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All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

Schlosser, Herbert↗
DOE OSTI2022

Intrinsic Halide Immiscibility in 2D Mixed-Halide Ruddlesden–Popper Perovskites

Halide alloying of 3D and 2D Ruddlesden–Popper lead halide perovskites (RPPs) allows their bandgaps to be fine-tuned for optoelectronic applications. Many studies of mixed-halide RPPs assume that halide mixing yields homogeneous alloys like in 3D lead halide perovskites, with halide segregation only occurring under perturbations like light or heat. Here we carefully investigate the mixed I/Br phases in solution grown microplates of three representative n = 1 and n = 2 RPP phases to reveal heterogeneous halide microscale domains – even in absence of photoinduced phase separation. Such halide immiscibility is revealed by X-ray diffraction and heterogeneity is confirmed by secondary ion mass spectrometry (SIMS) imaging, however, comparison with photoluminescence (PL) imaging results show how PL information alone can falsely imply homogeneous alloy formation in heterogeneous RPPs. Finally, we then demonstrate the use of spectral imaging as an alternative high-throughput tool for accurate halide phase characterization in mixed-halide RPPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Distinguishing Models for Mixed Halide Lead Perovskite Photosegregation via Terminal Halide Stoichiometry

Photoinduced halide segregation in mixed halide hybrid perovskites [i.e., APb(I 1–x Br x ) 3 ] represents an intrinsic instability that impedes their commercialization. Resolving this issue requires developing a microscopic understanding of the phenomenon. Key to this is distinguishing existing models of halide photosegregation by comparing their corresponding predictions to experiment. In this work, we test the temperature dependency of predicted perovskite terminal stoichiometries (x terminal ), following photosegregation, in single and double cation mixed halide perovskites. Our results show a general temperature invariance of x terminal . This largely supports the idea that band gap difference between parent and halide-segregated perovskite phases drives photosegregation. Beyond this, careful examination of temperature- and halide composition-dependent emission energies suggests an alternative explanation for the enhanced photostability of mixed cation/mixed halide perovskites, linked to band gap energy differences between parent and phase-segregated perovskite phases. Together, our results make inroads in clarifying the microscopic origin of mixed halide perovskite photosegregation and pave the way toward approaches that stabilize their use in applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Voltage-induced halide segregation greatly limits the optoelectronic applications of mixed-halide perovskite devices, but a mechanistic explanation behind this phenomenon remains unclear. In this work, we use electron microscopy and elemental mapping to directly measure the halide redistribution in mixed-halide perovskite solar cells with quasi-ion-impermeable contact layers under different bias polarities to find iodide and bromide accumulation at the cathode and anode, respectively. This is consistent with a mechanism based on preferential iodide oxidation at the anode, leading to unbalanced I$^{+}_{i}$, I$^{-}_{X}$, and Br$^{-}_{X}$ fluxes. Importantly, switching the anode from "inert" Au to "active" Ag prevents segregation because Ag oxidation precludes the oxidation of lattice iodide, which suggests employing redox-active additives as a general strategy to suppress halide segregation. Finally, these results show that halide perovskite devices operate as solid-state electrochemical cells when threshold voltages are exceeded, providing fresh insight to understand the impacts of voltage bias on halide perovskite devices.

14 SOLAR ENERGY↗
DOE OSTI2021

Photoinduced Halide Segregation in Ruddlesden–Popper 2D Mixed Halide Perovskite Films

2D lead halide perovskites, which exhibit bandgap tunability and increased chemical stability, have been found to be useful for designing optoelectronic devices. Reducing dimensionality with decreasing number of layers (n = 10–1) also imparts resistance to light-induced ion migration as seen from the halide ion segregation and dark recovery in mixed halide (Br:I = 50:50) perovskite films. The light-induced halide ion segregation efficiency, as determined from difference absorbance spectra, decreases from 20% to <1% as the dimensionality is decreased for 2D perovskite film from n = 10 to 1. The segregation rate constant (ksegregation), which decreases from 5.9 × 10 –3 s –1 (n = 10) to 3.6 × 10 –4 s –1 (n = 1), correlates well with nearly an order of magnitude decrease observed in charge-carrier lifetime (τ average = 233 ps for n = 10 vs τ avg = 27 ps for n = 1). The tightly bound excitons in 2D perovskites make charge separation less probable, which in turn decreases the halide mobility and resulting phase segregation. Furthermore, the importance of controlling the dimensionality of the 2D architecture in suppressing halide ion mobility is discussed.

14 SOLAR ENERGY↗
DOE OSTI2022

Iodine Electrochemistry Dictates Voltage‐Induced Halide Segregation Thresholds in Mixed‐Halide Perovskite Devices

Abstract Owing to straightforward stoichiometry–bandgap tunability, mixed‐halide perovskites are ideal for many optoelectronic devices. However, unwanted halide segregation under operational conditions, including light illumination and voltage bias, restricts practical use. Additionally, the origin of voltage‐induced halide segregation is still unclear. Herein, a systematic voltage threshold study in mixed bromide/iodide perovskite devices is performed and leads to observation of three distinct voltage thresholds corresponding to the doping of the hole transport material (0.7 ± 0.1 V), halide segregation (0.95 ± 0.05 V), and degradation (1.15 ± 0.05 V) for an optically stable mixed‐halide perovskite composition with a low bromide content (10%). These empirical threshold voltages are minimally affected by composition until very Br‐rich compositions, which reveals the dominant role of iodide/triiodide/iodine electrochemistry in voltage‐induced Br/I phase separation and transport layer doping reactions in halide perovskite devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Giant Apparent Optical Circular Dichroism in Thin Films of Bismuth-Based Hybrid Organic-Inorganic Metal Halide Semiconductor Through Preferred Orientation

Introducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self-assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)-4-methoxy-a-methylbenzylammonium, is incorporated to synthesize the bismuth-based hybrid organic-inorganic metal halide semiconductor, (R/S-MeOMePMA)BiI4. Thin films of this Bi-based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ˜0.1, close to the highest value observed in another chiral metal-halide semiconductor, (R-MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S-MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin-film orientation enables the control of gCD, with maximum value observed when its thin film has a well-crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal-halide materials and provides design rules for achieving large chiroptical response via morphology control.

chiroptic response↗
DOE OSTI2021

Reducing Surface Recombination Velocity of Methylammonium-Free Mixed-Cation Mixed-Halide Perovskites via Surface Passivation

We control surface recombination in the mixed-cation, mixed-halide perovskite, FA0.83Cs0.17Pb(I0.85Br0.15)3, by passivating nonradiative defects with the polymerizable Lewis base (3-aminopropyl)trimethoxysilane (APTMS). We demonstrate average minority carrier lifetimes >4 µs, nearly single exponential monomolecular photoluminescence decays, and high external photoluminescence quantum efficiencies (>20%, corresponding to ~97% of the maximum theoretical quasi-Fermi-level splitting) at low excitation fluence. We confirm both the composition and valence band edge position of the FA0.83Cs0.17Pb(I0.85Br0.15)3 perovskite using multi-institutional, cross-validated, X-ray photoelectron spectroscopy and UV photoelectron spectroscopy measurements. We extend the APTMS surface passivation to higher bandgap double-cation (FA and Cs) compositions (1.7, 1.75, and 1.8 eV) as well as the widely used triple-cation (FA, MA, and Cs) composition. Finally, we demonstrate that the average surface recombination velocity decreases from ~1000 to ~10 cm/s post APTMS passivation for FA0.83Cs0.17Pb(I0.85Br0.15)3. Our results demonstrate that surface-mediated recombination is the primary nonradiative loss pathway in many methylammonium (MA)-free mixed-cation mixed-halide films with a range of different bandgaps, which is a problem observed for a wide range of perovskite active layers and reactive electrical contacts. Our study also provides insights to develop passivating molecules that help reduce surface recombination in MA-free mixed-cation mixed-halide films and indicates that surface passivation and contact engineering will enable near-theoretical device efficiencies with these materials.

14 SOLAR ENERGY↗
DOE OSTI2024

3D Lead-Organoselenide-Halide Perovskites and their Mixed-Chalcogenide and Mixed-Halide Alloys

Here, we incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS ( + NH 3 (CH 2 ) 2 Se - ), which occupies both the X - and A + sites in the prototypical ABX 3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX 2 (X=Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77 Se and 207 Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX 2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable band gap decrease. Optical absorbance measurements indeed show band gaps of 2.07 and 1.86 eV for (SeCYS)PbX 2 with X=Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the band gap from 1.86 to 2.31 eV–straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the band gap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.

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

Unveiling the role of halide mixing in the crystallization kinetics and charge transfer mechanisms of wide-bandgap organic–inorganic halide perovskites

Understanding the crystallization kinetics of Br–I mixed-halide WBG perovskite films, and their correlation to the crystallographic structure and charge transfer dynamics, is critical for advancing WBG perovskite devices. Despite many efforts to increase the photovoltaic performances of wide-bandgap (WBG, with a Br content above 20%) perovskite solar cells based on bromine–iodine (Br–I) mixed-halide perovskites, understanding the crystallization kinetics of WBG perovskite films, as well as the role of Br mixing in the crystallization kinetics, is still lacking. Furthermore, an overlooked aspect is the correlation of the halide compositions, crystallization kinetics, crystallographic structure, and charge transfer dynamics. Here, we unveil that Br–I mixed-halide WBG perovskite films undergo two intrinsically different crystallization kinetic processes. One is the intermediate solvent-complex phase-assisted growth (I-rich), and the other is top-to-bottom downward growth (Br-rich). Such downward growth (including high Br concentrations) correlates with the formation of a highly vertically oriented perovskite film, which is accompanied by defect formation caused by a dissolving and recrystallization process coupled with halide homogenization. Consequently, Br-rich WBG perovskite films exhibit enhanced charge carrier transport, but are concurrently plagued by non-radiative charge recombination. Addressing this fundamental perspective is critical to precisely tailor Br-related crystallization, which significantly affects the structure and optoelectronic properties of WBG perovskite films and devices.

Li, Nian↗
DOE OSTI2023

Two-Factor Phase Separations in Mixed-Halide Quasi-2D Perovskite LEDs: Dimensionality and Halide Segregations

Quasi-2D halide perovskites have attracted much interest as a promising material for light-emitting diodes (LEDs) due to their tunability in quantum confinement and halide alloy formation to modulate the energy bandgap and emission color. However, two-factor phase separations with respect to heterogeneous quantum-well thicknesses and halide segregation are still crucial issues in quasi-2D perovskite LEDs, leading to low external quantum efficiencies (EQEs) and color shifts. In this work, we compare quasi-2D perovskite films using different cations to unveil the key contributions from the chemical design of organic cations. While mixing halide ions in conventional quasi-2D perovskite films induces micrometer-scale heterogeneity, new extended and twisted conjugated cations suppress the two-factor phase separations, leading to high EQEs of over 25% and controllable emission wavelengths across red and near-infrared regions. The fundamental insights in this work will provide guidance for advancing materials design and device performance in the future.

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

Local halide heterogeneity drives surface wrinkling in mixed-halide wide-bandgap perovskites

Compositional heterogeneity in wide-bandgap (1.8 - 2.1 eV) mixed-halide perovskites is a key bottleneck in the processing of high-quality solution-processed thin films and prevents their application in efficient multijunction solar cells. Notably, mixed-cation (formamidinium-methylammonium) wide-bandgap perovskite films are prone to form micrometer-scale wrinkles which can interfere with the smooth surfaces ideal for multijunction devices. Here, we study the formation dynamics of wrinkled mixed-halide perovskite films and its impact on the local composition and optoelectronic properties. We use in situ X-ray scattering during perovskite film formation to show that crystallization of bromide-rich perovskites precedes that of mixed-halide phases in wrinkled films cast using an antisolvent-based process. Using nanoscopic X­-ray fluorescence and hyperspectral photoluminescence imaging, we also demonstrate the formation of iodide- and bromide-rich phases in the wrinkled domains. This intrinsic spatial halide segregation results in an increased local bandgap variation and Urbach energy. Morphological disorder and compositional heterogeneity also aggravate the formation of sub-bandgap electronic defects, reducing photostability and accelerating light-induced segregation of iodide and bromide ions in thin films and solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Recent Progress in Cathode Materials for Sodium-Metal Halide Batteries

Transitioning from fossil-fuels to renewable energy sources is a critical goal of greenhouse gas re-duction and climate control. Major improvements have made wind and solar power increasingly cost-competitive with fossil fuels. However, the inherent intermittency of renewable power sources such motivates pairing these resources with energy storage. Electrochemical energy storage in batteries is widely used in many fields and increasingly for grid-level storage, but current battery technologies still fall short of performance, safety, and cost. This review focuses on sodium metal halide (Na-MH) batteries, such as well-known Na-NiCl2 batteries, as a promising solution to safe and economical grid-level energy storage. Important features of conventional Na-MH batteries are discussed, and recent literature on the development of intermediate temperature, low-cost cathodes for Na-MH batteries is highlighted. By employing lower cost metal halides (e.g. FeCl2, ZnCl2, and CuCl2, etc.) in the cathode and operating at lower temperatures (e.g. 190 °C vs. 280 °C), new Na-MH batteries have the potential to offer comparable performance at much lower overall costs, providing an exciting alternative technology to enable widespread adoption of renewables plus storage for the grid.

Zhan, Xiaowen↗