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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Pulling thin single crystal silicon wafers from a melt: The new leading-edge solar substrate

The Floating Silicon Method (FSM) has been established as a viable, stable method for growing single crystal ribbons directly from a silicon melt. With intense helium jet cooling to drive the linear progress of a [111] facet, pulled in the <110> direction, ribbons in the 0.6 – 3.0 mm thickness range can be grown at linear growth rates from 0.3 mm/s to >6 mm/s as reported in the literature. We report on recent progress towards growing (100) oriented ribbons with a net thickness of less than 200 microns and a ribbon width up to 18 cm using a stable, continuous process in the Leading Edge prototype furnace. Here, the 3D details of the single crystal growth are explained by extending the mechanics of the Limit Cycle Theory, with novel Internal Side Effect morphology described by a proposed Facet Flow Theory. Grown-in crystalline defect distributions are described as well as values of critical impurities like oxygen, carbon, dopants, and metals that are relevant for use as wafers for solar cells.

14 SOLAR ENERGY↗
DOE OSTI2025

Impact of lead on an axisymmetric, single bead blown powder DED overhung geometry

Metal additive manufacturing can be utilized for the near net-shape manufacture of components in a layer wise technique. Traditionally, the buildup process is conducted in the direction of gravity or bottom to top in the vertical orientation; however, with the availability of commercial systems with additive heads or fixturing that can index from vertical, and the need to manufacture larger parts without modifying available systems, the limitation of manufacturing from bottom to top is removed enabling the buildup of larger components printed at an angle from vertical. The effect of gravity on the melt pool and as-deposited component quality when printing off vertical is unknown in literature, especially for axisymmetric components. This understanding is critical for the advancement of manufacturing components of increased size in 4 and 5-axis additive systems. This investigation utilizes blown powder directed energy deposition to evaluate the change in as-printed geometry when the start point is altered in relation to gravity while the part rotates to manufacture an axisymmetric component. The objectives of this work are to determine the impact of the deposition location on the geometric variability on axisymmetric components. This investigation tests the hypothesis that differences in layer height exist due to a change in catchment efficiency when the deposition location is moved to a tangent of the round geometry due to a change in the melt pool dynamics. It was found the ideal deposition location when printing at 26.6-degrees from vertical was at −90-degrees from the top center point of the component, along the tangent, where gravity was pushing the melt pool down, but the rotation of the part was pulling the deposited material towards the top center of the component. This work provides an understanding of layer height stability and catchment efficiency to guide print orientation strategy for high-aspect ratio components. It was found the −90-degree lead deposition had the best layer height stability at 0.6 % as compared to the top-center at 6.3 % and +90-degree deposition location at 9.2 % for the nominal programmed layer height. The change in layer height also effected the final diameter the greatest for the top center deposition location where the diameter diverged by 2.5 % during the overbuild condition and converged by 0.6 %. In conclusion, this finding will increase the manufacturing efficiency of axisymmetric components by increasing the passive stability of the printing process for the successful manufacture of parts without the need for perfectly calibrated manufacturing parameters.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Catalysts by pyrolysis: Direct observation of transformations during re-pyrolysis of transition metal-nitrogen-carbon materials leading to state-of-the-art platinum group metal-free electrocatalyst

Transition metal-nitrogen-carbon (M-N-C) materials have been the focus of scientists’ efforts to address the rising need for earth-abundant materials solutions for energy technology and decarbonization of the economy. They are viewed as one of the most promising candidates to replace platinum group metal (PGM) catalysts in the fuel cell and energy conversion fields, including the application of oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. In the effort to improve M-N-C materials properties and achieve atomic dispersity of the transition metal in the carbonaceous matrix, a re-pyrolysis process has been proposed. This secondary heat treatment process of already obtained primary pyrolysis-derived M-N-C materials has been widely reported to substantially improve the electrochemical performance and operational stability of the catalysts. Here, we report a systematic investigation of this process used on samples of templated M-N-C catalysts to obtain state-of-the-art catalysts via in situ heating X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), and X-ray computed tomography (CT) characterization methods. It is found that the re-pyrolysis of M-N-C materials could result in the partial amorphization of the carbonaceous substrate. It causes the rearrangement and transformation of multitudinous N moieties, leading to optimization of their morphological display and association with atomically dispersed transition metal dopants. Ultimately, the re-pyrolysis results in an increase in uniformity of the active Fe-Nx sites distribution without the formation of nano-crystalline phases (metallic or carbide) and with overall preservation of the morphology of the carbonaceous framework achieved during the first formative pyrolysis step of the templated synthesis. Finally, these observations provide confirmation that empirically established re-pyrolysis is recommended to be used on all M-N-C materials despite the different synthesis routes to obtain a practical advanced catalytic material.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Multifunctional landscapes for dedicated bioenergy crops lead to low-carbon market-competitive biofuels

Switchgrass is a promising feedstock for cellulosic biorefineries, due to its ability to maintain comparatively high biomass yields across a wide range of soil and climatic conditions. However, there is an incomplete understanding of the economic and environmental tradeoffs associated with cultivating switchgrass on low-productivity land for conversion to biofuels. This study surveys prior literature and demonstrates a new integrated assessment framework, including agroecosystem, ecosystem services valuation, technoeconomic, and life-cycle assessment models, to quantify and contextualize the economic and environmental impacts of switchgrass cultivation on marginal land with downstream conversion to biofuels. Monetizing and incorporating the value of ecosystem services, such as improved water quality benefits from nitrate and sediment reductions, climate change mitigation benefits from CO 2 emission reduction, and recreational and pollination benefits from increased biodiversity, the modeled multifunctional landscape reduces the ethanol production cost by 33.3–58.9 cents/$\scriptsize{L}$-gasoline-equivalent ($\$$1.3–2.2/gge). Planting switchgrass in low productivity land improves soil health, resulting in the carbon footprint reduction credit of 12.8–20.2 gCO 2e /MJ. For an improved switchgrass-to-ethanol conversion pathway with the maximum benefits from ecosystem services, the minimum ethanol selling price and carbon footprint of ethanol, respectively, could reach to 31 cents/$\scriptsize{L}$-gasoline-equivalent (47% reduction relative to average gasoline price) and 3 gCO 2e /MJ (97% reduction relative to gasoline). In conclusion, this low carbon renewable ethanol leads to substantial State and/or Federal policy incentives (~$\$$1/$\scriptsize{L}$-gasoline-equivalent) providing a large benefit to biorefinery operators, farmers, and the public as a whole.

09 BIOMASS FUELS↗
DOE OSTI2026

Lead Isotope Fingerprinting of Nanoscale Mineral Particles via Single Particle Inductively Coupled Plasma Mass Spectrometry

Determining lead (Pb) isotopic ratios is of broad interest across chemical disciplines for source tracing and age determinations, but the technique is inherently limited when multiple sources of Pb are present in a single sample. Single particle methods offer a solution to directly resolve multiple distinct isotopic ratios within individual samples. In this study, single particle inductively coupled plasma-mass spectrometry (spICP-MS) was performed using time-of-flight (TOF) and multicollector (MC)-based platforms to measure the Pb isotopic composition of individual nanoscale particles. Distinct Pb isotope ratios were measured in particles from four powdered galena samples of different origins (average single-particle 206Pb/207Pb ratios ranging from 0.91 to 1.28) using both the TOF and the MC-based platforms. Differentiation of galena particles in a mixture (liberated grains and those hosted in a silicate matrix) was possible due to detecting their unique multielemental fingerprints. The differing behavior of the two galena samples during digestion was investigated; undigested galena particles trapped within silicate minerals were detected using spICP-MS, which has implications for Pb recovery in bulk-scale isotopic analysis. The multinuclide detection capability of the ICP-TOF-MS instrument allowed for the simultaneous detection of secondary constituent elements within the nanoparticles and the identification of multiple populations of isotopically distinct Pb-bearing particles in a copper ore sample, whereas the increased sensitivity of the MC instrument enabled quantification of 204Pb, allowing differentiation using multiple isotopic ratios. A single particle isotope ratio analysis module was developed within an open-source spICP-TOF-MS data processing platform, enabling its adoption across chemical disciplines.

Goodman, Aaron J. [University of Montreal, Quebec,↗
DOE OSTI2021

Fundamental Processes and Practical Considerations of Lead Chalcogenide Mesocrystals Formed via Self-Assembly and Directed Attachment of Nanocrystals at a Fluid Interface

Significant advances in the synthesis and processing of colloidal nanocrystals have given scientists and engineers access to a vast library of building blocks with precisely defined size, shape, and composition. These materials have inspired exciting prospects to enable bottom-up fabrication of programmable materials with properties by design. Successfully assembling and connecting the building blocks into superstructures in which constituent nanocrystals can purposefully interact requires robust understanding of and control over a complex interplay of dynamic physicochemical processes. Fluid interfaces provide an advantageous experimental workbench to both probe and control these processes. Despite the ostensible simplicity of fabricating nanocrystal assemblies at a fluid interface, sensitivity to processing conditions and limited reproducibility have underscored the complexity of this process. In situ studies have provided mechanistic insights into the competing dynamics of key subprocesses including solvent spreading and evaporation, superlattice formation, ligand detachment kinetics, and nanocrystal attachment. Understanding how these subprocesses influence the complex choreography of self-assembly, structure transformation, and oriented attachment processes presents a rich research challenge. In this context, we present a detailed methodology for self-assembly and attachment of lead chalcogenide nanocrystals at a liquid–gas interface as a model system for the fabrication of mono- and multilayer cubic connected superlattices. We discuss key experimental parameters such as the characteristics of the building blocks and processing conditions and detailed steps from colloidal nanocrystal injection to superlattice transfer. Furthermore, we hope that this Methods/Protocols paper will provide guidance for future advances in the exciting path toward bringing the prospect of nanocrystal-based programmable materials to fruition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

The limitations of three-dimensional (3D) perovskites are related to their narrow structural tunability of the organic cations and their moisture sensitivity. Herein, we report a new family of 3D cubic hybrid metal halides (T-Et 6 ) 3 Pb 11 X 31 (X = I, Br), where T is 1,3,5-tris-(4-aminophenyl)benzene. The materials are synthesized through an in situ N-alkylation of T and an efficient one-step solvothermal reaction containing ethanol, initiating a tunable synthetic avenue for the acquisition of structurally complex hybrid halides with luminophores. (T-Et 6 ) 3 Pb 11 X 31 consist of an unprecedented Ia3̅ framework of [Pb 11 X 31 ] 9– one-dimensional (1D) chains embedded with (T-Et 6 ) 3+ cations, affording an overall 3D topology. Here, the constituent [Pb 11 X 31 ] 9– chains include exclusively octahedral lead halide units with clusters of face- and edge-sharing connectivity, giving rise to weak broad emission centered at ~660 nm observed at 78 K. (T-Et 6 ) 3 Pb 11 I 31 demonstrates water stability for at least 7 days. Synthesis through ambient pressure results in tunable structural variations of zero-dimensional (0D) structures rendering T 7 Pb 3 Br 27 ·DMF and T 2 Sn 3 Br 18 ·4H 2 O·0.5Br 2 , both of which feature blue PL emission at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Layered and Low-Dimensional Lead, Silver, and Bismuth Halide Perovskites Directed by Halogen-Substituted Spacer Cations

Hybrid organic–inorganic metal halides provide a diverse parameter space in which the optoelectronic properties can be tuned through the composition. The compositional tunability extends to the metal site, which can be expanded from single valent metals (e.g., Pb 2+ ) to multivalent metals (e.g., Ag + and Bi 3+ ), and the dimension (2D, 1D, or 0D). However, a deeper understanding of how the organic cations template these metal halide structures is needed. Here, we synthesize and study the structures of a series of new layered and low-dimensional metal (Pb, Ag, and Bi) halides templated by the halogenated aryl spacer cations 2-chlorobenzylammonium (2ClBZ) and 3-chloro-2-fluorobenzylammonium (3Cl2FBZ). We report new lead perovskites, (3Cl2FBZ) 2 PbBr 4 , (2ClBZ) 3 PbI 5 , and (3Cl2FBZ) 2 PbI 4 , and compare them to their silver and/or bismuth analogs (2ClBZ) 4 AgBiBr 8 , (3Cl2FBZ) 4 AgBiBr 8 , (2ClBZ) 3 Bi 2 I 9 , and (3Cl2FBZ) 4 Bi 2 I 10 . In all structures, the halogen-substituted cations result in 2D or “pseudo-2D” layering, but the different halogen substituents introduce different distortions (tilting, octahedral distortion) and dimensional reduction to 1D or 0D depending on the metal and halide compositions. Optical absorption measurements reveal the bandgaps are tunable through metal sites, dimension, and cations to different extents. Furthermore, the 1D (3Cl2FBZ) 4 Bi 2 I 10 crystallizes in the noncentrosymmetric space group Cmc2 1 and exhibits second-harmonic generation (SHG). Furthermore, the organic–inorganic interactions and resultant structural distortions examined here provide insights toward the engineering of noncentrosymmetry and dimensional control in hybrid metal halide perovskites.

Cations↗
DOE OSTI2025

Bulky Cation-Modified Interfaces for Thermally Stable Lead Halide Perovskite Solar Cells

Charged conjugated organic molecules offer promising prospects for reducing nonradiative recombination at interfaces in perovskite solar cells, while protecting the active layer from moisture. However, several studies have shown that the heat induced diffusion of these cations leads to irreversible solar cell degradation. Passivation molecules for perovskite can reconstruct the film surface into lower-dimensional phases when exposed to thermal stress, impeding charge extraction and affecting the photoconversion efficiency (PCE) of devices. In this work, we study how molecular interactions between passivation molecules and 3D CsFAPbI 3 perovskite impact stability and charge extraction at the perovskite/hole transport layer interfaces. Two model π- conjugated molecules are studied: 2-([2,2′-bithiophen]-5-yl)ethan-1-aminium iodide (2TI) and 2-(3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴- quaterthiophen]-5-yl)ethan-1-ammonium iodide (4TmI). We demonstrate that the speed of surface layer reconstruction under thermal stress can be controlled by the cation size and correlate these structural changes with the solar cell performance and stability. Devices treated with 2TI and 4TmI achieve PCEs over 21% and maintain their performance under thermal stress. Our findings demonstrate that thermal stability in PSCs can be achieved via the design engineering of passivation agents, offering a blueprint for developing next-generation passivation molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Simulated Aquifer Heterogeneity Leads to Enhanced Attenuation and Multiple Retention Processes of Zinc

Alluvial aquifers serve as one of the main water sources for domestic, agricultural, and industrial purposes globally. Groundwater quality, however, can be threatened by naturally occurring and anthropogenic metal contaminants. Differing hydrologic and biogeochemical conditions between predominantly coarse-grained aquifer sediments and embedded layers or lenses of fine-grained materials lead to variation in metal behavior. Here, we examine processes controlling Zn partitioning within a dual-pore domain-reconstructed alluvial aquifer. Natural coarse aquifer sediments from the Wind River-Little Wind River floodplain near Riverton, WY, were used in columns with or without fine-grained lenses to examine biogeochemical controls on Zn concentrations, retention mechanisms, and transport. Furthermore, following the introduction of Zn to the groundwater source, Zn preferentially accumulated in the fine-grained lenses, despite their small volumetric contributions. While the clay fraction dominated Zn retention in the sandy aquifer, the lenses supported additional reaction pathways of retention—the reducing conditions within the lenses resulted in ZnS precipitation, overriding the contribution of organic matter. Zinc concentration in the groundwater controlled the formation of Zn-clays and Zn-layered double hydroxides, whereas the extent of sulfide production controlled precipitation of ZnS. Our findings illustrate how both spatial and compositional heterogeneities govern the extent and mechanisms of Zn retention in intricate groundwater systems, with implications for plume behavior and groundwater quality.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Water Defect Stabilizes the Bi 3+ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure

In this work, the aqueous hydration structure of Bi 3+ is probed using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations of ion-water clusters and of condensed-phase solutions. Anomalous features in the EXAFS spectra are found to be associated with a highly asymmetric first-solvent water shell. The aqueous chemistry and structure of the Bi 3+ ion is dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multi-modal distribution of waters in the first shell that are separated by about 0.2Å. The lone-pair structure is stabilized by a collective response of multiple waters that are localized near the lone-pair anti-bonding site. The findings indicate that the lone-pair stereochemistry of aqueous Bi 3+ plays a major role in the binding of water and ligands in aqueous solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites

Intrinsic photophysical origin of lead halide perovskites (LHPs) succeeding in optolectronic applications still remains hotly debated. In this study, by using the ultrafast X-ray transient absorption spectroscopy, we successfully tracked the fate of photogenerated charge carriers at room temperature within the thin films of two classic LHPs, namely MAPbBr 3 (MA: CH 3 NH 3 ) and FAPbBr 3 (FA: CH(NH 2 ) 2 ). We clearly observed in both thin films that the hole polaron is formed by localizing the photogenerated hole at Br 4p orbital and concurrently distorting the local structure surrounding Br atom after the photoexcitation. Furthermore, the bigger cation FA in the cavity of [PbBr 6 ] 4- octahedral framework induces larger hole polaron effect due to its p orbital hybridization into valence and conduction bands, correlating with the slower charge carrier recombination dynamics. Our direct experimental observation of the localized hole polaron in perovskites should advance the fundamental comprehension of charge carrier behavior within LHPs and their related devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Barrier Heights for Diels–Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules

Theoretical characterization of reactions of complex molecules depends on providing consistent accuracy for the relative energies of intermediates and transition states. Here we employ the DLPNO-CCSD(T) method with core–valence correlation, large basis sets, and extrapolation to the CBS limit to provide benchmark values for Diels–Alder transition states leading to competitive strained pentacyclic adducts. We then used those benchmarks to test a diverse set of wave function and density functional methods for the absolute and relative barrier heights of these transition states. Our results show that only a few of the tested density functionals can predict the absolute barrier heights satisfactorily, although relative barrier heights are more accurate. The most accurate functionals tested are ωB97M-V, M11plus, ωB97X-V, PBE-D3(0), M11, and MN15 with MUDs from best estimates less than 3.0 kcal. Furthermore, these findings can guide selection of density functionals for future studies of crowded, strained transition states of large molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

On the Interplay of Electronic and Lattice Screening on Exciton Binding in Two-Dimensional Lead Halide Perovskites

We use path integral Monte Carlo to study the energetics of excitons in layered, hybrid organic–inorganic perovskites in order to elucidate the relative contributions of dielectric confinement and electron–phonon coupling. While the dielectric mismatch between polar perovskite layers and nonpolar ligand layers significantly increases the exciton binding energy relative to their three-dimensional bulk crystal counterparts, formation of exciton polarons attenuates this effect. The contribution from polaron formation is found to be a nonmonotonic function of the lead halide layer thickness, which is clarified by a general variational theory. Accounting for both of these effects provides a description of exciton binding energies in good agreement with experimental measurements. By studying isolated layers and stacked layered crystals of various thicknesses, with ligands of varying polarity, we provide a systematic understanding of the excitonic behavior of this class of materials and how to engineer their photophysics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electronic Rearrangement in Steps of Reductive Elimination of Polar Electrophiles Leads to Refinement of Redox Events

The oxidative addition/reductive elimination of polar molecules such as methyl iodide at late metal centers has a strongly supported $S_{N^2}$ mechanism for many key organometallic complexes, including important industrial catalysts. In the reductive elimination direction, it is proposed that a ligand initially dissociates, typically a halide, followed by subsequent nucleophilic attack at the ligand trans to the now vacant site. The prevailing view is the metal reduction occurs upon transferring the electrophile in the $S_{N^2}$ step. Herein, we report the use of an ensemble of computational techniques to characterize the electronic structure of the reactants and intermediates along this reductive elimination pathway. These calculations demonstrate, unexpectedly, that the initiating loss of an anionic ligand from the octahedral highly oxidized structure leads to an electronic rearrangement that shifts electron density from the apical ligand back toward the metal resulting in an inversion of the electron flow between the metal and apical ligand. The anisotropic shift in electron density to the metal disproportionately affects the apical position, which is best described as a Pt → Me dative bond. With this Pt → Me bonding description, our interpretation of the IUPAC oxidation state formalism would assign the intermediate as Pt ΙΙ . Although counterintuitive, the formal and functional reduction of the metal thus occurs upon halide dissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Revisiting Structural and Electromechanical Properties of the Lead-free (K,Na)NbO 3 High-Piezoelectric Material

Having lead-free systems with excellent piezoelectric responses is crucial to the development of environmentally friendly electromechanical applications. In this work, we build an effective Hamiltonian model to explore the promising (K x Na 1–x )NbO 3 system, whose rich phase diagram near x = 50% remains poorly understood meanwhile exhibiting a colossal effective piezoelectric response. Thanks to the numerical implementation of this effective Hamiltonian scheme into a Monte Carlo Metropolis algorithm, we reveal striking features. First, a long-period state can be the ground state at low temperatures for some concentrations while only a short-period conventional polar ground state exists for larger x. Second, the electric field-driven transformation, via a first-order transition, of this long-period state into a short-period polar state creates large electromechanical strains (on the order of the percent) and is likely the origin of the colossal piezoelectric response reported in KNN, for which we evaluate an effective piezoelectric coefficient of several thousands of pC/N.

(K,Na)NbO3↗
DOE OSTI2026

Methyl Viologen Lead Iodide for Photocatalytic Reductive Coupling of Aromatic Carbonyls via Proton-Coupled Electron Transfer

Organic–inorganic metal halides (OIMHs) have emerged as promising photocatalysts for organic transformations due to their excellent optoelectronic properties. However, their instability, particularly under protic conditions, has limited their broader applications. Here, we report that a facilely prepared methyl viologen lead iodide (MVPb 2 I 6 ) powder can efficiently catalyze the visible-light-driven reductive coupling of aromatic aldehydes and ketones in protic solvents. Remarkably, MVPb 2 I 6 retains its structural integrity after photoreduction, highlighting its robustness. These results suggest that incorporating quaternary pyridinium cations into the OIMHs can enhance their stability and expand their applicability in photocatalytic organic synthesis.

organic-inorganic hybrid composites↗
DOE OSTI2020

Suppressing Cation Migration in Triple-Cation Lead Halide Perovskites

Ion migration represents an intrinsic instability of metal halide perovskite solar cells. In this work, we show that triple-cation FA x MA y Cs 1–x–y PbI 3 [FA + = (NH 2 ) 2 CH + , MA + = CH 3 NH 3 + ] active layers with mixed orthorhombic, post-perovskite (δ ortho -CsPbI 3 ), and cubic perovskite (α) phases (i.e., α/δ-phase FA x MA y Cs 1–x–y PbI 3 ) exhibit improved cation stability against applied bias relative to pure α-phase perovskites (i.e., FA 0.85 Cs 0.15 PbI 3 and FA 0.76 MA 0.15 Cs 0.09 PbI 3 ). Infrared photothermal heterodyne imaging and time-of-flight secondary ion mass spectrometry are used to visualize exclusive α-phase perovskite lateral device A + cation accumulation (depletion) at perovskite negative (positive) electrode interfaces. The resulting compositional heterogeneities lead to degradation. Operational stability testing of solar cells reveals similar degradation behavior; α/δ-phase FA x MA y Cs 1–x–y PbI 3 lateral devices/solar cells, by contrast, show improved stabilities. Enhanced α/δ-FA x MA y Cs 1–x–y PbI 3 stability is rationalized by δortho-phase inclusions, acting as barriers through which A + cations do not easily migrate. This study thus provides new insights into cation migration in FA x MAyCs 1–x–y PbI 3 perovskites and suggests a materials design strategy toward suppressing cation instabilities in hybrid perovskites.

14 SOLAR ENERGY↗