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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Lower-length-scale modeling of chemical additions, corrosion and fission products in select MSR base salts

Molten salts play a crucial role in advancing Generation IV nuclear energy technology, with chloride-based salts like NaCl-UCl 3 garnering significant attention due to their distinctive properties. However, the corrosive nature of molten salts causes the dissolution of chromium (Cr), leading to the formation of CrCl 2 and CrCl 3 species in molten chlorides. Moreover, the radioactive decay of nuclear fuel gives rise to fission products, including Cs, Sr, and I chlorides. The first part of this report presents a comprehensive study utilizing ab initio molecular dynamics (AIMD) simulations to investigate the properties of eutectic NaCl-UCl 3 molten salt in the presence of corrosion products (CrCl 2 and CrCl 3 ) and fission product (CsCl). The study focuses on essential structural and thermophysical properties such as density, mixing energy, coordination numbers (CN), and Radial Distribution Functions (RDF) of the salts with varying compositions of corrosion products and fission product, covering a range from 0% to 13.5%. The results offer valuable insights into the behavior of corrosion and fission products in uranium-based molten salts, providing essential data that can be used as input to the MTDB-TC and MSTDB-TP property databases being developed by the NEAMS program. Due to their favorable characteristics such as low melting points, high boiling points, and low costs, MgCl 2 +NaCl+KCl (MNK) eutectic salts have recently attracted attention as high-temperature heat transfer fluids. The incorporation of LiCl into MNK salts can further reduce their melting points and increase their specific heat capacities, which is de- sirable for high-temperature heat transfer applications. The second part of this report presents the development and validation of a new shell-model potential for the MgCl 2 +NaCl+KCl+LiCl system, which captures the polarization of Cl anions. The extensive comparison with experimental data and AIMD simulations demonstrates the accuracy and reliability of the potential. Furthermore, using this potential, we elucidate the intricate network structure in MNK eutectic salts that is formed through polyhedron sharing. This research contributes to a fundamental understanding of the atomic structures and thermophysical properties of multi-component molten salts, which is crucial for future development of heat transfer fluids for applications in molten salt reactors.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electron vacancy-level dependent hybrid photoionization of the F–@C60+molecule: A novel effect

Our previous studies [J. Phys. B 53, 125101 (2020); Euro. Phys. J. D 74, 191 (2020)] have predicted that the atom-fullerene hybrid photoionization properties for X = Cl, Br and I endohedrally confined in C60 are different before and after an electron transfers from C60 to the halogen. It was further found as a rule that the ionization dynamics is insensitive to the C60level the electron originates from to produce X–@C60+ . In the current study, we report an exception to this rule in F@C60. It is found that when the electron vacancy is situated in the C60level that participates in the hybridization in F–@C60+, the mixing becomes dramatically large leading to strong modifications in the photoionization of the hybrid levels. This novel effect is fundamentally based on a level-crossing phenomenon driven by the electron transfer in F@C60. But when the vacancy is at any other pure level of C60, the level-invariance is retained showing weak hybridization. Even though this case of F@C60 is an exception in the halogen@C60 series, the phenomenon can be more general and can occur with compounds of other atoms caged in a variety of fullerenes. Possible experimental studies are suggested to benchmark the present results.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Site-specific plan-view (S)TEM sample preparation from thin films using a dual-beam FIB-SEM

To fully evaluate the atomic structure, and associated properties of materials using transmission electron microscopy, examination of samples from three non-collinear orientations is needed. This is particularly challenging for thin films and nanoscale devices built on substrates due to limitations with plan-view sample preparation. In this work, a new method for preparation of high-quality, site-specific, plan-view TEM samples from thin-films grown on substrates, is presented and discussed. Here, it is based on using a dual-beam focused ion beam scanning electron microscope (FIB-SEM) system. To demonstrate the method, the samples were prepared from thin films of perovskite oxide BaSnO 3 grown on a SrTiO 3 substrate and metal oxide IrO 2 on a TiO 2 substrate, ranging from 20–80 nm in thicknesses using molecular beam epitaxy. While the method is optimized for the thin films, it can be extended to other site-specific plan-view samples and devices build on wafers. Aberration-corrected STEM was used to evaluate the quality of the samples and their applicability for atomic-resolution imaging and analysis.

BaSnO3↗
DOE OSTI2026

Oxygen Distribution and Segregation at Grain Boundaries in Nb and Ta-Encapsulated Nb Thin Films for Superconducting Qubits

We report on atomic-scale analyses of oxygen distribution and segregation at grain boundaries (GBs) of Nb and Ta-encapsulated Nb (Ta/Nb) thin films for superconducting qubits using atom probe tomography (APT) and transmission electron microscopy (TEM). We observe oxygen segregation at grain boundaries (GBs) relative to the oxygen concentration within the grains for both Nb and Ta-capped Nb thin films and find that a higher oxygen concentration in the interior of Nb grains leads to greater oxygen segregation levels at GBs. This finding reveals that the formation of a local equilibrium of oxygen concentration between GBs and grain interiors of Nb is the primary driving force of the oxygen segregation behaviors in Nb and Ta-capped Nb. The enrichment factors (CGB/Cgrain) for oxygen segregation at GBs in Nb and Ta-capped Nb range from 2.4 ± 0.3 to 2.7 ± 0.4. The current results also highlight that controlling oxygen impurities in Nb during film deposition and fabrication processing is important to concomitantly reducing the level of oxygen segregation at GBs in Nb. Finally, we find that increases in the oxygen concentration in both Nb grains and GBs correlate with a suppression in the critical temperature for superconductivity (Tc). Together, our comparative chemical and charge transport property analyses provide atomic-scale insights into a potential mechanism, contributing to the decoherence in superconducting qubits.

Lee, Jaeyel [Fermilab] (ORCID:0000000185429612)↗
DOE OSTI2024

Atomic-scale oxygen-vacancy engineering in Sub-2 nm thin Al 2 O 3 /MgO memristors

Ultrathin (sub-2 nm) Al 2 O 3 /MgO memristors were recently developed using an in vacuo atomic layer deposition (ALD) process that minimizes unintended defects and prevents undesirable leakage current. These memristors provide a unique platform that allows oxygen vacancies (V O ) to be inserted into the memristor with atomic precision and study how this affects the formation and rupture of conductive filaments (CFs) during memristive switching. Herein, we present a systematic study on three sets of ultrathin Al 2 O 3 /MgO memristors with V O -doping via modular MgO atomic layer insertion into an otherwise pristine insulating Al 2 O 3 atomic layer stack (ALS) using an in vacuo ALD. At a fixed memristor thickness of 17 Al 2 O 3 /MgO atomic layers (~1.9 nm), the properties of the memristors were found to be affected by the number and stacking pattern of the MgO atomic layers in the Al 2 O 3 /MgO ALS. Importantly, the trend of reduced low-state resistance and the increasing appearance of multi-step switches with an increasing number of MgO atomic layers suggests a direct correlation between the dimension and dynamic evolution of the conducting filaments and the V O concentration and distribution. Understanding such a correlation is critical to an atomic-scale control of the switching behavior of ultrathin memristors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Inorganic Water Repellent Coatings for Thermal Protection Insulation on an Aerospace Vehicle

The objective of this research was two-fold: first, to identify and test inorganic water-repellent materials that would be hydrophobic even after thermal cycling to temperatures above 600 C and, second, to develop a model that would link hydrophobicity of a material to the chemical properties of its constituent atoms. Four different materials were selected for detailed experimental study, namely, boron nitride, talc, molybdenite, and pyrophyllite, all of which have a layered structure made up of ionic/covalent bonds within the layers but with van der Waals bonds between the layers. The materials tested could be considered hydrophobic for a nonporous surface but none of the observed contact angles exceeded the necessary 90 degrees required for water repellency of porous materials. Boron nitride and talc were observed to retain their water-repellency when heated in air to temperatures that did not exceed 800 C, and molybdenite was found to be retain its hydrophobicity when heated to temperatures up to 600 C. For these three materials, oxidation and decomposition were identified to be the main cause for the breakdown of water repellency after repeated thermal cycling. Pyrophyllite shows the maximum promise as a potential water-repellent inorganic material, which, when treated initially at 900 C, retained its shape and remained hydrophobic for two thermal cycles where the maximum retreatment temperature is 900 C. A model was developed for predicting materials that might exhibit hydrophobicity by linking two chemical properties, namely, that the constituent ions of the compound belong to the soft acid-base category and that the fractional ionic character of the bonds be less than about 20 percent.

Fuerstenau, D. W.↗
NASA NTRS1997

Inorganic Water Repellent Coatings for Thermal Protection Insulation on an Aerospace Vehicle

The objective of this research was two-fold: first, to identify and test inorganic water-repellent materials that would be hydrophobic even after thermal cycling to temperatures above 600 C and, second, to develop a model that would link hydrophobicity of a material to the chemical properties of its constituent atoms. Four different materials were selected for detailed experimental study, namely, boron nitride, talc, molybdenite, and pyrophyllite, all of which have a layered structure made up of ionic/covalent bonds within the layers but with van der Waals bonds between the layers. The materials tested could be considered hydrophobic for a nonporous surface but none of the observed contact angles exceeded the necessary 90 degrees required for water repellency of porous materials. Boron nitride and talc were observed to retain their water-repellency when heated in air to temperatures that did not exceed 800 C, and molybdenite was found to be retain its hydrophobicity when heated to temperatures up to 600 C. For these three materials, oxidation and decomposition were identified to be the main cause for the breakdown of water repellency after repeated thermal cycling. Pyrophyllite shows the maximum promise as a potential water-repellent inorganic material, which, when treated initially at 900 C, retained its shape and remained hydrophobic for two thermal cycles where the maximum retreatment temperature is 900 C. A model was developed for predicting materials that might exhibit hydrophobicity by linking two chemical properties, namely, that the constituent ions of the compound belong to the soft acid-base category and that the fractional ionic character of the bonds be less than about 20 percent.

Fuerstenau, D. W.↗
DOE OSTI2025

Nanometer Resolution Structure‐Emission Correlation of Individual Quantum Emitters via Enhanced Cathodoluminescence in Twisted Hexagonal Boron Nitride

Understanding the atomic structure of quantum emitters, often originating from point defects or impuritie, is essential for designing and optimizing materials for quantum technologies such as quantum computing, communication, and sensing. Despite the availability of atomic-resolution scanning transmission electron microscopy and nanoscale cathodoluminescence microscopy, experimentally determining the atomic structure of individual emitters is challenging due to the conflicting needs for thick samples to generate strong cathodoluminescence signals and thin samples for structural analysis. To overcome this challenge, significantly enhanced cathodoluminescence at twisted interfaces is leveraged to achieve sub-nanometer localization precision for the first time in mapping individual quantum emitters in carbon-implanted hexagonal boron nitride. This unprecedent spatial sensitivity, together with correlative electron energy loss spectroscopy quantitative scanning transmission electron microscopy imaging, and first principles density functional theory calculations, enables the identification of the atomic structure of the 440 nm blue emitter in hexagonal boron nitride as a substituted vertical carbon dimer. Building on the atomic structure insights, nanoscale spatially precise creation of blue emitters is demonstrated by electron beam irradiation of carbon-coated hexagonal boron nitride. This advancement in correlating atomic structures with optical properties lays the foundation for a deeper understanding and precise engineering of quantum emitters, significantly advancing the development of cutting-edge quantum information technologies.

2D material↗
DOE OSTI2023

Does photoinduced structural change by β-rhombohedral boron occur at room temperature?

β-rhombohedral boron (β-B) is an intriguing solid among the elements. The crystal structure of β-B is widely accepted as a complex structure based on the B 12 clusters, and with a lot of intrinsic structural defects. In the last decade, β-B was proved to be the only elemental semiconductor that exhibits the self-compensation property accompanied by changing structural defects during atom doping. Moreover, it is reported that various physical properties of β-B change discontinuously around 550 K, which may originate from defect diffusion [S. Hoffmann and H. Werheit, Solid State Sciences 14, 1572 (2012)]. We previously reported that a volume expansion of about 1.5% takes place above this temperature (between 650 K and 850 K). On the other hand, this expanded structure is stable in dark conditions for more than 4.5 months. Finally, light irradiation at room temperature reverses the volume back to the initial state, and a possible scenario will be discussed in this paper.

36 MATERIALS SCIENCE↗
NASA NTRS1999

Mars 2001 Lander Mission: Measurement Synergy Through Coordinated Operations Planning And Implementation

The 2001 Mars Surveyor Program Mission includes an orbiter with a gamma ray spectrometer and a multispectral thermal imager, and a lander with an extensive set of instrumentation, a robotic arm, and the Marie Curie Rover. The Mars 2001 Science Operations Working Group (SOWG) is a subgroup of the Project Science Group that has been formed to provide coordinated planning and implementation of scientific observations, particularly for the landed portion of the mission. The SOWG will be responsible for delivery of a science plan and, during operations, generation and delivery of conflict-free sequences. This group will also develop an archive plan that is compliant with Planetary Data System (PDS) standards, and will oversee generation, validation, and delivery of integrated archives to the PDS. In this report we cover one element of the SOWG planning activities, the development of a plan that maximizes the scientific return from lander-based observations by treating the instrument packages as an integrated payload. Scientific objectives for the lander mission have been defined. They include observations focused on determining the bedrock geology of the site through analyses of rocks and also local materials found in the soils, and the surficial geology of the site, including windblown deposits and the nature and history of formation of indurated sediments such as duricrust. Of particular interest is the identification and quantification of processes related to early warm, wet conditions and the presence of hydrologic or hydrothermal cycles. Determining the nature and origin of duricrust and associated salts is -very important in this regard. Specifically, did these deposits form in the vadose zone as pore water evaporated from soils or did they form by other processes, such as deposition of volcanic aerosols? Basic information needed to address these questions includes the morphology, topography, and geologic context of landforms and materials exposed at the site, together with quantitative information on material mineralogy, chemistry, and physical properties (rock textures; soil grain size and shape distributions; degree and nature of soil induration; soil magnetic properties). The calibration targets provide radiometric and mineralogical control surfaces. The magnets allow observations of magnetic phases. Patch plates are imaged to determine adhesive and abrasive properties of soils. Coordinated mission planning is crucial for optimizing the measurement synergy among the packages included on the lander. This planning has already begun through generation of multi-sol detailed operations activities. One focus has been to develop a scenario to use the arm to dig a soil trench to a depth of tens of centimeters. The activity will be monitored through use of Pancam and RAC to ensure nominal operations and to acquire data to determine subsurface physical properties (e.g., angle of repose of trench walls). Pancam and Mini-TES observations would also provide constraints on mineralogy and texture for the walls and bottom of the trench during excavation. If desired, soils excavated at depth could be deposited on the surface and Mossbauer and APXS measurements could be acquired for these materials. Soil samples from various depths would be delivered to MECA for characterization of aqueous geochemistry and physical properties of soil grains, particularly size, shape, and hardness. These physical properties would be determined by optical and atomic force microscopy. When completed, detailed information of soil properties as a function of depth would be obtained. These various data sets would constrain our understanding of whether or not there are systematic variations in soil characteristics as a function of depth. These variations might be related, for example, to evaporative moisture losses and formation of salt deposits, thereby indicating water transport processes occurred fairly recently. Many other value-added measurement scenarios are being developed. For example, characterizing the nature and dynamics of dust deposition will be done using MIP/DART to provide deposition rates, Pancam and RAC imaging of lander and rover surfaces to extrapolate these measurements to other areas, and a variety of measurements to determine if the bulk loose soil has the same characteristics as dust that accumulates during the mission. Bedrock geology of the site is primarily an APEX-focus setting, mineralogy, and texture, and APXS data to be we interest will be to determine the extent to which rock hydrothermal processes, given that APEX is the precursor 4 and 2005 rover missions. Additional information is contained in the original.

Arvidson, R.↗
NASA NTRS2003

Optical measurements of gravity fields

Optical measurements of a gravitational field with sensitivity close to the sensitivity of atomic devices are possible if one detects properties of light after its interaction with optically thick atomic cloud moving freely in the gravity field. A nondestructive detection of a number of ultracold atoms in a cloud as well as tracking of the ground state population distribution of the atoms is possible by optical means.

whispering gallery modes microwave detection modul↗
DOE OSTI2021

A general strategy for preparing pyrrolic-N 4 type single-atom catalysts via pre-located isolated atoms

Single-atom catalysts (SACs) have been applied in many fields due to their superior catalytic performance. Because of the unique properties of the single-atom-site, using the single atoms as catalysts to synthesize SACs is promising. In this work, we have successfully achieved Co 1 SAC using Pt 1 atoms as catalysts. More importantly, this synthesis strategy can be extended to achieve Fe and Ni SACs as well. X-ray absorption spectroscopy (XAS) results demonstrate that the achieved Fe, Co, and Ni SACs are in a M1-pyrrolic N 4 (M= Fe, Co, and Ni) structure. Density functional theory (DFT) studies show that the Co(Cp) 2 dissociation is enhanced by Pt 1 atoms, thus leading to the formation of Co 1 atoms instead of nanoparticles. These SACs are also evaluated under hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the nature of active sites under HER are unveiled by the operando XAS studies. These new findings extend the application fields of SACs to catalytic fabrication methodology, which is promising for the rational design of advanced SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Measurements of the optical properties of thin films of silver and silver oxide

The optical properties of silver films and their oxides are measured to better characterize such films for use as sensors for atomic oxygen. Good agreement between properties of measured pure silver films and reported optical constants is observed. Similar comparisons for silver oxide have not been possible because of a lack of reported constants, but self-consistencies and discrepancies in our measured results are described.

Peters, Palmer N.↗
NASA NTRS2005

Variations in the Peak Position of the 6.2 micron Interstellar Emission Feature: A Tracer of N in the Interstellar Polycyclic Aromatic Hydrocarbon Population

This paper presents the results of an investigation of the molecular characteristics that underlie the observed peak position and profile of the nominal 6.2 micron interstellar emission band generally attributed to the CC stretching vibrations of polycyclic aromatic hydrocarbons (PAHs). It begins with a summary of recent experimental and theoretical studies ofthe spectroscopic properties of large (>30 carbon atoms) PAH cations as they relate to this aspect of the astrophysical problem. It then continues with an examination of the spectroscopic properties of a number of PAH variants within the context of the interstellar 6.2 micron emission, beginning with a class of compounds known as polycyclic aromatic nitrogen heterocycles (PANHs; PAHs with one or more nitrogen atoms substituted into their carbon skeleton). In this regard, we summarize the results of recent relevant experimental studies involving a limited set of small PANHs and their cations and then report the results of a comprehensive computational study that extends that work to larger PANH cations including many nitrogen-substituted variants of coronene(+) (C24H12(+)), ovalene(+) (C32H14(+)), circumcoronene(+) (C54H18(+)), and circum-circumcoronene(+) (C96H24(+)). Finally, we report the results of more focused computational studies of selected representatives from a number of other classes of PAH variants that share one or more of the key attributes of the PANH species studied. These alternative classes of PAH variants include (1) oxygen- and silicon-substituted PAH cations; (2) PAH-metal ion complexes (metallocenes) involving the cosmically abundant elements magnesium and iron; and (3) large, asymmetric PAH cations. Overall, the studies reported here demonstrate that increasing PAH size alone is insuEcient to account for the position of the shortest wavelength interstellar 6.2 micron emission bands, as had been suggested by earlier studies. On the other hand, this work reveals that substitution of one or more nitrogen atoms within the interior of the carbon skeleton of a PAH cation induces a significant blueshift in the position of the dominant CC stretching feature of these compounds that is suf6cient to account for the position of the interstellar bands. Subsequent studies of the effects of substitution by other heteroatoms (O and Si), metal ion complexation (Fe(+), Mg(+), and Mg(2+)), and molecular symmetry variation-all of which fail to reproduce the blueshift observed in the PANH cations-indicate that N appears to be unique in its ability to accommodate the position of the interstellar 6.2 micron bands while simultaneously satisfying the other constraints of the astrophysical problem. This result implies that the peak position of the interstellar feature near 6.2 micron traces the degree of nitrogen substitution in the population, that most of the PAHs responsible for the interstellar IR emission features incorporate nitrogen within their aromatic networks, and that a lower limit of 1%-2% of the cosmic nitrogen is sequestered within the interstellar PAH population. Finally, in view of the ubiquity and abundance of interstellar PAHs and the permanent dipoles and distinctive electronic structures of these nitrogen-substituted variants, this work impacts a wide range of observational phenomena outside of the infrared region of the spectrum including the forest of unidentified molecular rotational features and the anomalous Galactic foreground emission in the microwave, and the diffuse interstellar bands (DIBs) and other structure in the interstellar extinction curve in the ulhviolet/visible. These astrophysical ramifications are discussed, and the dipole moments and rotational constants are tabulated to facilitate further investigations of the astrophysical role of nitrogen-substituted aromatic compounds.

Hudgins, Douglas M.↗
DOE OSTI2024

Embracing disorder in quantum materials design

Many of the most exciting materials discoveries in fundamental condensed matter physics are made in systems hosting some degree of intrinsic disorder. While disorder has historically been regarded as something to be avoided in materials design, it is often of central importance to correlated and quantum materials. This is largely driven by the conceptual and theoretical ease to handle, predict, and understand highly uniform systems that exhibit complex interactions, symmetries, and band structures. In this Perspective, we highlight how flipping this paradigm has enabled exciting possibilities in the emerging field of high entropy materials, focusing primarily on high entropy oxide and chalcogenide quantum materials. These materials host high levels of cation or anion compositional disorder while maintaining unexpectedly uniform single crystal lattices. The diversity of atomic scale interactions of spin, charge, orbital, and lattice degrees of freedom are found to emerge into coherent properties on much larger length scales. Thus, altering the variance and magnitudes of the atomic scale properties through elemental selection can open new routes to tune global correlated phases, such as magnetism, metal–insulator transitions, ferroelectricity, and even emergent topological responses. The strategy of embracing disorder in this way provides a much broader pallet from which functional states can be designed for next-generation microelectronic and quantum information systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Embracing Disorder in Quantum Materials Design

Many of the most exciting materials discoveries in fundamental condensed matter physics are made in systems hosting some degree of intrinsic disorder. While disorder has historically been regarded as something to be avoided in materials design, it is often of central importance to correlated and quantum materials. This is largely driven by the conceptual and theoretical ease to handle, predict, and understand highly uniform systems that exhibit complex interactions, symmetries, and band structures. In this Perspective, we highlight how flipping this paradigm has enabled exciting possibilities in the emerging field of high entropy materials, focusing primarily on high entropy oxide and chalcogenide quantum materials. These materials host high levels of cation or anion compositional disorder while maintaining unexpectedly uniform single crystal lattices. The diversity of atomic scale interactions of spin, charge, orbital, and lattice degrees of freedom are found to emerge into coherent properties on much larger length scales. Thus, altering the variance and magnitudes of the atomic scale properties through elemental selection can open new routes to tune global correlated phases, such as magnetism, metal–insulator transitions, ferroelectricity, and even emergent topological responses. The strategy of embracing disorder in this way provides a much broader pallet from which functional states can be designed for next-generation microelectronic and quantum information systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Thermally Stable Single-Atom Heterogeneous Catalysts

Single-atom catalysts (SACs) have attracted extensive attention in fields related to energy, environment, and material sciences because of the high atom efficiency and the unique properties of these materials. Many approaches have hitherto been successfully established to prepare SACs, including impregnation, pyrolysis-involved processes, atom trapping, and coprecipitation. However, under typical reaction conditions, single atoms on catalysts tend to migrate or agglomerate, forming nanoclusters or nanoparticles, which lowers their surface free energy. Efforts are required to develop strategies for improving the thermal stability of SACs while achieving excellent catalytic performance. Here in this Progress Report, recent advances in the development of thermally durable single-atom heterogeneous catalysts are discussed. Several important preparation approaches for thermally stable SACs are described in this article. Fundamental understanding of the coordination structures of thermally stable single atom prepared by these methods is discussed. Furthermore, the catalytic performances of these thermally stable SACs are reviewed, including their activity and stability. Finally, a perspective of this important and rapidly evolving research field is provided.

coordination structure↗
DOE OSTI2024

Enhancing Chiroptoelectronic Activity in Chiral 2D Perovskites via Chiral–Achiral Cation Mixing

Rational design of chiral two-dimensional hybrid organic–inorganic perovskites is crucial to achieve chiroptoelecronic, spintronic, and ferroelectric applications. Here, in this study, an efficient way to manipulate the chiroptoelectronic activity of 2D lead iodide perovskites is reported by forming mixed chiral (R- or S-methylbenzylammonium (R-MBA + or S-MBA + )) and achiral (n-butylammonium (nBA + )) cations in the organic layer. The strongest and flipped circular dichroism signals are observed in (R/S-MBA 0.5 nBA 0.5 ) 2 PbI 4 films compared to (R/S-MBA) 2 PbI 4 . Moreover, the (R/S-MBA 0.5 nBA 0.5 ) 2 PbI 4 films exhibit pseudo-symmetric, unchanged circularly polarized photoluminescence peak as temperature increases. First-principles calculations reveal that mixed chiral–achiral cations enhance the asymmetric hydrogen-bonding interaction between the organic and inorganic layers, causing more structural distortion, thus, larger spin-polarized band-splitting than pure chiral cations. Temperature-dependent powder X-ray diffraction and pair distribution function structure studies show the compressed intralayer lattice with enlarged interlayer spacing and increased local ordering. Overall, this work demonstrates a new method to tune chiral and chiroptoelectronic properties and reveals their atomic scale structural origins.

2D perovskites↗