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At least 703 records · Page 39

Overcoming Degradation Pathways to Achieve Stable Blue Perovskite Light-Emitting Diodes

Mixed halide (Br/Cl) perovskite nanocrystals (NCs) that represent an advanced blue emitter commonly suffer from spectral instability and poor lifespan; notably, the lack of understanding of the failure mechanisms of these devices has restricted the future progress. Here, we determine that the degradation of CsPbBr x Cl 3– x NCs containing blue light-emitting diodes (LEDs) is due to the combination of two effects. Cl – drift among adjoining NCs under an electric field is found to induce a Cl-deficient material region in multiple NC layers, which dominates the unstable electroluminescence and causes fast degradation in the corresponding devices. In comparison, the monolayer NC devices that feature restricted anion drift pathways exhibit better operational stability; however, excess hole injection is demonstrated to induce irreversible chlorine loss in NCs. Such a process that largely arises from electrochemical oxidation of Cl – initiates a mild device failure in operation of tens of minutes. Through revealing these mechanisms, we modulate the devices’ construction and operational conditions to achieve a longer lifespan.

14 SOLAR ENERGY↗

Incorporating Electrochemical Halide Oxidation into Drift-Diffusion Models to Explain Performance Losses in Perovskite Solar Cells under Prolonged Reverse Bias

Partial shading of a solar module can induce a set of cells within the module to operate under reverse bias. Studies have shown that metal halide perovskite solar cells with a wide variety of compositions and contacts exhibit interesting behavior in reverse bias that includes both reversible performance loss and non-reversible degradation. In this paper, an advanced drift-diffusion approach incorporating an electrochemical term to explain the short-circuit, open circuit and fill factor losses that are experimentally measured after prolonged reverse bias is used. It is shown that holes can tunnel into the perovskite due to sharp band bending near the contact, accumulate within the bulk of the perovskite absorber, and trigger the oxidation of halides to form neutral halogens. The density of neutral halogens is much higher in reverse bias because there are hardly any electrons available to reduce the iodine. The resulting halogens act as bulk recombination centers. While the interstitial halogen density does decay when the cell is operated in forward bias, permanent degradation can occur if the iodine diffuses out of the perovskite layer. Finally, the ways in which changing parameters such as the mobile ion density or the series resistance at the contact can influence device performance and stability are discussed.

degradation↗

Evolution of the Space Station Robotic Manipulator

The Space Station Remote Manipulator System (SSRMS), Canadarm2, was launched in 2001 and deployed on the International Space Station (ISS). The Canadarm2 has been instrumental in ISS assembly and maintenance. Canadarm2 shares its heritage with the Space Shuttle Arm (Canadarm). This article explores the evolution from the Shuttle Canadarm to the Space Station Canadarm2 design, which incorporates a 7 degree of freedom design, larger joints, and changeable operating base. This article also addresses phased design, redundancy, life and maintainability requirements. The design of Canadarm2 meets unique ISS requirements, including expanded handling capability and the ability to be maintained on orbit. The size of ISS necessitated a mobile manipulator, resulting in the unique capability of Canadarm2 to relocate by performing a walk off to base points located along the Station, and interchanging the tip and base of the manipulator. This provides the manipulator with reach and access to a large part of the Station, enabling on-orbit assembly of the Station and providing support to Extra-Vehicular Activity (EVA). Canadarm2 is evolving based on on-orbit operational experience and new functionality requirements. SSRMS functionality is being developed in phases to support evolving ISS assembly and operation as modules are added and the Station becomes more complex. Changes to sustaining software, hardware architecture, and operations have significantly enhanced SSRMS capability to support ISS mission requirements. As a result of operational experience, SSRMS changes have been implemented for Degraded Joint Operations, Force Moment Sensor Thermal Protection, Enabling Ground Controlled Operations, and Software Commutation. Planned Canadarm2 design modifications include: Force Moment Accommodation, Smart Safing, Separate Safing, and Hot Backup. In summary, Canadarm2 continues to evolve in support of new ISS requirements and improved operations. It is a tribute to the design that this evolution can be accomplished while conducting critical on-orbit operations with minimal hardware changes.

Razvi, Shakeel↗

Study of the Staebler-Wronski degradation effect in a-Si:H based p-i-n solar cell

Conversion of solar energy into electricity using environmentally safe and clean photovoltaic methods to supplement the ever increasing energy needs has been a cherished goal of many scientists and engineers around the world. Photovoltaic solar cells on the other hand, have been the power source for satellites ever since their introduction in the early sixties. For widespread terrestrial applications, however, the cost of photovoltaic systems must be reduced considerably. Much progress has been made in the recent past towards developing economically viable terrestrial systems, and the future looks highly promising. Thin film solar cells offer cost reductions mainly from their low processing cost, low material cost, and choice of low cost substrates. These are also very attractive for space applications because of their high power densities (power produced per kilogram of solar cell pay load) and high radiation resistance. Amorphous silicon based solar cells are amongst the top candidates for economically viable terrestrial and space based power generation. Despite very low federal funding during the eighties, amorphous silicon solar cell efficiencies have continually been improved - from a low 3 percent to over 13 percent now. Further improvements have been made by the use of multi-junction tandem solar cells. Efficiencies close to 15 percent have been achieved in several labs. In order to be competitive with fossil fuel generated electricity, it is believed that module efficiency of 15 percent or cell efficiency of 20 percent is required. Thus, further improvements in cell performance is imperative. One major problem that was discovered almost 15 years ago in amorphous silicon devices is the well known Staebler-Wronski Effect. Efficiency of amorphous silicon solar cells was found to degrade upon exposure to sunlight. Until now their is no consensus among the scientists on the mechanism for this degradation. Efficiency may degrade anywhere from 10 percent to almost 50 percent within the first few months of operation. In order to improve solar cell efficiencies, it is clear that the cause or causes of such degradation must be found and the processing conditions altered to minimize the loss in efficiency. This project was initiated in 1987 to investigate a possible link between metallic impurities, in particular, Ag, and this degradation. Such a link was established by one of the NASA scientists for the light induced degradation of n+/p crystalline silicon solar cells.

Naseem, H. A.↗

Soil microbiome interventions for carbon sequestration and climate mitigation

Mitigating climate change in soil ecosystems involves complex plant and microbial processes regulating carbon pools and flows. Here, we advocate for the use of soil microbiome interventions to help increase soil carbon stocks and curb greenhouse gas emissions from managed soils. Direct interventions include the introduction of microbial strains, consortia, phage, and soil transplants, whereas indirect interventions include managing soil conditions or additives to modulate community composition or its activities. Approaches to increase soil carbon stocks using microbially catalyzed processes include increasing carbon inputs from plants, promoting soil organic matter (SOM) formation, and reducing SOM turnover and production of diverse greenhouse gases. Marginal or degraded soils may provide the greatest opportunities for enhancing global soil carbon stocks. Among the many knowledge gaps in this field, crucial gaps include the processes influencing the transformation of plant-derived soil carbon inputs into SOM and the identity of the microbes and microbial activities impacting this transformation. As a critical step forward, we encourage broadening the current widespread screening of potentially beneficial soil microorganisms to encompass functions relevant to stimulating soil carbon stocks. Moreover, in developing these interventions, we must consider the potential ecological ramifications and uncertainties, such as incurred by the widespread introduction of homogenous inoculants and consortia, and the need for site-specificity given the extreme variation among soil habitats. Incentivization and implementation at large spatial scales could effectively harness increases in soil carbon stocks, helping to mitigate the impacts of climate change.

54 ENVIRONMENTAL SCIENCES↗

Development of an Extreme Fast Charging Battery

The objective of the project is to research, develop, design, fabricate, and demonstrate extreme fast charging (XFC) Li-ion cells capable of a 10 min charge to deliver 180Wh/kg at the beginning of life (BoL) and sustain >500 XFC cycles with less than 20% capacity loss. The PI developed an asymmetric temperature modulation (ATM) charging strategy that charges a Li-ion cell at an elevated temperature of ~60oC and discharges at the ambient temperature. The elevated charging temperature eliminates Li plating, while the limited exposure time to 60oC effectively controls materials degradation, thereby enabling XFC with remarkable battery life. We developed and demonstrated 209 and 271 Wh/kg cells, both of which exceed the afore-mentioned target of delivering 180Wh/kg at BoL and sustaining 500+ XFC cycles with less than 20% loss.

25 ENERGY STORAGE↗

Effects of space exposure on thermal control coatings

Optical degradation of selected thermal control coatings exposed on LDEF Experiment A0034, 'Atomic Oxygen Stimulated Outgassing', attributable to effects of solar radiation, was significantly changed for specimens whose exposure included orbital atomic oxygen impingement. This LDEF experiment consisted of two passive modules, one exposed to the total space environment on the Leading Edge (RAM) and another exposed to the relative wake of the Trailing Edge. Evidence of atomic oxygen stimulated outgassing and the interrelated effects of the natural environment based on evaluation of the flight specimens will be discussed.

Linton, Roger C.↗

Innovative, Inexpensive Etching Technique Developed for Polymer Electro- Optical Structures

Electro-optic, polymer-based integrated optic devices for high-speed communication and computing applications offer potentially significant advantages over conventional inorganic electro-optic crystals. One key area of integrated optical technology--primary processing and fabrication--may particularly benefit from the use of polymer materials. However, as efforts concentrate on the miniaturization of electro-integrated circuit pattern geometries, the ability to etch fine features and smoothly sloped sidewalls is essential to make polymers useful for electro-integrated circuit applications. There are many existing processes available to etch polymer materials, but they all yield nearly vertical sidewalls. Vertical sidewalls are too difficult to reliably cover with a metal layer, and incomplete metalization degrades microwave performance, particularly at high frequency. However, obtaining a very sloped sidewall greatly improves the deposition of metal on the sidewall, leading to low-loss characteristics, which are essential to integrating these devices in highspeed electro-optic modulators. The NASA Lewis Research Center has developed in-house an inexpensive etching technique that uses a photolithography method followed by a simple, wet chemical etching process to etch through polymer layers. In addition to being simpler and inexpensive, this process can be used to fabricate smoothly sloped sidewalls by using a commercial none rodible mask: Spin-On-Glass. A commercial transparent material, Spin-On-Glass, uses processes and equipment similar to that for photoresist techniques.

Nguyen, Hung D.↗

BACKFLIP: A Comparison of Emerging Non-Fluoropolymer-Based, Co-Extruded PV Backsheets to Industry-Benchmark Technologies

As the photovoltaic (PV) industry is rapidly expanding around the world, there has been an increasing interest in extending the lifespan of PV modules. Concern has also emerged regarding the recyclability of modules and their component materials, including fluoropolymer-based backsheets. Laminated polyethylene-terephthalate (PET) core backsheets have traditionally been used in the PV industry, but new, co-extruded polyolefin (PO) backsheets show promise as an improved alternative. Mini-module and coupon samples of seven different backsheets (made of layers including contemporary PET and fluoropolymers, novel PO, and polyamide (PA) materials) were run through hygrometric- or UV photolytic-accelerated aging to identify and better understand each material’s degradation modes and the backsheets’ field reliability. In addition to the artificial aging, the natural weathering methods used in this study are described. The comprehensive set of chemical, mechanical, and structural characterizations at intermittent read points in this study is presented, including: visual appearance and color; gloss; mechanical tensile testing; I-V performance; electroluminescence (EL) imaging; dielectric breakdown; FTIR-chemical structure; X-ray-polymer structure (WAXS); and DSC-crystalline content. After 4000 h of aging, a strong correlation occurs between initial physical characteristics (mechanical tensile test) and operating performance (EL and I-V characteristics).

41 EE - Solar Energy Technologies Office (EE-4S)↗

BACKFLIP: A Comparison of Emerging Non-Fluoropolymer-Based, Co-Extruded PV Backsheets to Industry-Benchmark Technologies

As the photovoltaic (PV) industry is rapidly expanding around the world, there has been an increasing interest in extending the lifespan of PV modules. Concern has also emerged regarding the recyclability of modules and their component materials, including fluoropolymer-based backsheets. Laminated polyethylene-terephthalate (PET) core backsheets have traditionally been used in the PV industry, but new, co-extruded polyolefin (PO) backsheets show promise as an improved alternative. Mini-module and coupon samples of seven different backsheets (made of layers including contemporary PET and fluoropolymers, novel PO, and polyamide (PA) materials) were run through hygrometric- or UV photolytic-accelerated aging to identify and better understand each material's degradation modes and the backsheets' field reliability. In addition to the artificial aging, the natural weathering methods used in this study are described. The comprehensive set of chemical, mechanical, and structural characterizations at intermittent read points in this study is presented, including: visual appearance and color; gloss; mechanical tensile testing; I-V performance; electroluminescence (EL) imaging; dielectric breakdown; FTIR-chemical structure; X-ray-polymer structure (WAXS); and DSC-crystalline content. After 4000 h of aging, a strong correlation occurs between initial physical characteristics (mechanical tensile test) and operating performance (EL and I-V characteristics). This presentation focuses on gloss, FTIR, and breakdown voltage measurements. Results for MiMo power, grayness from EL imaging, optical micrscopy, and specimen morphology (on extraction when cut from MiMos) is also presented.

backsheet↗

TCCR Operational Summary and Optimization for Tank 9 Processing - 20314

Savannah River Remediation (SRR) manages and operates the liquid waste facilities at Savannah River Site (SRS) for the Department of Energy (DOE). Stored liquid waste is a complex mixture of insoluble solids (sludge) and soluble salts in an alkaline solution. SRR has deployed the Tank Closure Cesium Removal (TCCR) system, a tank-side ion exchange process, to remove radioactive cesium from salt waste and enable onsite disposal of the resulting decontaminated salt solution as low-level waste at the Saltstone facilities. The TCCR system consists of two prefilters, four ion exchange (IX) columns, one resin trap, and a ventilation system. The IX process uses a form of inorganic crystalline silicotitanate (CST), which has a high affinity for cesium and other alkali metals, strontium, and actinides. This process is currently deployed utilizing salt feed from Tank 10, with future plans to dissolve solid salt in Tank 9 and transfer the salt solution to Tank 10 for processing through TCCR. The feed for TCCR must be created from salt-cake in Tank 10 through a dissolution process. Once enough salt has been dissolved, a qualification process is entered. This process characterizes the feed and ensures the cesium loading on the columns will not cause boiling of waste within the columns during or after processing. Once the batch has been qualified, salt waste is fed to the TCCR system through a transfer pump in the center of the tank. The waste is filtered through a set of two shielded, dead-end prefilters that prevent solids buildup in the columns. The filtered salt solution then travels to the shielded IX columns, which can be operated individually or in series, where the cesium is sorbed on the CST media. The decontaminated salt solution (DSS) then travels through a resin trap and out of the module to Tank 11. TCCR has successfully processed approximately 795,000 L of Tank 10H radioactive salt waste over two batches to date. There has not yet been a system induced shutdown. The prefilters performed as expected with only minor degradation in recovery of differential pressure after a backflush sequence. The time between backflushes decreased as each batch reached the end of processing. The hydraulics in the IXCs mostly performed as expected at all flow rates, except for one IXC that will be further investigated during Batch 3 processing. The TCCR system has shown some opportunities for more efficient processing during the length of the demonstration so far. For future processing of material from Tank 9H through Tank 10H and the TCCR unit, TCCR 1A will implement changes to the prefilters and the IXCs. The prefilters will have an increased surface area and a new filter media in an effort to increase time between filter swaps and improve backwashing cleaning capability. The IXCs will have a reduced diameter to allow for increased heat transfer out of the column and increased loading of Cs-137. Additionally, a new form of CST with an increased kinetic performance is being investigated for use during TCCR 1A operation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Gene family expansions and transcriptome signatures uncover fungal adaptations to wood decay

Because they comprise some of the most efficient wood-decayers, Polyporales fungi impact carbon cycling in forest environment. Despite continuous discoveries on the enzymatic machinery involved in wood decomposition, the vision on their evolutionary adaptation to wood decay and genome diversity remains incomplete. We combined the genome sequence information from 50 Polyporales species, including 26 newly sequenced genomes and sought for genomic and functional adaptations to wood decay through the analysis of genome composition and transcriptome responses to different carbon sources. The genomes of Polyporales from different phylogenetic clades showed poor conservation in macrosynteny, indicative of genome rearrangements. We observed different gene family expansion/contraction histories for plant cell wall degrading enzymes in core polyporoids and phlebioids and captured expansions for genes involved in signalling and regulation in the lineages of white rotters. Furthermore, we identified conserved cupredoxins, thaumatin-like proteins and lytic polysaccharide monooxygenases with a yet uncharacterized appended module as new candidate players in wood decomposition. Given the current need for enzymatic toolkits dedicated to the transformation of renewable carbon sources, the observed genomic diversity among Polyporales strengthens the relevance of mining Polyporales biodiversity to understand the molecular mechanisms of wood decay.

59 BASIC BIOLOGICAL SCIENCES↗

A Multiomic Approach to Understand How Pleurotus eryngii Transforms Non-Woody Lignocellulosic Material

Pleurotus eryngii is a grassland-inhabiting fungus of biotechnological interest due to its ability to colonize non-woody lignocellulosic material. Genomic, transcriptomic, exoproteomic, and metabolomic analyses were combined to explain the enzymatic aspects underlaying wheat–straw transformation. Up-regulated and constitutive glycoside–hydrolases, polysaccharide–lyases, and carbohydrate–esterases active on polysaccharides, laccases active on lignin, and a surprisingly high amount of constitutive/inducible aryl–alcohol oxidases (AAOs) constituted the suite of extracellular enzymes at early fungal growth. Higher enzyme diversity and abundance characterized the longer-term growth, with an array of oxidoreductases involved in depolymerization of both cellulose and lignin, which were often up-regulated since initial growth. These oxidative enzymes included lytic polysaccharide monooxygenases (LPMOs) acting on crystalline polysaccharides, cellobiose dehydrogenase involved in LPMO activation, and ligninolytic peroxidases (mainly manganese-oxidizing peroxidases), together with highly abundant H2O2-producing AAOs. Interestingly, some of the most relevant enzymes acting on polysaccharides were appended to a cellulose-binding module. This is potentially related to the non-woody habitat of P. eryngii (in contrast to the wood habitat of many basidiomycetes). Additionally, insights into the intracellular catabolism of aromatic compounds, which is a neglected area of study in lignin degradation by basidiomycetes, were also provided. The multiomic approach reveals that although non-woody decay does not result in dramatic modifications, as revealed by detailed 2D-NMR and other analyses, it implies activation of the complete set of hydrolytic and oxidative enzymes characterizing lignocellulose-decaying basidiomycetes.

59 BASIC BIOLOGICAL SCIENCES↗

The status of lightweight photovoltaic space array technology based on amorphous silicon solar cells

Ultralight, flexible photovoltaic (PV) array of amorphous silicon (a-Si) was identified as a potential low cost power source for small satellites. A survey was conducted of the status of the a-Si PV array technology with respect to present and future performance, availability, cost, and risks. For existing, experimental array blankets made of commercial cell material, utilizing metal foil substrates, the Beginning of Life (BOL) performance at Air Mass Zero (AM0) and 35 C includes total power up to 200 W, power per area of 64 W/sq m and power per weight of 258 W/kg. Doubling of power per weight occurs when polyimide substrates are used. Estimated End of Life (EOL) power output after 10 years in a nominal low earth orbit would be 80 pct. of BOL, the degradation being due to largely light induced effects (-10 to -15 pct.) and in part (-5 pct.) to space radiation. Predictions for the year 1995 for flexible PV arrays, made on the basis of published results for rigid a-Si modules, indicate EOL power output per area and per weight of 105 W/sq m and 400 W/kg, respectively, while predictions for the late 1990s based on existing U.S. national PV program goals indicate EOL values of 157 W/sq m and 600 W/kg. Cost estimates by vendors for 200 W ultralight arrays in volume of over 1000 units range from $100/watt to $125/watt. Identified risks include the lack of flexible, space compatible encapsulant, the lack of space qualification effort, recent partial or full acquisitions of US manufacturers of a-Si cells by foreign firms, and the absence of a national commitment for a long range development program toward developing of this important power source for space.

Hanak, Joseph J.↗

CeO2 Nanoparticle Doping as a Probe of Active Site Speciation in the Catalytic Hydrolysis of Organophosphates

Organophosphate hydrolysis is important for degrading environmentally harmful compounds and recovering phosphate ions in biological molecules. CeO2 nanocrystals have been well-studied for dephosphorylation via hydrolysis owing to the accessible and tunable distribution of Ce3+ and Ce4+ ions. However, there remains uncertainty in the literature regarding which surface defect properties direct catalytic activity, such as the Ce3+/Ce4+ distribution, oxygen vacancies, faceting, and dopants, and to what degree they contribute to efficient hydrolysis. Trivalent (M3+) dopants serve as a tool for manipulating defects, including the concentration of Ce3+ and oxygen vacancies, thereby influencing the hydrolytic activity of CeO2. Herein, trivalent metal ions (M = Y3+, Cr3+, In3+, and Gd3+) were employed to modulate the active sites on the CeO2 nanocrystal surface, and the effects of each metal dopant on the cerium oxide active sites for organophosphate hydrolysis were investigated. M-doped CeO2 nanoparticles were synthesized via hydrothermal methods, followed by annealing to remove ligands and prime the nanocrystal surface for catalysis. Catalytic performance was evaluated using dimethyl-p¬-nitrophenyl phosphate (DMNP) as a model organophosphate substrate, with degradation monitored over time using UV-visible absorption spectroscopy. Powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy revealed successful doping of CeO2 in all cases, albeit with distinctive characteristics demonstrating how M3+ dopants affect catalysis. We show that CeO2 exhibits high sensitivity to dopants that generate lattice strain, Ce3+ ions, and oxygen vacancy defects. Consequently, achieving high catalytic efficiency within CeO2 requires a balanced active site ensemble, wherein defects are maintained at optimal concentrations and distributions on the nanocrystal surface.

Miura-Stempel, Emily L.↗

Influence of the Bulk Resistivity on Silicon Heterojunction Solar Cells and Module Reliability

Recent developments in industry on surface passivation open the possibility of using less doped substrates in silicon solar cells. In this report we investigate how the bulk resistivity affects the performance of silicon cells and the reliability of modules. Herein, n- and p-type silicon heterojunction cells with bulk resistivities between 3 and 15 000 Ωcm are studied. We measure the current–voltage characteristics of n-type cells across the resistivity range, and we find comparable responses to illumination intensities between 0.1 and 1 suns. The cells with bulk resistivities over 1000 Ωcm show breakdown voltages larger than -1000 V, almost two orders of magnitude higher than in typical commercial cells. Although modules have bypass-diodes to prevent cells from going into breakdown, higher breakdown voltages can improve the reliability of modules in case of bypass-diode failure and reduce the module cost by easing the number of bypass-diodes required. Finally, the cells have been submitted to light soaking. The float-zone p-type cells with bulk resistivities over 10 000 Ωcm are less sensitive to light-induced degradation than cells with bulk resistivities below 10 Ωcm. The former show to recover few hours after light soaking, while the latter recover only after dark annealing.

14 SOLAR ENERGY↗

Anion Exchange of Ruddlesden–Popper Lead Halide Perovskites Produces Stable Lateral Heterostructures

Heterostructures of three-dimensional (3D) halide perovskites are unstable because of facile anion interdiffusion at halide interfaces. Two-dimensional (2D) Ruddlesden–Popper halide perovskites (RPPs) show suppressed and anisotropic ion diffu-sion that could enable stable RPP heterostructures, yet the direct and general growth of lateral RPP heterostructures remains challenging. Here we show that halide miscibility in RPPs decreases with perovskite layer thickness (n), enabling the for-mation of sharp halide lateral heterostructures from n = 1 and 2 RP lead iodide microplates via anion exchange with hydro-gen bromide vapor. In contrast, RPPs with n = 3 form more diffuse lateral heterojunctions, more similar to those in 3D perov-skites. The anion exchange behaviors are further modulated by the spacer and A-site cations in the RPP structures. These new insights, and kinetic studies of the exchange reactions, enable the preparation of lateral heterostructures from various n = 2 RPPs that are more stable against anion interdiffusion and degradation for potential device applications.

Roy, Chris R.↗