregation of iron to the high phosphorus concentration emitter, and the dissolution and growth of iron-silicide precipitates. The ID process simulation can be solved in about 1 minute assuming standard processing conditions, allowing for rapid iteration. By wrapping the kinetics simulation tool with a genetic algorithm, global optima in the high-dimensional processing parameter space can be pursued for a given starting metal concentration and distribution. To inform and test the model, synchrotron-based X-ray fluorescence is employed with beam spot sizes less than 200 nm to identify iron-rich precipitates down to 10 nm in radius in industrial and research materials. Experimental X-ray fluorescence data confirm model predictions that iron remains in heavily-contaminated multicrystalline materials after a typical industrial phosphorus diffusion. Similar measurements of the iron-silicide precipitate distribution in multicrystalline silicon samples before and after higher-temperature gettering steps confirm that the higher the, by David P. Fenning., Ph. D.

A phosphorus diffusion gettering model is used to examine the efficacy of a standard gettering process on interstitial and precipitated iron in multicrystalline silicon. The model predicts a large concentration of precipitated iron remaining after standard gettering for most as-grown iron distributions. Although changes in the precipitated iron distribution are predicted to be small, the simulated post-processing interstitial iron concentration is predicted to depend strongly on the as-grown distribution of precipitates, indicating that precipitates must be considered as internal sources of contamination during processing. To inform and validate the model, the iron distributions before and after a standard phosphorus diffusion step are studied in samples from the bottom, middle, and top of an intentionally Fe-contaminated laboratory ingot. A census of iron-silicide precipitates taken by synchrotron-based X-ray fluorescence microscopy confirms the presence of a high density of iron-silicide precipitates both before and after phosphorus diffusion. A comparable precipitated iron distribution was measured in a sister wafer after hydrogenation during a firing step. The similar distributions of precipitated iron seen after each step in the solar cell process confirm that the effect of standard gettering on precipitated iron is strongly limited as predicted by simulation. Good agreement between the experimental and simulated data supports the hypothesis that gettering kinetics is governed by not only the total iron concentration but also by the distribution of precipitated iron. Finally, future directions based on the modeling are suggested for the improvement of effective minority carrier lifetime in multicrystalline silicon solar cells.

A phosphorus diffusion gettering model is used to examine the efficacy of a standard gettering process on interstitial and precipitated iron in multicrystalline silicon. The model predicts a large concentration of precipitated iron remaining after standard gettering for most as-grown iron distributions. Although changes in the precipitated iron distribution are predicted to be small, the simulated post-processing interstitial iron concentration is predicted to depend strongly on the as-grown distribution of precipitates, indicating that precipitates must be considered as internal sources of contamination during processing. To inform and validate the model, the iron distributions before and after a standard phosphorus diffusion step are studied in samples from the bottom, middle, and top of an intentionally Fe-contaminated laboratory ingot. A census of iron-silicide precipitates taken by synchrotron-based X-ray fluorescence microscopy confirms the presence of a high density of iron-silicide precipitates both before and after phosphorus diffusion. A comparable precipitated iron distribution was measured in a sister wafer after hydrogenation during a firing step. The similar distributions of precipitated iron seen after each step in the solar cell process confirm that the effect of standard gettering on precipitated iron is strongly limited as predicted by simulation. Good agreement between the experimental and simulated data supports the hypothesis that gettering kinetics is governed by not only the total iron concentration but also by the distribution of precipitated iron. Finally, future directions based on the modeling are suggested for the improvement of effective minority carrier lifetime in multicrystalline silicon solar cells.

The evolution during silicon solar cell processing of performance-limiting iron impurities is investigated with synchrotron-based x-ray fluorescence microscopy. We find that during industrial phosphorus diffusion, bulk precipitate dissolution is incomplete in wafers with high metal content, specifically ingot border material. Postdiffusion low-temperature annealing is not found to alter appreciably the size or spatial distribution of FeSi[subscript 2] precipitates, although cell efficiency improves due to a decrease in iron interstitial concentration. Gettering simulations successfully model experiment results and suggest the efficacy of high- and low-temperature processing to reduce both precipitated and interstitial iron concentrations, respectively., United States. Dept. of Energy (Contract DE-FG36-09GO1900), Spanish Ministry of Science and Innovation (Thincells Project TEC2008-06798-C03-02)

Synchrotron-based X-ray fluorescence microscopy is applied to study the evolution of iron silicide precipitates during phosphorus diffusion gettering and low-temperature annealing. Heavily Fe-contaminated ingot border material contains FeSi2 precipitates after rapid in-line P-diffusion firing, suggesting kinetically limited gettering in these regions. An impurity-to-efficiency (I2E) gettering model is developed to explain the results. The model demonstrates the efficacy of high- and medium-temperature processing on reducing the interstitial iron population over a range of process parameters available to industry., United States. Dept. of Energy (contract number DE-FG36-09GO1900), National Science Foundation (U.S.) (NSF Graduate Research Fellowship), Barcelona Chamber of Commerce (MIT-Spain/La Cambra de Barcelona Seed Fund)

The extraction of metal impurities during phosphorus diffusion gettering (PDG) is one of the crucial process steps when fabricating high-efficiency solar cells using low-cost, lower-purity silicon wafers. In this work, we show that for a given metal concentration, the size and density of metal silicide precipitates strongly influences the gettering efficacy. Different precipitate size distributions can be already found in silicon wafers grown by different techniques. In our experiment, however, the as-grown distribution of precipitated metals in multicrystalline Si sister wafers is engineered through different annealing treatments in order to control for the concentration and distribution of other defects. A high density of small precipitates is formed during a homogenization step, and a lower density of larger precipitates is formed during extended annealing at 740º C. After PDG, homogenized samples show a decreased interstitial iron concentration compared to as-grown and ripened samples, in agreement with simulations.

Coupled device and process silumation tools, collectively known as technology computer-aided design (TCAD), have been used in the integrated circuit industry for over 30 years. These tools allow researchers to quickly converge on optimized devide designs and manufacturing processes with minimal experimental expenditures. The PV industry has been slower to adopt these tools, but is quickly developing competency in using them. This paper introduces a predictive defect engineering paradigm and simulation tool, while demonstrating its effectiveness at increasing the performance and throughput of current industrial processes. the impurity-to-efficiency (I2E) simulator is a coupled process and device simulation tool that links wafer material purity, processing parameters and cell desigh to device performance. The tool has been validated with experimental data and used successfully with partners in industry. The simulator has also been deployed in a free web-accessible applet, which is available for use by the industrial and academic communities.

Coupled device and process silumation tools, collectively known as technology computer-aided design (TCAD), have been used in the integrated circuit industry for over 30 years. These tools allow researchers to quickly converge on optimized devide designs and manufacturing processes with minimal experimental expenditures. The PV industry has been slower to adopt these tools, but is quickly developing competency in using them. This paper introduces a predictive defect engineering paradigm and simulation tool, while demonstrating its effectiveness at increasing the performance and throughput of current industrial processes. the impurity-to-efficiency (I2E) simulator is a coupled process and device simulation tool that links wafer material purity, processing parameters and cell desigh to device performance. The tool has been validated with experimental data and used successfully with partners in industry. The simulator has also been deployed in a free web-accessible applet, which is available for use by the industrial and academic communities.

The extraction of metal impurities during phosphorus diffusion gettering (PDG) is one of the crucial process steps when fabricating high-efficiency solar cells using low-cost, lower-purity silicon wafers. In this work, we show that for a given metal concentration, the size and density of metal silicide precipitates strongly influences the gettering efficacy. Different precipitate size distributions can be already found in silicon wafers grown by different techniques. In our experiment, however, the as-grown distribution of precipitated metals in multicrystalline Si sister wafers is engineered through different annealing treatments in order to control for the concentration and distribution of other defects. A high density of small precipitates is formed during a homogenization step, and a lower density of larger precipitates is formed during extended annealing at 740º C. After PDG, homogenized samples show a decreased interstitial iron concentration compared to as-grown and ripened samples, in agreement with simulations.

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2010., Cataloged from PDF version of thesis., Includes bibliographical references (p. 97-103)., A theoretical framework is presented in this work for retrograde melting in silicon driven by the retrograde solubility of low-concentration metallic solutes at temperatures above the binary eutectic. High enthalpy of formation of point defects in silicon leads to retrograde solubility for a number of solutes, including many 3d transition metals. The Ni-Si system is used to demonstrate that in silicon under supersaturated conditions, such solutes precipitate out into liquid droplets. Synchrotron-based Xray Absorption Microspectroscopy measurements provide experimental confirmation of such phase transitions and the underlying thermodynamics. Finally, the potential for using retrograde melting to improve the electronic minority carrier lifetime of low quality silicon solar cell materials is considered., by David P. Fenning., S.M.

The introduction of a low-temperature (LT) tail after P emitter diffusion was shown to lead to considerable improvements in electron lifetime and solar cell performance by different researchers. So far, the drawback of the investigated extended gettering treatments has been the lack of knowledge about optimum annealing times and temperatures and the important increase in processing time. In this manuscript, we calculate optimum annealing temperatures of Fe-contaminated Si wafers for different annealing durations. Subsequently, it is shown theoretically and experimentally that a relatively short LT tail of 15 min can lead to a significant reduction of interstitial Fe and an increase in electron lifetime. Finally, we calculate the potential improvement of solar cell efficiency when such a short-tail extended P diffusion gettering is included in an industrial fabrication process.

The introduction of a low-temperature (LT) tail after P emitter diffusion was shown to lead to considerable improvements in electron lifetime and solar cell performance by different researchers. So far, the drawback of the investigated extended gettering treatments has been the lack of knowledge about optimum annealing times and temperatures and the important increase in processing time. In this manuscript, we calculate optimum annealing temperatures of Fe-contaminated Si wafers for different annealing durations. Subsequently, it is shown theoretically and experimentally that a relatively short LT tail of 15 min can lead to a significant reduction of interstitial Fe and an increase in electron lifetime. Finally, we calculate the potential improvement of solar cell efficiency when such a short-tail extended P diffusion gettering is included in an industrial fabrication process.

Hierarchically organized porous carbonized-Co3O4 inverse opal nanostructures (C-Co3O4 IO) are synthesized via complementary colloid and block copolymer self-assembly, where the triblock copolymer Pluronic P123 acts as the template and the carbon source. These highly ordered porous inverse opal nanostructures with high surface area display synergistic properties of high energy density and promising bifunctional electrocatalytic activity toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). It is found that the as-made C-Co3O4 IO/Ketjen Black (KB) composite exhibits remarkably enhanced electrochemical performance, such as increased specific capacity (increase from 3591 to 6959 mA h g−1), lower charge overpotential (by 284.4 mV), lower discharge overpotential (by 19.0 mV), and enhanced cyclability (about nine times higher than KB in charge cyclability) in Li–O2 battery. An overall agreement is found with both C-Co3O4 IO/KB and Co3O4 IO/KB in ORR and OER half-cell tests using a rotating disk electrode. This enhanced catalytic performance is attributed to the porous structure with highly dispersed carbon moiety intact with the host Co3O4 catalyst.