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Spin-orbit coupling controlled ground states in the double perovskite iridates $\textit{A}_2\textit{B}$IrO$_6$ ($\textit{A}$ = Ba, Sr; $\textit{B}$ = Lu, Sc)

Iridates with the 5$d^4$ electronic configuration have attracted recent interest due to reports of magnetically ordered ground states despite longstanding expectations that their strong spin-orbit coupling would generate a $\textit{J}$ = 0 electronic ground state for each Ir 5+ ion. The major focus of prior research has been on the double perovskite iridates Ba 2 YIrO 6 and Sr 2 YIrO 6 , where the nature of the ground states (i.e., ordered vs nonmagnetic) is still controversial. Here, in this work, we present neutron powder diffraction, high-energy-resolution fluorescence-detected x-ray absorption spectroscopy (HERFD-XAS), resonant inelastic x-ray scattering (RIXS), magnetic susceptibility, and muon spin relaxation data on the related double perovskite iridates Ba 2 LuIrO 6 , Sr 2 LuIrO 6 , Ba 2 ScIrO 6 , and Sr 2 ScIrO 6 that enable us to gain a general understanding of the electronic and magnetic properties for this family of materials. Our HERFD-XAS and RIXS measurements establish $\textit{J}$ = 0 electronic ground states for the Ir 5+ ions in all cases, with similar values for Hund's coupling $J_H$ and the spin-orbit coupling constant $λ_{\text{SOC}}$. Our bulk susceptibility and muon spin relaxation data find no evidence for long-range magnetic order or spin freezing, but they do exhibit weak magnetic signals that are consistent with extrinsic local moments. Our results indicate that the large $λ_{\text{SOC}}$ is the key driving force behind the electronic and magnetic ground states realized in the $5d^4$ double perovskite iridates, which agrees well with conventional wisdom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distribution Grid Modeling Using Smart Meter Data

The knowledge of distribution grid models, including topologies and line impedances, is essential for grid monitoring, control and protection. However, such information is often unavailable, incomplete or outdated. The increasing deployment of smart meters (SMs) provides a unique opportunity to tackle this issue. This paper proposes a two-stage framework for distribution grid modeling using SM data. In the first stage, the network topology is identified by reconstructing a weighted Laplacian matrix of distribution networks. In the second stage, a least absolute deviations (LAD) regression model is developed for estimating line impedance of a single branch based on the nonlinear (inverse) power flow model, wherein a conductor library is leveraged to narrow down the solution space. The LAD regression model is originally a mixed-integer nonlinear program whose continuous relaxation is still non-convex. Furthermore, we specially address its convex relaxation and discuss the exactness. The modified regression model is then embedded within a bottom-up sweep algorithm to achieve the identification across the network in a branch-wise manner. Numerical results on the IEEE 13-bus, 37-bus and 69-bus test feeders validate the effectiveness of the proposed methods.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Development and validation of time‐domain 1 H‐NMR relaxometry correlation for high‐throughput phenotyping method for lipid contents of lignocellulosic feedstocks

Abstract The bioenergy crops such as energycane, miscanthus, and sorghum are being genetically modified using state of the art synthetic biotechnology techniques to accumulate energy‐rich molecules such as triacylglycerides (TAGs) in their vegetative cells to enhance their utility for biofuel production. During the initial genetic developmental phase, many hundreds of transgenic phenotypes are produced. The efficiency of the production pipeline requires early and minimally destructive determination of oil content in individuals. Current screening methods require time‐intensive sample preparation and extraction with chemical solvents for each plant tissue. A rapid screen will also be needed for developing industrial extraction as these crops become available. In the present study, we have devised a proton relaxation nuclear magnetic resonance ( 1 H‐NMR) method for single‐step, non‐invasive, and chemical‐free characterization of in‐situ lipids in untreated and pretreated lignocellulosic biomass. The systematic evaluation of NMR relaxation time distribution provided insight into the proton environment associated with the lipids in the biomass. It resolved two distinct lipid‐associated subpopulations of proton nuclei that characterize total in‐situ lipids into bound and free oil based on their “molecular tumbling” rate. The T1T2 correlation spectra also facilitated the resolution of the influence of various pretreatment procedures on the chemical composition of molecular and local 1 H population in each sample. Furthermore, we show that hydrothermally pretreated biomass is suitable for direct NMR analysis unlike dilute acid and alkaline pretreated biomass which needs an additional step for neutralization.

pretreatment↗

Monolithic Multigrid Methods for Magnetohydrodynamics

The magnetohydrodynamics equations model a wide range of plasma physics applications and are characterized by a nonlinear system of partial differential equations that strongly couples a charged fluid with the evolution of electromagnetic fields. After discretization and linearization, the resulting system of equations is generally difficult to solve due to the coupling between variables and the heterogeneous coefficients induced by the linearization process. In this paper, we investigate multigrid preconditioners for this system based on specialized relaxation schemes that properly address the system structure and coupling. Here, three extensions of Vanka relaxation are proposed and applied to problems with up to 170 million degrees of freedom and fluid and magnetic Reynolds numbers up to 400 for stationary problems and up to 20,000 for time-dependent problems.

97 MATHEMATICS AND COMPUTING↗

Electrochemical Response of Alkaline Batteries Subject to Quasi-Static and Dynamic Loading

We report electrochemical changes were successfully monitored through the coupling of external loading, electrochemical impedance spectroscopy (EIS), and distribution of relaxation times (DRT) analysis. The development of the testing methods allows for detailed observation of changes due to mechanical loading and distinguishes responses between different cell geometries. Comparison of the force vs displacement, voltage vs displacement, and distribution of relaxation times plots to the different cell geometries display failure modes specific to geometry as well as the impact of different loading profiles. Numerical modeling confirmed the movement within individual cells and predicted locations with the most deformation based on the external loading condition applied. The results gathered from combining mechanical loading, electrochemical response, and numerical modeling, yield a viable approach to establishing an improved understanding of the effects of mechanical loading on the electrochemical response of multiple battery geometries and the methods herein may be extensible to additional battery chemistries.

25 ENERGY STORAGE↗

Characteristics of Ultralow Aspect Ratio Toroidal Plasmas and Non-Solenoidal Startup and Edge Stability Studies at Near-Unity Aspect Ratio (Final Report)

This grant supported a long-term research and development program to explore the physics and technology of spherical tokamak (ST) plasma behavior at near-unity aspect ratio ( A ). The PEGASUS Toroidal Experiment is a university-scale ( R ) ~ 0.40 m, α ~ .35 m, I p ≤ 0.3 MA, B T ≤ 0.15 T) experiment that accesses A → 1, to provide large values of the normalized plasma current, I N = I p /α B T , or equivalently the toroidal field utilization factor I p / I TF . The research activities focused on: 1) developing the technique of Local Helicity Injection (LHI) as a viable means of initiating and growing an ST plasma without the use of a central solenoid; 2) exploring the equilibrium and stability properties of spherical tokamak plasmas at extremely low aspect ratio; and 3) obtaining new insights in the properties of the enhanced confinement H-mode regime at A ~ 1. The initial (Phase I) facility employed a unique high-stress central solenoid Ohmic for current drive and heating with simple magnet current waveforms. A subsequent major upgrade (Phase II) offered more flexible control of the plasma evolution along with a powerful LHI system for plasma initiation, heating and sustainment. The LHI technique consists of injection of high-density current streams into vacuum toroidal and vertical magnetic fields. These streams become unstable and support magnetic reconnection to allow the system to relax into a tokamak-like magnetic configuration. This program focused on: 1) development of electron current sources that provide sufficiently high injection currents in the challenging edge plasma region; 2) validation of theoretical limits to achievable I p arising from magnetic helicity and energy conservation plus absolute limits arising from relaxation to a minimal energy states; 3) tests of a power balance model to describe the evolution of the plasma current I p (t); and 4) study of magnetic fluctuations and their role in the I p evolution. This culminated in the production of toroidal currents of I p ≥ 0.2 MA with only ~8 kA of injected current. Operation with Ohmic induction alone in Phase I created plasmas with soft limits on the achievable I p and field utilization ( I p / I TF ~ 1) due to the onset of large low-order (2/1 or 3/2) internal resonant tearing modes. With the expanded capabilities in Phase II operation, methods employed to mitigate those modes and achieve I p / I TF > 1 were: 1) I TF ramp-downs; 2) non-solenoidal startup via LHI; and 3) extremely low I TF Ohmic operations assisted by LHI current injector pre-ionization. Extensive use of LHI-driven startup and drive for non-solenoidal operation produced favorable current profiles to stably operate tokamak plasmas with unprecedentedly high I N = I p / aB T ~ 15 and I p / I TF > 2. With strong reconnection-driven anomalous ion heating, this in turn provided access to tokamak plasmas with B t up to 100%, a world record 2 times higher than that previously achieved in advanced or spherical tokamaks. This high B t regime had a large fraction (~50%) of the plasma volume in a region of an absolute minimum- B configuration. The MHD stability limit in this regime was the ideal external kink mode without a stabilizing wall. These results provided the first demonstration of access to tokamak plasmas with very high B t , high i N , high elongation κ, and low internal inductance ℓ i , and as such served as a proof-ofprinciple for access to this long-sought ST regime. The naturally low B T needed for stability at A ≤ 1.2 reduces the L-H mode power threshold, P LH , so that H-mode plasmas were achieved with Ohmic heating alone. The power threshold for the transition to the H-mode regime was found to be 10× the accepted values from the ITER international scaling, confirming initial trends indicated by experiments on MAST and NSTX, and suggesting that the physics behind this transition is not yet fully understood. The density dependence of the transition and the observed insensitivity to whether the plasma is bounded by a limiter or magnetic divertor are consistent with the recent FM 3 model. Multiple unstable toroidal magnetic modes were measured during ELM (Edge Localized Mode) crashes, with generally lower toroidal mode numbers than seen at higher A , which was attributed to the larger peeling mode instability drive at low A . First-ever edge current profile measurements through an ELM crash showed current-carrying filaments were generated, as seen in ELM simulations and in electromagnetic blob transport theory.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Innovative Method for Welding in Generation 3 CSP to Enable Reliable Manufacturing of Solar Receivers to withstand Daily Cycling at Temperatures Above 700°C (Final Technical Report)

Inconel® Alloy 740H® (alloy 740H) was the first age-hardenable nickel-based alloy approved by the ASME Boiler & Pressure Vessel Code for use in pressure-boundary applications. Over the past ~20 years the alloy has been optimized for weldability and high-temperature stability, approved for use in different applications. Development of a supply chain combined with the advantageous properties of the alloy (high-temperature creep strength, oxidation and corrosion resistance, etc.) have resulted in the alloy being applied to new high-temperature power cycle demonstration projects, and of particular interest are applications to concentrating solar power (CSP) to enable higher-efficiency Generation 3 CSP systems and the corresponding supercritical CO 2 (sCO 2 ) power cycle components (heat exchangers, piping, etc.). The high allowable stresses of alloy 740H also make it a desirable material for current Generation 2 CSP solar power receivers to improve cyclic capability and/or reduce receiver height. Recent experiences in demonstration projects utilizing alloy 740H identified cracking issues during welding and fabrication. In this project, a detailed study was done to confirm and clarify the Stress Relaxation Cracking (SRxC) mechanism, also known as stress relief cracking or strain-age cracking (SAC), during post-weld heat-treatment (PWHT). This involved detailed microscopy and advanced characterization to understand the root cause(s) of three failures obtained from industry. Based in-part on these findings, a targeted laboratory based SRxC test method was utilized to evaluate variables such as heat-to-heat variations, strain level, PWHT temperature, and starting material condition on three heats of alloy 740H. Industrial shop welding of cold-worked plates was also conducted. The research showed the following: SRxC was confirmed as the cracking mechanism for all field failures; Stress state (from residual stresses, constraint, deformation, and local stress concentrations) was playing a significant role in field failures and laboratory testing confirmed increasing susceptibility for all heats with increasing strain levels. High levels of microstructural strain were identified at crack initiation locations, in some cases leading to local recrystallization; Precipitate free zones (PFZs) at grain boundaries were found at relaxation cracks and crack initiation locations uniquely associated with SRxC in alloy 740H. Laboratory testing reproduced this microstructural feature which had only previously been reported in long-term creep testing of weldments. Advanced nano-scale characterization confirmed the presence of a moving boundary leading to coarsening of precipitates and PFZs where damage accumulated; The research suggested heat-to-heat variations due to local chemistry and processing may influence SRxC susceptibility, but more work is needed to fully clarify these effects. To disseminate the key learnings from this research to the scientific and engineering communities and alloy 740H end users, multiple technical publications and presentations were made, an industrial alloy 740H users meeting was held, and a new industry guideline specification document which can be directly implemented by end-users of alloy 740H was produced.

14 SOLAR ENERGY↗

Impact of Plate Thickness and Joint Geometry on Residual Stresses in 347H Stainless Steel Welds

Weldments of 347H stainless steel are potentially susceptible to stress relaxation cracking at elevated service temperatures. Mitigation of stress relaxation cracking susceptibility within a multipass weld requires a good understanding of welding practices and manufacturing techniques to control high tensile residual stresses. Here in this work, the dependence of residual stress distribution in 347H stainless steel on base plate thickness, joint geometry design, and preheating condition was systematically investigated by using three-dimensional finite element models. The finite element models were validated through good agreement between neutron diffraction measurements and calculated elastic strains. The single-V-groove welds with and without a preheating step all produced similar peak von Mises residual stresses, above 450 MPa, within both the fusion zone and heat-affected zone (HAZ). In plates thicker than 0.5 in. (12.7 mm), high tensile residual stress could be observed in a relatively large area, from the middle of the plate thickness to underneath the top surface. A double-V groove shifted the high tensile stress area to the middle thickness of the weld. A single-J-groove weld was able to confine the residual stress to a very small region near the middle thickness within the fusion zone and suppressed the von Mises residual stress within the HAZ to below 400 MPa.

14 SOLAR ENERGY↗

Optimizing ensemble NV − spin properties of fluorescent diamond microparticles by systematic low pressure high temperature annealing

Low pressure high temperature annealing is a means for driving nitrogen and defect diffusion in diamond to reduce internal lattice damage without the need for technically complicated high-pressure cells. Herein, we perform a systematic time (5, 15, and 30 min) and temperature (1200 °C–1800 °C) study of effects of low-pressure high temperature annealing on photoluminescence, spin concentrations, and spin relaxation properties of NV centers in ca. 3 μm synthetic type 1b diamond particles. Annealing in the temperature range of ca. 1400 °C–1700 °C for even 5 min leads to a higher optically detected magnetic resonance contrast as compared to standard annealing at 900 °C for 2 h. Particles annealed at 1700 °C for 5 min exhibit a contrast close to about 13% as compared to about 9% for those annealed at 900 °C for 2 h. A reduction in the zero-field splitting strain parameter from E ≈ 4.5 MHz to ≈ 2.5 MHz and spectral linewidth from Δν ≈ 7 MHz to ≈ 4 MHz are observed even after 5 min annealing at 1700 °C. Improvements in these spectral parameters resulted in a roughly 2-fold reduction in the noise level of temperature monitoring experiment utilizing an ensemble of NV centers in the particles. Annealing in the temperature range of 1600 °C for 15 or 30 min or 1700 °C for 5 min resulted in NV T 1 relaxation times approaching ca. 5 ms typically observed for bulk diamond. Quantitative electron paramagnetic resonance (EPR) allowed for estimations of thermal activation energies of paramagnetic center annihilation. Monitoring the primary defect concentration (P1 and other defects with half integer spins) and utilizing second order kinetic modeling, an activation energy of 3.63 ± 0.28 eV was estimated. Alternatively, using the NV half field EPR signal and first order kinetic modeling, a similar activation energy 3.89 ± 0.29 eV was estimated.

NV centers↗

Photometric and Kinematic Study of the Open Clusters SAI 44 and SAI 45

We carry out a detailed photometric and kinematic study of the poorly studied sparse open clusters SAI 44 and SAI 45 using ground-based BVR {sub c} I {sub c} data supplemented by archival data from Gaia eDR3 and Pan-STARRS. The stellar memberships are determined using a statistical method based on Gaia eDR3 kinematic data, and we found 204 members in SAI 44 while only 74 members are identified in SAI 45. The average distances to SAI 44 and SAI 45 are calculated to be 3670 ± 184 and 1668 ± 47 pc. The logarithmic age of the clusters are determined to be 8.82 ± 0.10 and 9.07 ± 0.10 yr for SAI 44 and SAI 45, respectively. The color–magnitude diagram of SAI 45 hosts an extended main-sequence turnoff (eMSTO). The apparent age spread is found to be similar to the apparent age spread predicted on the basis of the age spread and cluster age relation predicted by rotation models. This indicates that eMSTO is a stellar evolution rather than star formation phenomenon in SAI 45. We conclude that eMSTO in SAI 45 is mainly caused by the different rotation rates of stars as the SYCLIST synthetic population with different rotation rates was able to reproduce the observed eMSTO, and stars in the red part of the eMSTO were preferentially concentrated in the inner region, which again hints at different rotations being the reason for the extension in the upper MS. This finding supports the theory attributing the origin of eMSTO to the different rotations of eMSTO stars. The mass function slopes are obtained as -2.24 ± 0.66 and -2.58 ± 3.20 in the mass rages 2.426–0.990 M{sub ⊙} and 2.167–1.202 M{sub ⊙} for SAI 44 and SAI 45, respectively. SAI 44 exhibits the signature of mass segregation while we found weak evidence of mass segregation in SAI 45 possibly due to tidal stripping. The dynamical relaxation times of these clusters indicate that both clusters are in a dynamically relaxed state. Using the AD-diagram method, the apex coordinates are found to be ([[Formula]], -[[Formula]]) for SAI 44 and (-[[Formula]], -[[Formula]]) for SAI 45. The average space velocity components of the clusters SAI 44 and SAI 45 are calculated in units of km s{sup -1} as (-15.14 ± 3.90, -19.43 ± 4.41, -20.85 ± 4.57) and (28.13 ± 5.30, -9.78 ± 3.13, -19.59 ± 4.43), respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Droop-Free Distributed Control for AC Microgrids

In this chapter, droop-free distributed control for AC microgrids is discussed. The hierarchical structure of microgrid control is first introduced. Secondary level controls both with and without droop are discussed. Then two droop-free distributed controls are presented: one achieves average voltage regulation and perfect power sharing, and the other one achieves average voltage regulation, voltage variance regulation, and relaxed reactive power sharing. For the latter droop-free control, the relaxed reactive power sharing is achieved through a special distributed generator (DG) that will not participate in reactive power sharing.

Mohiuddin, Sheik Mohammad↗

Broadband, High-Speed, and Large-Amplitude Dynamic Optical Switching with Yttrium-Doped Cadmium Oxide

Transparent conducting oxides, such as doped indium oxide, zinc oxide, and cadmium oxide (CdO), have recently attracted attention as tailorable materials for applications in nanophotonic and plasmonic devices such as low-loss modulators and all-optical switches due to their tunable optical properties, fast optical response, and low losses. Here, optically induced extraordinarily large reflection changes (up to 135%) are demonstrated in bulk CdO films in the mid-infrared wavelength range close to the epsilon near zero (ENZ) point. To develop a better understanding of how doping level affects the static and dynamic optical properties of CdO, the evolution of the optical properties with yttrium (Y) doping is investigated. An increase in the metallicity and a blueshift of the ENZ point with increasing Y-concentrations is observed. Broadband all-optical switching from near-infrared to mid-infrared wavelengths is demonstrated. The major photoexcited carrier relaxation mechanisms in CdO are identified and it is shown that the relaxation times can be significantly reduced by increasing the dopant concentration in the film. Our report could pave the way to practical dynamic and passive optical and plasmonic devices with doped CdO spanning wavelengths from the ultraviolet to the mid-infrared region.

42 ENGINEERING↗

Abnormal Slow Phonon Dynamics Toward Prolonging Excited States Dynamics Enabled by Crystalline‐Assembling Donor–Acceptor Molecules

Phonon dynamics are a critical factor to control the optical properties of excited states in light-emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor-acceptor (D–A) molecules [2-(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation-modulated Raman spectroscopy, we find that the crystalline-lattice vibrations monitored by Raman-scattering laser beam of 785 nm demonstrate an un-usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline-assembling the D–A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline-assembling the D–A molecules into dipolar crystal. Here, this hypothesis can be verified by directly suppressing the phonon dynamics through freezing D–A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s- after removing photoexcitation. Clearly, crystalline-assembling D–A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.

36 MATERIALS SCIENCE↗

Atomic Structure of the Initial Nucleation Layer in Hexagonal Perovskite BaRuO 3 Thin Films

Hexagonal perovskites are an attractive family of materials due to their various polymorphs and rich structure–property relationships. BaRuO 3 (BRO) is a prototypical hexagonal perovskite, in which the electromagnetic properties are significantly modified depending on its lattice structure. Whereas thin-film synthesis would allow the study of the diverse properties of hexagonal perovskites by epitaxially stabilizing various metastable polymorphs, the epitaxial growth of hexagonal perovskites, especially at the initial growth stage, is yet to be addressed. In this study, it is shown that an intriguing nucleation behavior takes place during the initial stabilization of a hexagonal 9R BRO thin film deposited on a (111) SrTiO 3 (STO) substrate. It is found that a nanoscale strained layer composed of different RuO 6 octahedral stacking is initially formed at the interface followed by a relaxed single crystal 9R BRO thin film. Within the interface layer, hexagonal BRO is nucleated on the (111) STO substrate by both face- and corner-sharing octahedra. More interestingly, it is found that boundaries between differently stacked nucleation layers (heterostructural boundaries) facilitate strain relaxation, in addition to the formation of conventional misfit dislocations evolved from homostructural boundaries. The observations reveal an important underlying mechanism to understand the thin-film epitaxy and strain accommodation in hexagonal perovskites.

36 MATERIALS SCIENCE↗

Defect Generation and Evolution in Irradiated Epitaxial Films and Heterostructures of Fe 3 O 4 and Cr 2 O 3

Abstract The functionality of nuclear structural materials, sensors, and microelectronics in harsh environments such as radiation relies on understanding defect generation and evolution processes in oxide layers. The initial radiation response of epitaxial thin films of Fe 3 O 4 (111), Cr 2 O 3 (0001), and Fe 3 O 4 (111)/Cr 2 O 3 (0001) heterostructures deposited on Al 2 O 3 (0001) by oxygen‐assisted molecular beam epitaxy and irradiated with 200 keV He + is characterized. X‐ray diffraction and X‐ray absorption near edge spectroscopy showed that the Cr 2 O 3 layers underwent significant lattice expansion and disordering under irradiation, whereas the Fe 3 O 4 layers do not exhibit noticeable changes. In contrast, positron annihilation spectroscopy revealed an evolution of cation vacancy point defects in the Fe 3 O 4 layers into larger vacancy clusters with increasing irradiation, while the cation vacancies in Cr 2 O 3 remained primarily as single vacancies and small clusters. The results suggest that the Fe 3 O 4 lattice can utilize the free volume of the larger vacancy clusters to relax but the small vacancies in the Cr 2 O 3 lattice do not facilitate relaxation. Comparing defect concentrations in the single layer films versus the heterostructure suggests that point defects may cross the interface from Fe 3 O 4 into Cr 2 O 3 . Together, these results enhance the understanding of the initial defect evolution mechanisms in oxide layers in harsh irradiation environments.

36 MATERIALS SCIENCE↗

Exploring Transport Behavior in Hybrid Perovskites Solar Cells via Machine Learning Analysis of Environmental-Dependent Impedance Spectroscopy

Hybrid organic–inorganic perovskites are one of the promising candidates for the next-generation semiconductors due to their superlative optoelectronic properties. However, one of the limiting factors for potential applications is their chemical and structural instability in different environments. Herein, the stability of (FAPbI3)0.85(MAPbBr3)0.15 perovskite solar cell is explored in different atmospheres using impedance spectroscopy. An equivalent circuit model and distribution of relaxation times (DRTs) are used to effectively analyze impedance spectra. DRT is further analyzed via machine learning workflow based on the non-negative matrix factorization of reconstructed relaxation time spectra. This exploration provides the interplay of charge transport dynamics and recombination processes under environment stimuli and illumination. The results reveal that in the dark, oxygen atmosphere induces an increased hole concentration with less ionic character while ionic motion is dominant under ambient air. Under 1 Sun illumination, the environment-dependent impedance responses show a more striking effect compared with dark conditions. In this case, the increased transport resistance observed under oxygen atmosphere in equivalent circuit analysis arises due to interruption of photogenerated hole carriers. The results not only shed light on elucidating transport mechanisms of perovskite solar cells in different environments but also offer an effective interpretation of impedance responses.

36 MATERIALS SCIENCE↗

Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature

Time-resolved X-ray (Tr-XAS) and optical transient absorption (OTA) spectroscopy in the pico-microsecond time scale coupled with Density Functional theory calculations are applied to study the light-induced spin crossover processes of a Fe-based macrocyclic complex in solution. Tr-XAS analysis after light illumination shows the formation of a seven-coordinated high spin quintet metastable state which relaxes to a six-coordinated high spin configuration before decaying to ground state. Kinetic analysis of the macrocyclic complex reveals an unprecedented long-lived decay lifetime of ~42.6 µs. Comparative studies with a non-macrocyclic counterpart illustrate a significantly shortened ~568-old decay lifetime of ~75 ns, and highlight the importance of the ligand arrangement in stabilizing the reactivity of the excited state. Lastly, OTA analysis shows the seven-coordinated high spin state to be formed within ~6.2 ps. Finally, these findings provide a complete understanding of the spin crossover reaction and relaxation pathways of the macrocyclic complex, and reveal the importance of a flexible coordination environment for their rational design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗