Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Halide”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
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 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 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 OSTI2025

In Situ Electrochemistry of Buried Interfaces in Metal Halide Perovskites: Probing Energy Bands, Halide Redox Activity, and Kinetics

Control over charge injection and extraction processes across buried interfaces is fundamental for all (opto)electronic multilayer device platforms, necessitating detailed understanding of local structural and chemical differences that promote defect formation, distort energetic band-edge alignments, and alter charge transport processes. Herein, the implementation of a low-cost electroanalytical methodologies’ tool suite is described to quantitatively characterize buried interfaces and redox reactions in printable, mixed electrical–ionic, and redox-active metal halide perovskites and a prototypical hole-transporting nickel oxide (NiO x ) thin film. The objective is to demonstrate the power of electrochemical methodologies to improve the nanoscale understanding of complex interfaces within optoelectronic devices by providing case studies on how to: i) differentiate between electronic and chemical properties in NiO x contacts; ii) measure changes in reversibility of halide redox reactions via NiO x surface states; iii) assess energy alignment and charge transport across (modified) buried interfaces; and iv) quantify defects at buried interfaces that change with modifiers and differences in perovskite processing, including increasing defect concentrations when films are slot-die-coated versus spin-cast. The collective approach addresses major challenges in understanding the precise energy landscape and interface reactivity under relevant electric fields that mimic operando conditions (away from equilibrium) and across length scales in thin film device formats.

(spectro)electrochemistry↗
NASA NTRS1982

Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

Allamandola, Louis J.↗
NASA NTRS1982

Method and apparatus for convection control of metallic halide vapor density in a metallic halide laser

An apparatus is disclosed in which a reservoir containing copper chloride is heated so that the copper chloride is maintained in a liquid form. The apparatus includes a means for flowing a buffer gas (which in the exemplary embodiment is neon) over the liquid copper chloride to provide a mixture of copper chloride vapor and neon above the liquid copper chloride. A conduit provides fluid communication between the reservoir containing the copper chloride vapor/neon mixture and the laser. The copper chloride vapor density in the laser is related to the liquid copper chloride temperature and the neon flow rate through the reservoir. In accordance with a further feature of the exemplary embodiment, neon is also provided directly to the laser in order to provide a further means of controlling the copper chloride vapor density in the laser.

Pivirotto, T. J.↗
DOE OSTI2026

Light-Driven Iodine Loss and Photoluminescence Homogenization in Mixed-Halide Perovskite Semiconductors

Carrier-induced instabilities in lead halide perovskites are often investigated as either transient phenomena, e.g., photoinduced halide segregation or permanent performance changes, e.g., photodegradation, while the mechanistic links between them remain unclear. Here, we aim to connect these observations by studying a model mixed-halide system, MAPb(Br x I 1–x ) 3 . By combining grazing-incidence X-ray diffraction, photothermal deflection spectroscopy, and photoluminescence measurements with hyperspectral microscopy, we investigate the role of mobile halide defects and local chemistry on reversible and long-term instabilities in these materials. Our results show that mixed-halide perovskites are uniquely susceptible to photoinduced changes with illumination driving initial iodide redistribution (i.e., halide segregation), eventual selective iodine expulsion, and subsequent changes in photoinduced halide segregation behavior. By quantifying structural and compositional changes, we estimate an approximately 3–5% iodine loss in our mixed-halide samples after only 24 h of illumination. Further, using microscale measurements, we identify pre-existing iodide-rich domains as key contributors to both the observed transient photostability and permanent iodine loss in MAPbBrI 2 , and see evidence that extended light soaking results in iodide redistribution that improves optoelectronic homogeneity. Overall, our results emphasize the importance of carrier-induced halide oxidation in creating a dynamic defect landscape in mixed-halide perovskites and provide a framework for interpreting apparent light-driven changes in optoelectronic behavior through the lens of permanent compositional changes.

electrical conductivity↗
DOE OSTI2025

Design principles of spacer cations for suppressing phase segregation in 2D halide perovskites

Suppression of photoinduced halide segregation in mixed halide perovskites remains a significant challenge for their application as wide bandgap semiconductors in solar cells. In addition to stability issues, halide segregation leads to a loss in power conversion efficiency in solar cells and a shift in emission wavelength in light-emitting devices. However, employing low-dimensional halide perovskites, such as two-dimensional (2D) or quasi-2D structures, offers a strategy to mitigate this segregation. Here, we have systematically studied how the molecular structure and binding configuration of spacer cations, ranging from linear alkyl chains to aromatic structures, affect photoinduced halide segregation across both Ruddlesden–Popper (RP) and Dion–Jacobson (DJ) frameworks in 2D mixed halide perovskites (Br : I = 50 : 50). Aromatic spacer cations within the DJ perovskite configuration were found to suppress segregation most effectively. For example, the halide segregation rate in a 2D mixed halide perovskite film with the DJ phase using the aromatic spacer cation 1,4-phenylenedimethanammonium (PDMA) was 9.3 × 10 −4 s −1 —an order of magnitude lower than that observed with linear 2D RP perovskites employing butylammonium (BA) as the spacer cation (6.1 × 10 −3 s −1 ). Spectroscopic studies detailing the influence of spacer cation selection in mixed halide perovskites for suppressing phase segregation are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Stabilizing Iodine in 2D Mixed Halide Perovskites: Dion–Jacobson Versus Ruddlesden–Popper Phases

Iodine electrochemistry plays an important role in driving iodide‐oxidation induced halide migration in 3D halide perovskites. When subjected to light illumination or electrochemical bias, mixed halide perovskites undergo halide segregation followed by iodine expulsion from the crystal lattices. To mitigate such intrinsic halide ion mobility in 3D perovskites, lower‐dimensional (2D) perovskites are employed as barriers to stabilize the perovskite layers. Interestingly, 2D halide perovskites also exhibit halide ion mobility that is dependent on the binding configuration, viz., Ruddlesden–Popper (RP) and Dion–Jacobson (DJ) phases. Hybrid RP‐DJ perovskites with a mixed Br:I ratio of 50:50 show increased stability following continuous photoirradiation. Spectroscopic studies that probe iodine migration and expulsion in photoirradiated 2D films of different configurations are presented here. The effective strategy of blending two different 2D phases (RP‐DJ) offers new opportunities to develop stable 2D/3D perovskite interfaces in solar cells.

2D halide perovskites↗
DOE OSTI2024

Spectroelectrochemical insights into the intrinsic nature of lead halide perovskites

Abstract Lead halide perovskites have emerged as a new class of semiconductor materials with exceptional optoelectronic properties, sparking significant research interest in photovoltaics and light-emitting diodes. However, achieving long-term operational stability remains a critical hurdle. The soft, ionic nature of the halide perovskite lattice renders them vulnerable to various instabilities. These instabilities can be triggered by factors such as photoexcitation, electrical bias, and the surrounding electrolyte/solvent or atmosphere under operating conditions. Spectroelectrochemistry offers a powerful approach to bridge the gap between electrochemistry and photochemistry (or spectroscopy), by providing a comprehensive understanding of the band structure and excited-state dynamics of halide perovskites. This review summarizes recent advances that highlight the fundamental principles, the electronic band structure of halide perovskite materials, and the photoelectrochemical phenomena observed upon photo- and electro-chemical charge injections. Further, we discuss halide instability, encompassing halide oxidation, vacancy formation, ion migration, degradation, and sequential expulsion under electrical bias. Spectroelectrochemical studies that provide a deeper understanding of interfacial processes and halide mobility can pave the way for the design of more robust perovskites, accelerating future research and development efforts. Graphical Abstract

Min, Seonhong↗
DOE OSTI2025

Tuning Solvation Dynamics of Electrolytes at Their Eutectic Point Through Halide Identity

Deep eutectic solvents (DESs) are regarded as highly promising solvent systems for redox flow batteries. DESs, composed of choline halides (ChX, X = F − , Cl − , Br − , I − ) and ethylene glycol (EG), exhibit distinct physicochemical properties at their eutectic points, including halide-dependent phase behavior, viscosity, polarity, conductivity, and solvation dynamics. In this study, we investigate the effects of the halide identity on the solvation properties of ChX:EG mixtures at varying mol % of ChX salt content. The solvatochromic polarity based on ET(30) measurements indicates higher polarity for larger halides (I − > Br − ) than for smaller halides (Cl − > F − ), which exhibit larger compensating solvation shells. The ionic conductivity follows the trend of the solvent fluidity (the inverse of the viscosity), namely ChCl > ChBr > ChI > ChF, influenced by the ion mobility and solvodynamic radii. Measurements of the liquidus temperatures (T L ) reveal that the system with ChCl exhibits the deepest eutectic point (at ~20 mol % ChCl), while ChBr and ChI have shallower minima at ~10 mol % ChBr and ~3 mol % ChI, respectively. ChF does not display a eutectic transition but instead appears to readily supercool at salt concentrations above 30 mol % ChF. Consistent with the phase transition measurements, femtosecond transient absorption spectroscopy shows that in the ChCl system, the solvation dynamics become faster with an increasing salt concentration up to ~16.67 mol %, after which the dynamics slow down with further increases in the salt content. The ChF-based system exhibits similar behavior, though with slower dynamics. In contrast, the solvation dynamics of the systems containing ChBr and ChI monotonously slow down with an increasing salt concentration, in agreement with the phase transition measurements, which show that the eutectic points occur at low salt concentrations. These measurements suggest that the solvent composition and, in particular, the identity of the halide anion play a significant role in the solvation behavior of these ethylene-glycol-based DESs, offering a foundation for tuning the DES properties for specific applications.

Biochemistry & Molecular Biology↗
DOE OSTI2025

Halide perovskite-polymer composite film for bright and stable light-emitting devices

Stability is the primary hindrance for the application of halide perovskite material in light-emitting devices, solar cells, and other devices. In this work, halide perovskite and polymer composite film have been prepared for stable and bright light-emitting devices. Pure-phase Cs4PbBr6 crystals have been synthesized, and their photoluminescence (PL) properties and fluorescence lifetimes have been investigated. The Cs 4 PbBr 6 crystals exhibited high uniformity but underwent rapid photodegradation under light irradiation. To address this issue, we prepared bright light-emitting devices using composite of Cs 4 PbBr 6 crystals and polyethylene oxide (PEO) as the emission layer. The aim was to improve the optical and physical properties of halide perovskites, such as photodegradation and stability. PEO, with its excellent film-forming ability, created a uniform and dense film on the halide perovskite surface, filling microscopic defects and providing a protective barrier. FTIR, morphology, and PL analyses confirmed the protective role of the halide perovskite and polymer composite film. The composite film light-emitting devices demonstrated improved stability and higher PL brightness, with a peak brightness approaching 3 × 10 8 cd/m 2 , which was approximately 75% higher than the pure halide perovskite devices.

Composite film↗
DOE OSTI2026

Photophysical Properties and Phase Behavior of Ultrawide Photovoltaic Bandgap Cesium–Lead-Based Triple Halide Perovskites

Metal halide perovskite films in the top cell of triple-junction tandems require bandgaps around 2.0 eV to achieve current matching, assuming that the middle absorbing layer is the commonly used FAPbI 3 composition and the bottom cell has a bandgap around 1.1 eV. Unfortunately, mixed organic/inorganic metal halide perovskites that have the necessary Br content to reach a bandgap of 2.0 eV segregate into iodine-rich and bromine-rich phases under illumination, limiting their obtainable voltage. Previous reports have shown improved photostability using either Cs-based inorganic compositions or Cl incorporation on the X-site. Here, we investigate the inorganic triple halide compositional space CsPb­(I 1–x–y Br y Cl x ) 3 where bandgaps near 2.0 eV are expected based on the knowledge that CsPbI2Br has a bandgap of 1.90 eV. Incorporation of Cl occurs readily for x ≤ 0.07–0.10 within perovskites with a Br content of 0.3 ≤ y ≤ 0.42. When x >0.1, X-ray diffraction and photoluminescence (PL) measurements indicate that multiple compositional phases form. We hypothesize that the variable sizes of the three halide ions are not supported within the rigid Cs lattice, resulting in the formation of multiple compositional phases. The photoluminescence quantum yield of the single-phase compositional space–CsPb­(I 1–x–y Br y Cl x ) 3 where x ≤ 0.07was typically 0.001–0.004%, most likely as a result of a high defect density, including mobile iodine species. PL light-soaking measurements of many perovskite compositions with bandgaps in the range of 1.89–2.05 eV demonstrate that phase segregation occurs when initial bandgaps are above 1.95 eV regardless of halide content: indicating further iodide oxidation and corresponding migration under illumination. The conclusion is that further compositional or additive engineering is necessary for the development of inorganic triple halide compositions that accomplish the elusive goal of fabricating high-quality and photostable 2.0 eV films for use in multijunction tandems.

Electrical conductivity↗
NASA NTRS1973

Flame inhibition by hydrogen halides - Some spectroscopic measurements

The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

Lerner, N. R.↗
DOE OSTI2025

Trade‐Off Between Toxicity and Efficiency in Tin‐ versus Lead‐Based Halide Perovskites

Toxicity remains one of the major challenges that prevent Pb-based halide perovskites from widespread utilization. Ideally, non-toxic alternatives can be identified while still maintaining the superior power conversion efficiency of the Pb-based perovskite solar cells. Using the currently most promising candidate, the Sn-based halide perovskites, as an example, we show that a trade-off exists between toxicity and efficiency in the Sn- versus Pb-based halide perovskites. Indeed, the dominant nonradiative recombination center in the Sn-based halide perovskites differs from the one in its Pb-based counterparts, resulting in the nonradiative capture coefficient in CsSnI 3 being an order of magnitude higher than that in CsPbI 3 . We attribute this difference to the band alignment. Here, our results indicate that development of halide perovskites beyond the Pb and Sn bases is essential for efficient yet environmentally friendly perovskite solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dual modulation of the anion-driven thermodynamic properties of aqueous choline halide-based deep eutectic solvents

Deep eutectic solvents (DESs) are considered tunable solvents because their specific properties can be achieved based on the choice of components and their relative concentrations in a mixture. In this article, we investigate the influence of the variation in halide ions (F − , Cl − , Br − , I − ) of choline salts used on the thermodynamic and physicochemical properties of choline halide-based DESs. Our findings show that the density of choline halide-based DESs decreases nonlinearly with an increasing mole fraction of water, following a trend based on the size of the halides, with choline iodide showing the highest density. Temperature-dependent density data reveal that the thermal expansion coefficient decreases slightly with increasing water content, indicating a more stable volume at a higher mole fraction of water. The excess molar volume (V E ) of the DES mixtures exhibits complex behavior depending on the choline halide used, with both negative and positive V E values observed across different water mole fractions. These variations are linked to the hydrogen bonding interactions between the DES components and water molecules. In addition, viscosities decrease with increasing water content, suggesting the disruption of hydrogen bonding networks and enhanced mobility of the ions, which contributes to the observed increase in conductivity. The excess molar Gibbs energies, enthalpies, and entropies of activation have also been determined.

Choline halide↗
DOE OSTI2025

Hybrid Metal Halides: Advancing Optoelectronic Materials (Final Technical Report)

Hybrid metal halides, particularly main group halide perovskites, are a unique class of materials that offer exceptional optoelectronic properties along with a remarkable materials design space. Initial research on this class of materials was driven by the ability of the prototype hybrid 3D perovskite-structured compound methylammonium lead iodide to function as the active layer in thin film solar cells. It is now known that this class of materials comprise a large family with tunable band gaps, relatively high charge carrier mobilities in both single crystal and polycrystalline forms, and relatively low concentrations of (deleterious) electrically active states within the band gap. Beyond applications in solar cells, the potential of these materials has been extended to emitters in light emitting diodes, and active components of radiation detectors. Complementing new functionality, the design space for hybrid metal halides continues to increase with discovery of new structural motifs. In this project, the combination of organic and inorganic functionalities has been employed to open pathways to the design and synthesis new, functional hybrid metal halides. Beyond the simple perovskites, Ruddlesden-Popper and Dion-Jacobsen compounds, and other variants, such as the newly advanced “hollow” perovskites have been studied. The materials have provided routes to understanding the unique electronic properties of hybrid metal halides because of their natural quantum well structures as well as other means of controlling band gaps and band dispersions. Understanding these materials, including the design rules for their formation, their structures and compositions in bulk and in thin films form, and the role of local (non-crystallographic) structure has an important aspect of this endeavor. The goal of advancing new materials and new fundamental understanding within this deceptively simple, yet fascinating class of compounds, so richly endowed with interesting and useful functionality, has been fulfilled.

36 MATERIALS SCIENCE↗