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At least 91 records · Page 5

In situ investigation of the formation and metastability of formamidinium lead tri-iodide perovskite solar cells

Organic–inorganic perovskites have emerged as an important class of next generation solar cells due to their remarkably low cost, band gap, and sub-900 nm absorption onset. Here, we show a series of in situ observations inside electron microscopes and X-ray diffractometers under device-relevant synthesis conditions focused on revealing the crystallization process of the formamidinium lead-triiodide perovskite at the optimum temperature of 175 °C. Direct in situ observations of the structure and chemistry over relevant spatial, temporal, and temperature scales enabled identification of key perovskite formation and degradation mechanisms related to grain evolution and interface chemistry. The lead composition was observed to fluctuate at grain boundaries, indicating a mobile lead-containing species, a process found to be partially reversible at a key temperature of 175 °C. Using low energy electron microscopy and valence electron energy loss spectroscopy, lead is found to be bonded in the grain interior with iodine in a tetrahedral configuration. At the grain boundaries, the binding energy associated with lead is consequently shifted by nearly 2 eV and a doublet peak is resolved due presumably to a greater degree of hybridization and the potential for several different bonding configurations. At the grain boundaries there is adsorption of hydrogen and OH¯ ions as a result of residual water vapor trapped as a non-crystalline material during formation. Lastly, insights into the relevant formation and decomposition reactions of formamidinium lead iodide at low to high temperatures, observed metastabilities, and relationship with the photovoltaic performance were obtained and used to optimize device processing resulting in conversion efficiencies of up to 17.09% within the stability period of the devices.

14 SOLAR ENERGY↗

Plasma-gun-assisted field-reversed configuration formation in a conical θ-pinch

We show through injection of plasma via an annular array of coaxial plasma guns, during the pre-ionization phase of field-reversed configuration (FRC) formation how to catalyze the bulk ionization of a neutral gas prefill in the presence of a strong axial magnetic field and change the character of outward flux flow during field-reversal from a convective process to a much slower resistive diffusion process. Our approach has been found to significantly improve FRC formation in a conical θ-pinch, resulting in a ~350% increase in trapped flux at typical operating conditions, an expansion of accessible formation parameter space to lower densities and higher temperatures, and a reduction or elimination of several deleterious effects associated with the pre-ionization phase.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Jet formation in cerium metal to examine material strength

Examining the evolution of material properties at extreme conditions advances our understanding of numerous high-pressure phenomena from natural events like meteorite impacts to general solid mechanics and fluid flow behavior. Recent advances in synchrotron diagnostics coupled with dynamic compression platforms have introduced new possibilities for examining in-situ, spatially resolved material response with nanosecond time resolution. In this work, we examined jet formation from a Richtmyer-Meshkov instability in cerium initially shocked into a transient, high-pressure phase, and then released to a low-pressure, higher-temperature state. Cerium's rich phase diagram allows us to study the yield stress following a shock induced solid-solid phase transition. X-ray imaging was used to obtain images of jet formation and evolution with 2–3 μm spatial resolution. From these images, an analytic method was used to estimate the post-shock yield stress, and these results were compared to continuum calculations that incorporated an experimentally validated equation-of-state (EOS) for cerium coupled with a deviatoric strength model. Reasonable agreement was observed between the calculations and the data illustrating the sensitivity of jet formation on the yield stress values. The data and analysis shown here provide insight into material strength during dynamic loading which is expected to aid in the development of strength aware multi-phase EOS required to predict the response of matter at extreme conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

In-situ synchrotron micro-diffraction study of surface, interface, grain structure, and strain/stress evolution during Sn whisker/hillock formation

We have performed X-ray synchrotron micro-diffraction measurements to study the processes controlling the formation of hillocks and whiskers in Sn layers on Cu. The studies were done in real-time on Sn layers that were electro-deposited immediately before the X-ray measurements were started. This enabled a region of the sample to be monitored from the as-deposited state until after a hillock feature formed. In addition to measuring the grain orientation and deviatoric strain (via Laue diffraction), the X-ray fluorescence was monitored to quantify the evolution of the Sn surface morphology and the formation of intermetallic compound (IMC) at the Sn-Cu interface. The results capture the simultaneous growth of the feature and the corresponding film stress, grain orientation, and IMC formation. The observations are compared with proposed mechanisms for whisker/hillock growth and nucleation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Plume dynamics and gas-phase molecular formation in transient laser-produced uranium plasmas

The dynamics of expansion, thermodynamics, and chemical reactions in laser-produced plasmas is of general interest for all laser ablation applications. This study investigates the complex morphology and behavior of reactive species in nanosecond laser-produced uranium plasmas. Comparing plasma morphology in various inert and reactive ambient gases provides information about the role of gas-phase chemistry in plume hydrodynamics. Background gases including nitrogen and argon foster collisional interactions leading to more significant plume confinement and the increase in persistence of uranium species. On the other hand, environments containing reactive gases such as oxygen promote chemical reactions between the plasma and ambient species. By comparing the expansion dynamics of uranium plumes in nitrogen, air, and argon, we discover that chemical reactions modify the hydrodynamics of the plume at later times of its evolution in the air background. Furthermore, we observe that varying the concentration of oxygen in the fill gas promotes different reaction pathways that lead to the formation of uranium oxides. The reaction pathways from atoms to diatomic to polyatomic molecules strongly vary with ambient oxygen concentration. Lower oxygen concentrations enhance the formation of uranium monoxide from atomic uranium, whereas higher oxygen concentrations tend to depopulate both atomic uranium and uranium monoxide concentrations through the formation of more complex uranium oxides.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

THE STAR FORMATION HISTORY OF BCGs TO z = 1.8 FROM THE SpARCS/SWIRE SURVEY: EVIDENCE FOR SIGNIFICANT IN SITU STAR FORMATION AT HIGH REDSHIFT

We present the results of an MIPS-24 μm study of the brightest cluster galaxies (BCGs) of 535 high-redshift galaxy clusters. The clusters are drawn from the Spitzer Adaptation of the Red-Sequence Cluster Survey, which effectively provides a sample selected on total stellar mass, over 0.2 < z < 1.8 within the Spitzer Wide-Area Infrared Extragalactic (SWIRE) Survey fields. Twenty percent, or 106 clusters, have spectroscopically confirmed redshifts, and the rest have redshifts estimated from the color of their red sequence. A comparison with the public SWIRE images detects 125 individual BCGs at 24 μm ≳ 100 μJy, or 23%. The luminosity-limited detection rate of BCGs in similar richness clusters (N{sub gal} > 12) increases rapidly with redshift. Above z ∼ 1, an average of ∼20% of the sample have 24 μm inferred infrared luminosities of L{sub IR} > 10{sup 12} L{sub ⊙}, while the fraction below z ∼ 1 exhibiting such luminosities is <1%. The Spitzer-IRAC colors indicate the bulk of the 24 μm detected population is predominantly powered by star formation, with only 7/125 galaxies lying within the color region inhabited by active galactic nuclei (AGNs). Simple arguments limit the star formation activity to several hundred million years and this may therefore be indicative of the timescale for AGN feedback to halt the star formation. Below redshift z ∼ 1, there is not enough star formation to significantly contribute to the overall stellar mass of the BCG population, and therefore BCG growth is likely dominated by dry mergers. Above z ∼ 1, however, the inferred star formation would double the stellar mass of the BCGs and is comparable to the mass assembly predicted by simulations through dry mergers. We cannot yet constrain the process driving the star formation for the overall sample, though a single object studied in detail is consistent with a gas-rich merger.

79 ASTRONOMY AND ASTROPHYSICS↗

LOW TEMPERATURE FORMATION OF NITROGEN-SUBSTITUTED POLYCYCLIC AROMATIC HYDROCARBONS (PANHs)—BARRIERLESS ROUTES TO DIHYDRO(iso)QUINOLINES

Meteorites contain bio-relevant molecules such as vitamins and nucleobases, which consist of aromatic structures with embedded nitrogen atoms. Questions remain over the chemical mechanisms responsible for the formation of nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) in extraterrestrial environments. By exploiting single collision conditions, we show that a radical mediated bimolecular collision between pyridyl radicals and 1,3-butadiene in the gas phase forms nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) 1,4-dihydroquinoline and to a minor amount 1,4-dihydroisoquinoline. The reaction proceeds through the formation of a van der Waals complex, which circumnavigates the entrance barrier implying it can operate at very low kinetic energy and therefore at low temperatures of 10 K as present in cold molecular clouds such as TMC-1. The discovery of facile de facto barrierless exoergic reaction mechanisms leading to PANH formation could play an important role in providing a population of aromatic structures upon which further photo-processing of ice condensates could occur to form nucleobases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Band Energy Dependence of Defect Formation in the Topological Semimetal Cd3As2

Cadmium Arsenide (Cd3As2) is a prototypical Dirac semimetal that manifests topological properties in a 3D bulk material. In defect-free Cd3As2, the Fermi level lies at a minimum in the density of states at the Dirac point, but experimentally it forms with excess electron carriers and an elevated EF, thereby masking the topological features. To computationally study the self-doping of Cd3As2, we combine density functional theory (DFT) calculations for defect formation energies with quasi-particle self-consistent GW (QSGW) electronic structure calculations. We demonstrate an innate dependence of the point defect formation energies on carrier concentrations and use the QSGW calculated density of states to extrapolate formation energies to arbitrary electron concentrations. This approach allows the quantitative modeling of thermodynamic defect equilibria in topological semimetals and is used to predict how Cd3As2 growth conditions affect the position of EF relative to the Dirac point.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗

A Novel Resilience-Oriented Cellular Grid Formation Approach for Distribution Systems with Behind-the-Meter Distributed Energy Resources

This paper presents a resilience-oriented cellular grid formation approach to achieve scalable and reconfigurable community microgrid operations for distribution systems with behind-the-meter distributed energy resources. A set of interconnected solar photovoltaics, energy storage systems, and load is termed as a cell, implying a subset of the grid that can operate independently using its own resources. Cells are identified such that each cell inherently has sufficient energy resources to black start and can provide a certain level of backup power for its load under the loss of utility power supply. The proposed cell formation approach builds on a unique self-organizing map-based method (SomRes) to quantify a system's resilience. Using SomRes and a non-dominated sorting-based genetic algorithm (NSGA-II), a fast and efficient cell formation algorithm is developed to identify cells in a distribution system that are resilient against extreme events. The efficacy of the proposed approach is demonstrated on a numerical model of a real distribution feeder in Colorado, United States.

distributed energy resource↗

GMC Collisions as Triggers of Star Formation. III. Density and Magnetically Regulated Star Formation

We study giant molecular cloud (GMC) collisions and their ability to trigger star cluster formation. We further develop our three-dimensional magnetized, turbulent, colliding GMC simulations by implementing star formation subgrid models. Two such models are explored: (1) “Density-Regulated,” i.e., fixed efficiency per free-fall time above a set density threshold and (2) “Magnetically Regulated,” i.e., fixed efficiency per free-fall time in regions that are magnetically supercritical. Variations of parameters associated with these models are also explored. In the non-colliding simulations, the overall level of star formation is sensitive to model parameter choices that relate to effective density thresholds. In the GMC collision simulations, the final star formation rates and efficiencies are relatively independent of these parameters. Between the non-colliding and colliding cases, we compare the morphologies of the resulting star clusters, properties of star-forming gas, time evolution of the star formation rate (SFR), spatial clustering of the stars, and resulting kinematics of the stars in comparison to the natal gas. We find that typical collisions, by creating larger amounts of dense gas, trigger earlier and enhanced star formation, resulting in 10 times higher SFRs and efficiencies. The star clusters formed from GMC collisions show greater spatial substructure and more disturbed kinematics.

79 ASTRONOMY AND ASTROPHYSICS↗

Blob Formation and Ejection in Coronal Jets due to the Plasmoid and Kelvin–Helmholtz Instabilities

We perform 2D resistive magnetohydrodynamic simulations of coronal jets driven by flux emergence along the lower boundary. The reconnection layers are susceptible to the formation of blobs that are ejected in the jet. Our simulation with low plasma β (Case I) shows that magnetic islands form easily and propagate upward in the jet. These islands are multithermal and thus are predicted to show up in hot channels (335 Å and 211 Å) and the cool channel (304 Å) in observations by the Atmospheric Imaging Assembly (AIA) on the Solar Dynamics Observatory . The islands have maximum temperatures of 8 MK, lifetimes of 120 s, diameters of 6 Mm, and velocities of 200 km s{sup −1}. These parameters are similar to the properties of blobs observed in extreme-ultraviolet (EUV) jets by AIA. The Kelvin–Helmholtz instability develops in our simulation with moderately high plasma β (Case II) and leads to the formation of bright vortex-like blobs above the multiple high magnetosonic Mach number regions that appear along the jet. These vortex-like blobs can also be identified in the AIA channels. However, they eventually move downward and disappear after the high magnetosonic Mach number regions disappear. In the lower plasma β case, the lifetime for the jet is shorter, the jet and magnetic islands are formed with higher velocities and temperatures, the current-sheet fragments are more chaotic, and more magnetic islands are generated. Our results show that the plasmoid instability and Kelvin–Helmholtz instability along the jet are both possible causes of the formation of blobs observed at EUV wavelengths.

79 ASTRONOMY AND ASTROPHYSICS↗

Precision Formation Keeping at L2 Using the Autonomous Formation Flying Sensor

Recent advances in formation keeping for large numbers of spacecraft using the Autonomous Formation Flying are presented. This sensor, currently under development at JPL, has been identified as a key component in future formation flying spacecraft missions. The sensor provides accurate range and bearing measurements between pairs of spacecraft using GPS technology. Previous theoretical work by the authors has focused on developing a decentralized scheduling algorithm to control the tasking of such a sensor between the relative range and bearing measurements to each node in the formation. The resulting algorithm has been modified to include switching constraints in the sensor. This paper also presents a testbed for real time validation of a sixteen-node formation based on the Stellar Imager mission. Key aspects of the simulation include minimum fuel maneuvers based on free-body dynamics and a three body propagator for simulating the formation at L2.

McLoughlin, Terence H.↗

Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

Sutter, B.↗

Smectite Formation in the Presence of Sulfuric Acid: Implications for Acidic Smectite Formation on Early Mars

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (approximately 200 degC). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH less than or equal to 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH approximately 3 and trioctahedral smectite saponite at final pH approximately 4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Smectite↗

Synthesis and structural characterization of 2,2’-bipyridine zinc formate: Analysis of formate bonding and hydrosilylation of CO 2 and carbonyl compounds

The zinc formate compound (bipy)Zn(O 2 CH) 2 is obtained via the reaction of Zn(O 2 CH) 2 with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O 2 CH) 2 may be formed from zinc hydride via addition of bipy followed by addition of (i) HCO 2 H and (ii) CO 2 . The molecular structure of (bipy)Zn(O 2 CH) 2 has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and monodentate formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O 2 CH) 2 participates in hydrosilylation transformations involving CO 2 and carbonyl compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Methods for Assessing Kinetic Factors in the Reduction of CO 2 to Formate: Implications for Improving Electrocatalyst Design

hermochemical insights are often employed in the rationalization of reactivity and in the design of electrocatalysts for CO 2 reduction reactions targeting C–H bond-containing products. This work identifies experimental methods for assessing kinetic aspects of reactivity. These methods are illustrated using [Fe 4 N(CO) 12 ] - , which produces formate from CO 2 at -1.2 V versus SCE in either a MeCN/H 2 O solvent (95:5) or pH 6.5 buffered water. Elementary rates for each reaction step are identified along with the rate-determining step (RDS) as C–H bond formation. Transition state kinetics were determined from an Eyring analysis for the rate-determining C–H bond formation step using temperature-dependent electrochemical measurements. A lower measured Δ G ‡ (298 K, 12.3 ± 0.1 kcal mol –1 ) in a pH 6.5 aqueous solution, compared with a Δ G ‡ (298 K) of 15.0 ± 0.1 kcal mol –1 in a MeCN/H 2 O solvent (95:5), correlates with faster observed reaction rates and provides a kinetic rationalization for the solvent-dependent chemistry. Taken together, the experimentally determined kinetic insights highlight that enhancement of the local concentration of CO 2 at catalyst–hydride sites should be a primary focus of ongoing catalyst design. This will both enhance reaction rates and increase selectivity for C–H bond formation over competing H–H bond formation, because that step is fast in H 2 evolution reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New Particle Formation and Growth in an Isoprene-Dominated Ozark Forest: From Sub-5 nm to CCN-Active Sizes

Particle Investigations at a Northern Ozarks Tower: NOx, Oxidant, Isoprene Research (PINOT-NOIR) were conducted in a Missouri forest dominated by isoprene emissions, from May to October 2012. This study presents results of new particle formation (NPF) and the growth of new particles to cloud condensation nuclei (CCN)-active sizes (~100 nm) observed from this field campaign. The measured sub-5 nm particles were up to ~20000 cm-3 during a typical NPF event. Nucleation rates J1 were relatively high (11.0±10.6 cm-3s-1), and one order of magnitude higher than formation rates of 5 nm particles (J5). Sub-5 nm particle events were observed on 64% of the measurement days, with a high preference in biogenic volatile organic compounds (BVOCs)- and SO2-poor northwesterly (90%) air masses than in BVOCs-rich southerly air masses (13%). About 80% of sub-5 nm particle events led to the further growth. While high temperatures and high aerosol loadings in the southerly air masses were not favorable for nucleation, high BVOCs in the southerly air masses facilitated the growth of new particles to CCN-active sizes. In overall, 0.4-9.4% of the sub-5 nm particles grew to CCN-active sizes within a NPF event. During a regional NPF event period that took place consecutively over several days, concentrations of CCN size particles increased by a factor of 5 in average. This enhanced production of CCN particles from new particles was commonly observed during all 13 regional NPF events observed during the campaign.

cloud condensation nuclei, isoprene, BVOC↗

Star Formation Histories from Spectral Energy Distributions and Color–magnitude Diagrams Agree: Evidence for Synchronized Star Formation in Local Volume Dwarf Galaxies over the Past 3 Gyr

Star formation histories (SFHs) reveal physical processes that influence how galaxies form their stellar mass. We compare the SFHs of a sample of 36 nearby (D ≲ 4 Mpc) dwarf galaxies from the ACS Nearby Galaxy Survey Treasury (ANGST), inferred from the color–magnitude diagrams (CMDs) of individually resolved stars in these galaxies, with those reconstructed by broadband spectral energy distribution (SED) fitting using the dense basis SED-fitting code. When comparing individual SFHs, we introduce metrics for evaluating SFH reconstruction techniques. For both the SED and CMD methods, the median normalized SFH of galaxies in the sample shows a period of quiescence at lookback times of 3–6 Gyr followed by rejuvenated star formation over the past 3 Gyr that remains active until the present day. To determine if these represent special epochs of star formation in the D <4 Mpc portion of the Local Volume, we break this ANGST dwarf galaxy sample into subsets based on specific star formation rate and spatial location. Modulo offsets between the methods of about 1 Gyr, all subsets show significant decreases and increases in their median normalized SFHs at the same epochs, and the majority of the individual galaxy SFHs are consistent with these trends. These results motivate further study of potential synchronized star formation quiescence and rejuvenation in the Local Volume as well as development of a hybrid method of SFH reconstruction that combines CMDs and SEDs, which have complementary systematics.

79 ASTRONOMY AND ASTROPHYSICS↗