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At least 1,081 records · Page 60

Bromine Incorporation and Suppressed Cation Rotation in Mixed-Halide Perovskites

Engineering the composition of perovskite active layers has been critical in increasing the efficiency of perovskite solar cells (PSCs) to more than 25% in the latest reports. Partial substitutions of the monovalent cation and the halogen have been adopted in the highest-performing devices, but the precise role of bromine incorporation remains incompletely explained. Here we use quasi-elastic neutron scattering (QENS) to study, as a function of the degree of bromine incorporation, the dynamics of organic cations in triple-cation lead mixed-halide perovskites. We find that the inclusion of bromine suppresses low-energy rotations of formamidinium (FA), and we find that inhibiting FA rotation correlates with a longer-lived carrier lifetime. When the fraction of bromine approaches 0.15 on the halogen site—a composition used extensively in the PSC literature—the fraction of actively rotating FA molecules is minimized: indeed, the fraction of rotating FA is suppressed by more than 25% compared to the bromine-free perovskite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preface for frontiers of magnetic reconnection research in heliophysical, astrophysical, and laboratory plasmas

Magnetic reconnection—the topological rearrangement of magnetic field—underlies many explosive phenomena across a wide range of natural and laboratory plasmas.3 It plays a pivotal role in electron and ion heating, particle acceleration to high energies, energy transport, and self-organization. Reconnection can have a complex relationship with turbulence at both large and small scales, leading to various effects that are only beginning to be understood. In heliophysics, magnetic reconnection plays a key role in solar flares, coronal mass ejections, coronal heating, solar wind dissipation, the interaction of interplanetary plasma with magnetospheres, dynamics of planetary magnetospheres such as magnetic substorms, and the heliospheric boundary with the interstellar medium. Here, the magnetic reconnection is integral to the solar and planetary dynamo processes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Excited State Dynamics of a Conformationally Fluxional Copper Coordination Complex

The conversion of solar energy into chemical fuel represents a capstone goal of the 21st century and has the potential to supply terawatts of power in a globally distributed manner. However, the disparate time scales of photodriven charge separation (~fs) and steps in chemical reactions (~μs) represent an inherent bottleneck in solar-to-fuels technology. Here to address this discrepancy, we are developing earth-abundant coordination complexes that undergo light-induced conformational rearrangements such that charge separation (CS) is hastened, while charge recombination (CR) is slowed. To these ends, we report the preparation and characterization of a new series of conformationally fluxional copper coordination complexes that contain a twisted intramolecular charge transfer (TICT) fluorophore as part of their ligand scaffold. Structural and spectroscopic characterization of the Cu(I) and Cu(II) complexes formed with these ligands in their ground states establish oxidation state-dependent conformational dynamicity, while time-resolved emission and transient absorption spectroscopies define the photopysical parameters of photo-induced excited states. Building on initial reports with a related set of molecules, the improved ligand design presented here greatly simplifies the observed photophysics, effectively shutting down unwanted ligand-centered excited states previously observed. Finally, time-dependent density functional theory (TDDFT) analyses reveal an unusual metal-to-TICT electronic transition only reported once before, and though the formation of a CS state is not observed directly through experiments, TDDFT geometry optimizations in the excited states support the formation of transient Cu(II) CS species, lending credence to the potential success of our approach. These studies establish a clear model for the excited state dynamics at play in proof-of-concept systems and clarify key design parameters for future optimizations toward achieving long-lived CS via photoinduced conformational gating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stochastic modeling of sunshine number data

In this paper, we will present a unified statistical modeling framework for estimation and forecasting sunshine number (SSN) data. Sunshine number has been proposed earlier to describe sunshine time series in qualitative terms (Theor Appl Climatol 72 (2002) 127-136) and since then, it was shown to be useful not only for theoretical purposes but also for practical considerations, e.g. those related to the development of photovoltaic energy production. Statistical modeling and prediction of SSN as a binary time series has been challenging problem, however. Our statistical model for SSN time series is based on an underlying stochastic process formulation of Markov chain type. We will show how its transition probabilities can be efficiently estimated within logistic regression framework. In fact, our logistic Markovian model can be relatively easily fitted via maximum likelihood approach. This is optimal in many respects and it also enables us to use formalized statistical inference theory to obtain not only the point estimates of transition probabilities and their functions of interest, but also related uncertainties, as well as to test of various hypotheses of practical interest, etc. It is straightforward to deal with non-homogeneous transition probabilities in this framework. Very importantly from both physical and practical points of view, logistic Markov model class allows us to test hypotheses about how SSN dependents on various external covariates (e.g. elevation angle, solar time, etc.) and about details of the dynamic model (order and functional shape of the Markov kernel, etc.). Therefore, using generalized additive model approach (GAM), we can fit and compare models of various complexity which insist on keeping physical interpretation of the statistical model and its parts. After introducing the Markovian model and general approach for identification of its parameters, we will illustrate its use and performance on high resolution SSN data from the Solar Radiation Monitoring Station of the West University of Timisoara.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Solar neutrino measurements in Super-Kamiokande-IV

We report that upgraded electronics, improved water system dynamics, better calibration and analysis techniques allowed Super-Kamiokande-IV to clearly observe very low-energy B 8 solar neutrino interactions, with recoil electron kinetic energies as low as ~ 3.5 MeV . Super-Kamiokande-IV data-taking began in September of 2008; this paper includes data until February 2014, a total livetime of 1664 days. The measured solar neutrino flux is ( 2.308 ± 0.020 ( stat ) - 0.040 + 0.039 ( syst ) ) × 1 0 6 / ( cm 2 sec ) assuming no oscillations. The observed recoil electron energy spectrum is consistent with no distortions due to neutrino oscillations. An extended maximum likelihood fit to the amplitude of the expected solar zenith angle variation of the neutrino-electron elastic scattering rate in SK-IV results in a day/night asymmetry of ( - 3.6 ± 1.6 ( stat ) ± 0.6 ( syst ) ) % . The SK-IV solar neutrino data determine the solar mixing angle as sin 2 θ 12 = 0.327 - 0.031 + 0.026 , all SK solar data (SK-I, SK-II, SK III and SK-IV) measures this angle to be sin 2 θ 12 = 0.334 - 0.023 + 0.027 , the determined mass-squared splitting is Δ m 21 2 = 4.8 - 0.8 + 1.5 × 10 - 5 eV 2 .

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Solar wind conditions leading to efficient radiation belt electron acceleration: A superposed epoch analysis

In this study by determining preferential solar wind conditions leading to efficient radiation belt electron acceleration is crucial for predicting radiation belt electron dynamics. Using Van Allen Probes electron observations (>1 MeV) from 2012 to 2015, we identify a number of efficient and inefficient acceleration events separately to perform a superposed epoch analysis of the corresponding solar wind parameters and geomagnetic indices. By directly comparing efficient and inefficient acceleration events, we clearly show that prolonged southward Bz, high solar wind speed, and low dynamic pressure are critical for electron acceleration to >1 MeV energies in the heart of the outer radiation belt. We also evaluate chorus wave evolution using the superposed epoch analysis for the identified efficient and inefficient acceleration events and find that chorus wave intensity is much stronger and lasts longer during efficient electron acceleration events, supporting the scenario that chorus waves play a key role in MeV electron acceleration.

58 GEOSCIENCES↗

Formation trajectories of solution-processed perovskite thin films from mixed solvents

The engineering of mixed-solvent formulations and their evaporation conditions are key to reproducible perovskite coatings for high-performance photovoltaics. Here, we report a lumped-parameter evaporation model to predict the evolution of a perovskite ink liquid film over time (solvent ratio, solute concentration, and film thickness). The drying-rate model is validated via in situ film-thickness measurements, and the predicted transient liquid film state is mapped as a process path. These methods allow for the prediction of process sensitivity to local environmental factors and the understanding and visualization of a broader processing parameter space enabled through the coupling of process and ink engineering. Process maps are applied to create a new framework for scalable perovskite coating development with a goal of improving the reproducibility and transferability of perovskite fabrication. This approach is demonstrated with blade-coated FA 0.83 Cs 0.17 PbI 3 photovoltaic devices, improving the photovoltaic conversion efficiency from 17.5% ± 1.7% to 20.3% ± 0.6%.

14 SOLAR ENERGY↗

Quantifying Large Lattice Relaxations in Photovoltaic Devices

Temporal variations of Cu(In,Ga)Se 2 photovoltaic device properties during light exposure at various temperatures and voltage biases for times up to 100 h are analyzed using the kinetic theory of large lattice relaxations. Open-circuit voltage and p-type doping increased with charge injection and decreased with temperature at low injection conditions. Furthermore, lattice relaxation can account for both trends and activation energies extracted from the data are approximately 0.9 and 1.2 eV for devices with lower and higher sodium content, respectively. In these devices, increased sodium content resulted in higher initial p-type doping with greater stability. First-principles calculations providing revised activation energies for the (V Se -V Cu ) complex suggest that this defect does not account for the metastability observed here.

14 SOLAR ENERGY↗

Effect of Quartz Aperture Covers on the Fluid Dynamics and Thermal Efficiency of Falling Particle Receivers

Falling particle receivers are an emerging technology for use in concentrating solar power systems. In this paper, quartz half-shells are investigated for use as full or partial aperture covers to reduce receiver thermal losses. Quartz half-shell aperture covers offer the ability to minimally interfere with incoming solar radiation from the heliostat field while obstructing thermal radiation and advection from leaving the receiver cavity. The fluid dynamics and heat transfer of a receiver subdomain and surrounding air are modeled using ANSYS®FLUENT We compare the percentage of total incident solar power lost due to conduction through the receiver walls, advective losses through the aperture, and radiation exiting the aperture. Contrary to expected outcomes, results show that quartz aperture covers can increase radiative losses and result in modest to nonexistent reductions in advective losses. The increased radiative losses are driven by elevated quartz half-shell temperatures and have the potential to be mitigated by active cooling and/or material selection. Quartz half-shell total transmissivity was measured experimentally using a radiometer and the National Solar Thermal Test Facility heliostat field with values up to 0.97 ± 0.01. Quartz half-shell aperture covers did not yield expected efficiency gains in numerical results due to increased radiative losses, but efficiency improvement in some numerical results and the performance of quartz half-shells subject to concentrated solar radiation suggest that quartz half-shell aperture covers should be investigated further.

14 SOLAR ENERGY↗

Dynamics of Coronal Hole Boundaries

Remote and in situ observations strongly imply that the slow solar wind consists of plasma from the hot, closed-field corona that is released onto open magnetic field lines. The Separatrix Web theory for the slow wind proposes that photospheric motions at the scale of supergranules are responsible for generating dynamics at coronal-hole boundaries, which result in the closed plasma release. We use three-dimensional magnetohydrodynamic simulations to determine the effect of photospheric flows on the open and closed magnetic flux of a model corona with a dipole magnetic field and an isothermal solar wind. A rotational surface motion is used to approximate photospheric supergranular driving and is applied at the boundary between the coronal hole and helmet streamer. The resulting dynamics consist primarily of prolific and efficient interchange reconnection between open and closed flux. The magnetic flux near the coronal-hole boundary experiences multiple interchange events, with some flux interchanging over 50 times in one day. Additionally, we find that the interchange reconnection occurs all along the coronal-hole boundary and even produces a lasting change in magnetic-field connectivity in regions that were not driven by the applied motions. Our results show that these dynamics should be ubiquitous in the Sun and heliosphere. We discuss the implications of our simulations for understanding the observed properties of the slow solar wind, with particular focus on the global-scale consequences of interchange reconnection.

79 ASTRONOMY AND ASTROPHYSICS↗

Ruddlesden–Popper Perovskites with Narrow Phase Distribution for Air-Stable Solar Cells

2D Ruddlesden-Popper perovskites have risen to prominence as stable and efficient photovoltaic materials because of their structural diversity, rich photophysics, and low moisture ingression. However, thin films processed from stoichiometric precursor solutions possess a broad phase distribution of different number of inorganic layers with random crystal orientation, crippling device performance. The effect of methylammonium chloride (MACI) and 3-amino4-phenolsulfonic acid (APSA) on the fabrication of perpendicularly oriented (PEA) 2 MA 4 Pb 5 I 16 films with narrow phase distribution using antisolvent and hot-casting processing techniques is investigated. MACI plays a critical role in suppressing parasitic n ≤ 2 and 3D-like phases. APSA performs the dual function of trap passivation and further narrowing phase polydispersity through strong coordination with Pb 2+ . Ex situ grazing-incident wide-angle X-Ray scattering (GIWAXS) and ultrafast spectroscopic characterization reveal uniformly mixed-phase distribution with disordered orientation in antisolvent treated films, while additive-assisted hot-casting treatment results in oriented, reverse-graded phase distribution, i.e., small-n on the film surface and large-n at the bottom. Arising thin films enable efficient p-i-n solar cells with an efficiency of 14.34%, and a V oc of 1.20 V, retaining 96% initial efficiency after 1440 h under ambient conditions (RH = 50-60%) without encapsulation.

36 MATERIALS SCIENCE↗

Electronic and Vibrational Coherence in Heterogeneous Electron Transfer (Final Report)

Interfacial electron transfer reactions constitute key physical phenomena central to a variety of energy related transport and conversion processes such as catalysis, photocatalysis, photovoltaics, energy storage, molecular electronics, etc. Heterogeneous material systems like organic/inorganic interfaces are of particular interest because they provide great potential to tailor properties according to application specific requirements. While electron transfer dynamics has been studied intensively in heterogeneous systems many questions remain unanswered. The significance of electronic-vibrational coupling and coherence is one aspect that has yet to be fully explored. The objective of this project is to develop and implement new ultrafast spectroscopic techniques based on pump four-wave mixing spectroscopy (pump-FWM) for studying the dynamics of vibrational coupling and coherence in heterogeneous electron transfer (HET) at molecule/semiconductor interfaces. The implementation of the spectroscopic setup allows to explore different four-wave mixing techniques and thus to identify a suitable approach to study the significance of vibrational as well as electronic coherence in HET.

14 SOLAR ENERGY↗

As‐Doped Polycrystalline CdSeTe: Localized Defects, Carrier Mobility and Lifetimes, and Impact on High‐Efficiency Solar Cells

Abstract The efficiency potential for single‐junction photovoltaics (PV) is described by the detailed balance model, which requires the elimination of nonradiative recombination and perfect minority carrier collection. Improvements in GaAs, Si, and perovskite PV follow this model. It might be more complex for CdTe, a leading thin‐film PV technology. While lifetime, passivation, and doping goals for 25% efficient CdTe solar cells are largely reached, voltage is ≈20% below the detailed balance limit. Why is that? In Se‐alloyed CdSe x Te 1‐x (Se is required for >20% efficiency) additional losses can occur due to electrostatic and bandgap fluctuations and due to electronic trap states. To understand mechanisms limiting CdSeTe solar cell performance and to suggest improvements, carrier dynamics, and transport in CdSe x Te 1‐x with variation in Se composition and as doping is analyzed. It is shown that trapping, likely due to anion‐site defects and their complexes, is correlated with low charge carrier mobility of 0.1–0.6 cm 2 (Vs) −1 . Even with 1000 ns charge carrier lifetimes, carrier diffusion length is less than the absorber thickness, reducing efficiency to ≈23%. Device simulations are used to analyze the performance of CdSe x Te 1‐x solar cells; thermodynamic models are not sufficient for absorbers with electronic disorder and trapping.

14 SOLAR ENERGY↗

Wind Loading on Parabolic Trough Collectors: Wind and Structural Loads Measurements at an Operational Powerplant

Concentrated Solar Power (CSP) is a promising method for using solar power for electricity generation with thermal energy storage for industrial applications. Solar collectors constitute almost 1/3 of the total cost of the power plant. One of the primary drivers of unrealiability of these collectors is wind-driven loading of mirrors, support structures, and drives. To date, the design of the solar collector structures has relied on data from wind tunnels that do not adequately capture the dynamic effects observed at scale. NREL initiated a field measurement campaign at the operational Nevada Solar One (NSO) parabolic trough powerplant. At this plant, parabolic trough solar collectors track the sun from east to west in the course of a day and face varying wind loads depending on the wind properties and the angle of the troughs. The aim of the project is a detailed characterization of prevailing wind and turbulence conditions and resulting operational loads on parabolic troughs, providing insights into structural dynamic response, and generating a comprehensive wind-loading dataset for validating simulations of wind loading on collector structures. The measurements at NSO consist of sonic anemometers on masts at different heights to characterize the incoming flow and conditions at four trough rows at the edge of the trough field. In addition, a Doppler Lidar scans the horizontal plane above the troughs. The wind measurements at NSO have been continuously collecting data since October 2021 and are combined with structural load measurements that started in November 2022. The load measurements were installed on the same four outermost trough rows and include support structure bending moments, drive torque moments, dynamic accelerations of the spaceframe, mirror displacement, and tilt angles. Measurements are planned to continue until May 2023, providing a first-of-a-kind, high-resolution multi-month dataset of combined wind and load measurements. In this presentation, we show first results of the measurement campaign. Based on the measurements, we identified three main factors altering the flow over the parabolic troughs: Wind speed, wind direction, and the angle of the parabolic troughs. Most interactions between incoming wind and the trough field are observed when the wind blows perpendicular to the trough rows. In this case, the first rows experience the highest wind speed and block the downwind rows, creating conditions with decreased wind speed and enhanced turbulence within the trough field. Also, turbulent length scales are smaller after the first row. This leads to the highest static loads (bending and torque moments) at the first row but potentially increased dynamic loads within the field. We illustrate our findings with case studies focused on different wind conditions and will present fatigue analysis to highlight the impact of wind-driven loads on collector structures.

CSP collectors↗

THREE-DIMENSIONAL FEATURES OF THE OUTER HELIOSPHERE DUE TO COUPLING BETWEEN THE INTERSTELLAR AND INTERPLANETARY MAGNETIC FIELDS. IV. SOLAR CYCLE MODEL BASED ON ULYSSES OBSERVATIONS

The solar cycle has a profound influence on the solar wind (SW) interaction with the local interstellar medium (LISM) on more than one timescales. Also, there are substantial differences in individual solar cycle lengths and SW behavior within them. The presence of a slow SW belt, with a variable latitudinal extent changing within each solar cycle from rather small angles to 90 Degree-Sign , separated from the fast wind that originates at coronal holes substantially affects plasma in the inner heliosheath (IHS)-the SW region between the termination shock (TS) and the heliopause (HP). The solar cycle may be the reason why the complicated flow structure is observed in the IHS by Voyager 1. In this paper, we show that a substantial decrease in the SW ram pressure observed by Ulysses between the TS crossings by Voyager 1 and 2 contributes significantly to the difference in the heliocentric distances at which these crossings occurred. The Ulysses spacecraft is the source of valuable information about the three-dimensional and time-dependent properties of the SW. Its unique fast latitudinal scans of the SW regions make it possible to create a solar cycle model based on the spacecraft in situ measurements. On the basis of our analysis of the Ulysses data over the entire life of the mission, we generated time-dependent boundary conditions at 10 AU from the Sun and applied our MHD-neutral model to perform a numerical simulation of the SW-LISM interaction. We analyzed the global variations in the interaction pattern, the excursions of the TS and the HP, and the details of the plasma and magnetic field distributions in the IHS. Numerical results are compared with Voyager data as functions of time in the spacecraft frame. We discuss solar cycle effects which may be reasons for the recent decrease in the TS particles (ions accelerated to anomalous cosmic-ray energies) flux observed by Voyager 1.

79 ASTRONOMY AND ASTROPHYSICS↗

Intelligent Facades for High Performance Green Buildings. Final Technical Report

Intelligent Facades for High Performance Green Buildings: Previous research and development of intelligent facades systems has been limited in their contribution towards national goals for achieving on-site net zero buildings, because this R&D has failed to couple the many qualitative requirements of building envelopes such as the provision of daylighting, access to exterior views, satisfying aesthetic and cultural characteristics, with the quantitative metrics of energy harvesting, storage and redistribution. To achieve energy self-sufficiency from on-site solar resources, building envelopes can and must address this gamut of concerns simultaneously. With this project, we have undertaken a high-performance building- integrated combined-heat and power concentrating photovoltaic system with high temperature thermal capture, storage and transport towards multiple applications (BICPV/T). The critical contribution we are offering with the Integrated Concentrating Solar Façade (ICSF) is conceived to improve daylighting quality for improved health of occupants and mitigate solar heat gain while maximally capturing and transferring on- site solar energy. The ICSF accomplishes this multi-functionality by intercepting only the direct-normal component of solar energy (which is responsible for elevated cooling loads) thereby transforming a previously problematic source of energy into a high- quality resource that can be applied to building demands such as heating, cooling, dehumidification, domestic hot water, and possible further augmentation of electrical generation through organic Rankine cycles. With the ICSF technology, our team is addressing the global challenge in transitioning commercial and residential building stock towards on-site clean energy self-sufficiency, by fully integrating innovative environmental control systems strategies within an intelligent and responsively dynamic building envelope. The advantage of being able to use the entire solar spectrum for active and passive benefits, along with the potential savings of avoiding transmission losses through direct current (DC) transfer to all buildings systems directly from the site of solar conversion, gives the system a compounded economic viability within the commercial and institutional building markets.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electronic Delocalization, Vibrational Dynamics and Energy Transfer in Organic Chromophores

The efficiency of materials developed for solar energy and technological applications depends on the interplay between molecular architecture and light-induced electronic energy redistribution. The spatial localization of electronic excitations is very sensitive to molecular distortions. Vibrational nuclear motions can couple to electronic dynamics driving changes in localization. The electronic energy transfer among multiple chromophores arises from several distinct mechanisms that can give rise to experimentally measured signals. Atomistic simulations of coupled electron-vibrational dynamics can help uncover the nuclear motions directing energy flow. Through careful analysis of excited state wave function evolution and a useful fragmenting of multichromophore systems, through-bond transport and exciton hopping (through-space) mechanisms can be distinguished. Such insights are crucial in the interpretation of fluorescence anisotropy measurements and can aid materials design. Finally, this Perspective highlights the interconnected vibrational and electronic motions at the foundation of nonadiabatic dynamics where nuclear motions, including torsional rotations and bond vibrations, drive electronic transitions.

36 MATERIALS SCIENCE↗

Anatomy of Local Structural Disorder of Ni(II) Species in MgCl 2 –KCl Molten Salts

Understanding the speciation of metal ions dissolved in molten salts (MS) is critical for enabling a broad range of high-temperature energy applications, including MS nuclear reactors and concentrated solar power plants. However, due to the inherent dynamicity of metal species in the MS environment and the strong temperature dependencies of their multiple coexisting forms, they are difficult to resolve structurally. Herein, we show that combining in situ X-ray absorption spectroscopy (XAS) with ab initio molecular dynamics (AIMD) simulations is necessary to uncover and quantify the coexisting coordination states of Ni(II) in molten MgCl 2 –KCl mixtures and explain how the temperature and salt composition control their relative populations. Furthermore, from the interionic angle and distance distributions of nickel in different coordination states obtained from AIMD simulations, it is evident that for each coordination state, the width and skewness of their bonding distributions increase with increasing coordination number. In conclusion, the combination of XAS with first-principles modeling to resolve metastable metal species in MS is critical for understanding their behavior over a wide range of temperatures and chemical environments in nuclear and solar applications.

36 MATERIALS SCIENCE↗