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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Discovery of a Ferromagnetic Nickel Chalcogenide Nanocluster Ni 3 S 3 H(PEt 3 ) 5

Atomically precise ligated nanoclusters (NC) are promising cluster-based materials with novel molecular architectures and tunable magnetic properties. Herein, the synthesis and characterization of a nickel sulfide NC Ni 3 S 3 H(PEt 3 ) 5 (PEt 3 = triethylphosphine) with distinct magnetic properties are reported. Magnetization measurements reveal its magnetic moment of 1.5 µ B in the solid phase, consistent with the existence of one unpaired electron predicted by density functional theory (DFT) calculations. Additionally, experimental measurements indicate the presence of ferromagnetic ordering within each Ni 3 S 3 H(PEt 3 ) 5 NC and strong coercivity at temperatures below 20 K. Ion mobility-mass spectrometry is employed in conjunction with DFT calculations and collision cross-section simulations to investigate the structure of the isolated Ni 3 S 3 H(PEt 3 ) 5 . Theoretical studies show that [Ni 3 S 3 H(PEt 3 ) 5 ] + has a planar Ni 3 S 3 core where three Ni atoms are arranged in a triangle with three bridging S atoms residing in the same plane. This structure is preserved in both solution and solid phases, which is confirmed by spectroscopic studies of Ni 3 S 3 H(PEt 3 ) 5 . Additionally, DFT calculations indicate that all spins at the Ni sites are aligned parallel, confirming the presence of ferromagnetic coupling. Overall, this study provides key insights into the structure and magnetic properties of Ni 3 S 3 H(PEt 3 ) 5 , which will facilitate the design of new NC-based magnetic materials.

Nickel sulfide nanocluster↗
DOE OSTI2026

Cryo-EM visualization of viruses from partially irrigated soils

Viruses are numerically the most abundant forms on Earth, and most are present in soil. Even though viruses are highly abundant in soil and critical to rhizosphere function, visualizing the diverse morphotypes within soil has been challenging. The difficulty is primarily due to the heterogenous nature of isolated suspensions that typically contain nanometer to micron scale debris which renders protein crystallography for structural studies unfeasible and hinders cryo-electron microscopy due to ice thickness and contrast issues. Here we employed and compared a simple spin filtration method to cleanup solutions of extracted viruses for direct observation with cryo-electron microscopy. The method employs common physical biochemical separation steps to remove large and small debris which dramatically improves image quality and preservation of structural features to permit visualizing morphotypes not typically seen with conventional negative stain approaches. In addition to tailed and non-tailed polyhedral phages, several under reported or novel morphotypes of soil viruses are directly visualized as a particle library with both 2D and 3D information.

cryo-EM↗
NASA NTRS1992

Breccia dikes from the Beaverhead Impact structure, southwest Montana

While shatter cones are generally accepted as indicators of meteorite impact, older petrologic features are not widely recognized in the geologic community. Breccia dikes are one such feature. They are found in many large impact structures occurring over an area at least as extensively as shatter cones. Breccia dikes will survive moderate degrees of metamorphism and tectonism, unlike many other microscopic features (shocked quartz grains, high-pressure polymorphs, etc.) and even large-scale features such as annular or bowl-shaped topographic features. Thus, they are important diagnostic criteria, especially for large, poorly preserved impact structures. The Beaverhead Impact structure is a recently discovered, deeply eroded impact structure in southwestern Montana. The remains of the structure are delineated by the occurrence of shatter cones, found in an area greater than 200 sq km, occurring within the Cabin thrust plate, part of the Cretaceous Sevier fold and thrust system. The distribution of shatter cones is further truncated by Tertiary normal faults. The present remains represent an allochthonous fragment of a larger structure.

Fiske, P. S.↗
DOE OSTI2025

Bismuthene Under Cover: Graphene Intercalation of a Large Gap Quantum Spin Hall Insulator

Abstract The quantum spin Hall insulator bismuthene, a two‐third monolayer of bismuth on SiC(0001), is distinguished by helical metallic edge states that are protected by a groundbreaking 800 meV topological gap, making it ideal for room temperature applications. This massive gap inversion arises from a unique synergy between flat honeycomb structure, strong spin orbit coupling, and an orbital filtering effect that is mediated by the substrate. However, the rapid oxidation of bismuthene in air has severely hindered the development of applications, so far confining experiments to ultra‐high vacuum conditions. Intercalating bismuthene between SiC and a protective sheet of graphene, this barrier is successfully overcome. As demonstrated by scanning tunneling microscopy and photoemission spectroscopy, graphene intercalation preserves the structural and topological integrity of bismuthene, while effectively shielding it from oxidation in air. Hereby, hydrogen is identified as the critical process gas that was missing in previous bismuth intercalation attempts. These findings facilitate ex‐situ experiments and pave the way for the development of bismuthene based devices, signaling a significant step forward in the development of next‐generation technologies.

Chemistry↗
DOE OSTI2026

Manufacturing Full-Scale High Gradient Copper Accelerators: Electron Beam Welding and Allied Processes

This DOE ARDAP-funded study examines the technical and business feasibility of manufacturing high-gradient normal conducting RF (NCRF) copper accelerating structures using electron beam welding (EBW) instead of conventional high-temperature brazing. The core motivation is material performance: brazing softens copper significantly, while hard copper alloys have demonstrated ~75% higher operational gradients in SLAC tests, making cold-joining techniques highly attractive. EBW, applied to split-cell (half or quadrant) structure designs, preserves copper hardness away from the weld joint and simplifies machining — but industrial process optimization remains immature and a substantial learning curve is expected. The business case was modeled for two scenarios: a greenfield EBW linac company (> $10M upfront costs, viable above ~30 units/year) and an EBW division added to an existing accelerator firm to reduce risk and upfront costs, at the expense of being less optimal structure for the higher volume production. The study concludes that without a significant increase in demand, private investment alone cannot sustain this capability, and recommends federal support through R&D grants, procurement incentives, and CAPEX cost-sharing to incubate domestic EBW-NCRF manufacturing — with the existing-company model.

43 PARTICLE ACCELERATORS↗
NASA NTRS2000

Aerogel Projects Ongoing in MSFC's Engineering Directorate

When we speak of an aerogel material, we are referring more to process and structure am to a specific substance. Aerogel, considered the lightest solid material, has been made from silica for seventy years. Resorcinol-formaldehyde, organic aerogels have been developed more recently. However, aerogel can be made from almost any type of substance, even lead. Because an aerogel is mostly air (about 99 %), the solid substance used will affect the weight very little. The term "aerogel" connotes the sol-gel process used to manufacture the material. The aerogel begins as a liquid "sol," becomes a solid "alcogel," and is then dried to become an "aerogel." The final product has a unique structure, useful for exploitation. It is an "open pore" system with nano-sized particles and pores, has very high surface area, and is highly interconnected. Besides low weight, aerogels have ultimate (lowest) values in other properties: thermal conductivity, refractive index, sound speed, and dielectric constant. Aerogels were first prepared in 1931 by Steven Kistler, who used a supercritical drying step to replace the liquid in a gel with air, preserving the structure (1). Kistler's procedure involved a water-to-alcohol exchange step; in the 1970's, this step was eliminated when a French investigator introduced the use of tetramethylorthosilicate. Still, alcohol drying involved dangerously high temperatures and pressures. In the 1980's, the Microstructured Materials Group at Berkeley Laboratory found that the alcohol in the gel could be replaced with liquid carbon dioxide before supercritical drying, which greatly improved safety (2). 'Me most recent major contribution has been that of Deshpande, Smith and Brinker in New Mexico, who are working to eliminate the supercritical drying step (3). When aerogels were first being developed, they were evaporatively dried. However, the wet gel, when dried, underwent severe shrinkage and cracking; this product was termed "xerogel." When the autoclave drying step was introduced, the final product was without cracks and showed only minimal shrinkage; this product was termed "aerogel." In the 1990's, Deshpande, Smith and Brinker developed an evaporative drying procedure in which the wet gel is chemically "capped" so that the material, which undergoes shrinkage, springs back to its original size when evaporatively dried. This new type of xerogel, while uncracked and almost the same size as the wet gel, differs from the autoclave-dried product in that it is less porous (approximately 70%, as compared to 99% for aerogels).

Shular, David A.↗
DOE OSTI2020

Sparse and Random Sampling Techniques for High-Resolution, Full-Field, BSS-Based Structural Dynamics Identification from Video

Video-based techniques for identification of structural dynamics have the advantage that they are very inexpensive to deploy compared to conventional accelerometer or strain gauge techniques. When structural dynamics from video is accomplished using full-field, high-resolution analysis techniques utilizing algorithms on the pixel time series such as principal components analysis and solutions to blind source separation the added benefit of high-resolution, full-field modal identification is achieved. An important property of video of vibrating structures is that it is particularly sparse. Typically video of vibrating structures has a dimensionality consisting of many thousands or even millions of pixels and hundreds to thousands of frames. However the motion of the vibrating structure can be described using only a few mode shapes and their associated time series. As a result, emerging techniques for sparse and random sampling such as compressive sensing should be applicable to performing modal identification on video. This work presents how full-field, high-resolution, structural dynamics identification frameworks can be coupled with compressive sampling. The techniques described in this work are demonstrated to be able to recover mode shapes from experimental video of vibrating structures when 70% to 90% of the frames from a video captured in the conventional manner are removed.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Metalorganic chemical vapor deposition of ZnGeN 2 films on GaN: effects of cation stoichiometry on surface morphology and crystallinity

Novel optoelectronic device designs based on the heterostructures of III-N and II-IV-N 2 are promising to advance device performance significantly. For example, by utilizing InGaN-ZnGeN 2 quantum well (QW) structures instead of pure InGaN, the band structure engineering in the QW active region can lead to improved electron-hole wavefunction overlap, and thus enhance the radiative efficiency for photon generation. These novel heterostructures have great potential to address the current challenge of low quantum efficiency in InGaN QW based light emitting diodes emitting in green and beyond. The materials development of ZnGeN 2 is still at an early stage as compared to the much matured GaN material system. In an ideal octet rule preserving ordered structure of ZnGeN 2 , every N atom is coordinated by exactly two Zn and two Ge atoms. However, local violation of octet rule can be caused by non-ideal coordination of N by the cations. The disordered structure is thermodynamically less favorable but can still be achieved, for example, in kinetics-limited growth regime. The ordered ZnGeN 2 has a bandgap very close to that of GaN (~3.4 eV) and a lattice mismatch of <0.1% with GaN. Interestingly, the valence band of ZnGeN 2 has been predicted to be ~1 eV above that of GaN, which has inspired novel designs for high efficiency light emitters. In this work, we investigated the metalorganic chemical vapor deposition (MOCVD) of ZnGeN 2 films on GaN/c-sapphire templates. Diethylzinc (DEZn), germane (GeH4) and ammonia were used as the precursors for Zn, Ge and N, respectively. A systematic study was conducted to investigate the cation stoichiometry as a function of growth temperature (TG), total reactor pressure (P) and DEZn/GeH 4 molar flow rate ratio (RII/IV). Under the investigated growth window, the Zn/(Zn+Ge) composition in the films, determined from energy dispersive X-ray spectroscopy, decreased monotonically with increase in TG but increased with increase in P and RII/IV. Atom probe tomography data did not indicate the presence of any secondary phases such as Zn 3 N 2 or Ge 3 N 4 . The surface morphology and crystallinity of the grown films had strong correlation with the Zn/(Zn+Ge) composition. The scanning electron microscopy images showed that the near-stoichiometric films have planar surfaces whereas Zn-rich films had crystallites on their surface and the Zn-poor films had faceted surface. Scanning transmission electron microscopy (STEM) imaging revealed that the Zn-rich and Zn-poor films have columnar and filament-like morphology, respectively, whereas the near-stoichiometric films have continuous film-like cross-sectional morphology. TEM nano-diffraction patterns as well as X-ray diffraction 2θ-ω scan profiles indicate that the near stoichiometric films are single crystalline. Nano-diffraction pattern of the stoichiometric films resembled that of a disordered ZnGeN 2 structure. Room temperature Raman spectra of near-stoichiometric films showed only the phonon density of states like features of a cation disordered ZnGeN 2 . Cathodoluminescence and photoluminescence spectra measured at different temperatures had similar features with peak emission wavelength at ~ 2 eV. In conclusion, the stoichiometry of ZnGeN 2 films can be widely tuned by tuning the MOCVD growth parameters. The surface morphology and the crystallinity of the films were found to have strong correlation with the Zn/(Zn+Ge) composition. The stoichiometric ZnGeN 2 films grown on GaN were demonstrated with uniform surface morphology and high crystalline quality. The results from this work will provide pathway to implement ZnGeN 2 in device structures.

Karim, Md Rezaul↗
DOE OSTI2021

Liquid-induced topological transformations of cellular microstructures

The fundamental topology of cellular structures—the location, number and connectivity of nodes and compartments—can profoundly affect their acoustic, electrical5, chemical, mechanical and optical properties, as well as heat, fluid and particle transport. Approaches that harness swelling, electromagnetic actuation and mechanical instabilities in cellular materials have enabled a variety of interesting wall deformations and compartment shape alterations, but the resulting structures generally preserve the defining connectivity features of the initial topology. Achieving topological transformation presents a distinct challenge for existing strategies: it requires complex reorganization, repacking, and coordinated bending, stretching and folding, particularly around each node, where elastic resistance is highest owing to connectivity. Here we introduce a two-tiered dynamic strategy that achieves systematic reversible transformations of the fundamental topology of cellular microstructures, which can be applied to a wide range of materials and geometries. Our approach requires only exposing the structure to a selected liquid that is able to first infiltrate and plasticize the material at the molecular scale, and then, upon evaporation, form a network of localized capillary forces at the architectural scale that ‘zip’ the edges of the softened lattice into a new topological structure, which subsequently restiffens and remains kinetically trapped. Reversibility is induced by applying a mixture of liquids that act separately at the molecular and architectural scales (thus offering modular temporal control over the softening–evaporation–stiffening sequence) to restore the original topology or provide access to intermediate modes. Guided by a generalized theoretical model that connects cellular geometries, material stiffness and capillary forces, we demonstrate programmed reversible topological transformations of various lattice geometries and responsive materials that undergo fast global or localized deformations. In conclusion, we then harness dynamic topologies to develop active surfaces with information encryption, selective particle trapping and bubble release, as well as tunable mechanical, chemical and acoustic properties.

42 ENGINEERING↗
NASA NTRS1993

Giant radiating dyke swarms on Earth and Venus

On Earth, giant radiating dyke swarms are usually preserved as fan-shaped fragments which have been dismembered from their original configuration by subsequent plate tectonic rifting events. Analysis of the largest fragments and consideration of their original configuration has led to the idea that many swarms are plume related, and that dyke swarms radiate away from plume centers. Magellan radar data reveal abundant intact giant radiating swarms on Venus which are similar in scale and pattern to those on Earth. The absence of intense weathering and plate tectonic processes on Venus accounts for the preservation of the primary radiating patterns. It is characteristic of both Earth and Venus that giant radiating dikes are emplaced laterally for distances of at least 2000 km away from plume centers. At distances beyond the influence of the plume on both Earth and Venus, the radiating dyke pattern is often swept into a linear pattern aligned with the regional stress field. There is tremendous potential synergism between the characterization and analysis of terrestrial dyke swarms (where significant erosion has revealed their structure and emplacement directions at depth) and the giant swarms of Venus (where the complete circumferential structure is preserved, and the surface fracture systems above near surface dikes and the nature of the central source regions are revealed). In this study, we report on the characteristics of radial dyke swarms on Earth and Venus and draw some preliminary comparisons from the two perspectives. In summary, on both planets there is evidence for plume-related magmatic centers associated with vertical and lateral injection of magma over considerable distances (up to at least 2000 km). The abundance of very broadly radiating swarms on Venus supports the notion that the swarms on Earth were radiating over broad sectors at the time of intrusion but were dissected by later events. The Venus data show that a swarm can change from radiating (proximal) to regional (distal) subparallel orientations. An implication for Earth is that many regional linear swarms which do not have a radiating pattern may be due to fragmentation of the swarm during later plate tectonic rifting. Completion of the global classification and census of Venus features, comparison to the terrestrial synthesis, and documentation of the mode of emplacement of dikes in these environments (buffered and unbuffered conditions) should lead to additional general insight into mechanisms of formation and evolution and their relation to plumes.

Ernst, Richard E.↗
DOE OSTI2021

A Method to Preserve Wetland Roots and Rhizospheres for Elemental Imaging

Roots extensively interact with their soil environment but visualizing such interactions between roots and the surrounding rhizosphere is challenging. The rhizosphere chemistry of wetland plants is particularly challenging to capture because of steep oxygen gradients from the roots to the bulk soil. Here a protocol is described that effectively preserves root structure and rhizosphere chemistry of wetland plants through slam-freezing and freeze drying. Slam-freezing, where the sample is frozen between copper blocks pre-cooled with liquid nitrogen, minimizes root damage and sample distortion that can occur with flash-freezing while still minimizing chemical speciation changes. While sample distortion is still possible, the ability to obtain multiple samples quickly and with minimal cost increases the potential to obtain satisfactory samples and optimizes imaging time. The data show that this method is successful in preserving reduced arsenic species in rice roots and rhizospheres associated with iron plaques. This method can be adopted for studies of plant-soil relationships in a wide variety of wetland environments that span concentration ranges from trace-element cycling to phytoremediation applications.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2005

The Plunge Phase of Friction Stir Welding

Torque and plunge force during the initial plunge phase in Friction Stir Welding were measured for a 0.5 inch diameter pin entering a 2219 aluminum alloy plate. Weld structures were preserved for metallographic observation by making emergency stops at various plunge depths. The plunging pin tool is seen to be surrounded by a very fine grained layer of recrystallized metal extending substantially below the bottom of the pin, implying a shear interface in the metal below and not at the tool-metal interface. Torque and plunge force during the initial plunge phase in Friction Stir Welding are calculated from a straight forward model based on a concept to plastic flow in the vicinity of the plunging tool compatible with structural observations. The concept: a disk of weld metal seized to and rotating with the bottom of the pin is squeezed out laterally by the plunge force and extruded upwards in a hollow cylinder around the tool. As the shear surface separating rotating disk from stationary weld metal engulfs fresh metal, the fresh metal is subjected to severe shear deformation, which results in its recrystallization. Encouraging agreement between computations and measured torque and plunge force is obtained.

Nunes, Arthur↗
DOE OSTI2022

Time-discretization of a plasma-neutral MHD model with a semi-implicit leapfrog algorithm

The semi-implicit leapfrog time-discretization is a workhorse algorithm for initial-value MHD codes to bridge between vastly separated time scales. Inclusion of atomic interactions with neutrals breaks the functional structure of the MHD equations that exploited by the leapfrog. In this work, we address how to best integrate atomic physics into the semi-implicit leapfrog. Following the Crank-Nicolson method, one approach is to time-center the atomic interactions in the linear solver and use a Newton method to include the nonlinear contributions. Alternatively, another family of methods are based on operator-splitting the terms associated with the atomic interactions using a Strang-splitting technique. These methods naturally break equations into constituent ODE and PDE parts and preserve the structure exploited by the semi-implicit leapfrog. We study the accuracy and efficiency of these methods through a battery of 0D and 1D cases and show that a second-order-in-time Douglas-Rachford inspired coupling between the ODE and PDE advances is effective in reducing the time-discretization error to be comparable to that of Crank-Nicolson with Newton iteration of the nonlinear terms. Splitting ODE and PDE parts results in independent matrix solves for each field which reduces the computational cost considerably and provides parallelization over species relative to Crank-Nicolson.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Impact of storage and extraction methods on peat soil microbiomes

Recovered microbial community structure is known to be influenced by sample storage conditions and nucleic acid extraction methods, and the impact varies by sample type. Peat soils store a large portion of soil carbon and their microbiomes mediate climate feedbacks. Here, we tested three storage conditions and five extraction protocols on peat soils from three physicochemically distinct habitats in Stordalen Mire, Sweden, revealing significant methodological impacts on microbial (here, meaning bacteria and archaea) community structure. Initial preservation method impacted alpha but not beta diversity, with in-field storage in LifeGuard buffer yielding roughly two-thirds the richness of in-field flash-freezing or transport from the field on ice (all samples were stored at −80 °C after return from the field). Nucleic acid extraction method impacted both alpha and beta diversity; one method (the PowerSoil Total RNA Isolation kit with DNA Elution Accessory kit) diverged from the others (PowerMax Soil DNA Isolation kit-High Humic Acid Protocol, and three variations of a modifiedPowerMax Soil DNA/RNA isolation kit), capturing more diverse microbial taxa, with divergent community structures. Although habitat and sample depth still consistently dominated community variation, method-based biases in microbiome recovery for these climatologically-relevant soils are significant, and underscore the importance of methodological consistency for accurate inter-study comparisons, long-term monitoring, and consistent ecological interpretations.

Science & Technology - Other Topics↗
NASA NTRS1995

Modification of Experimental Protocols for a Space Shuttle Flight and Applications for the Analysis of Cytoskeletal Structures During Fertilization, Cell Division , and Development in Sea Urchin Embryos

To explore the role of microgravity on cytoskeletal organization and skeletal calcium deposition during fertilization, cell division, and early development, the sea urchin was chosen as a model developmental system. Methods were developed to employ light, immunofluorescence, and electron microscopy on cultures being prepared for flight on the Space Shuttle. For analysis of microfilaments, microtubules, centrosomes, and calcium-requiring events, our standard laboratory protocols had to be modified substantially for experimentation on the Space Shuttle. All manipulations were carried out in a closed culture chamber containing 35 ml artificial sea water as a culture fluid. Unfertilized eggs stored for 24 hours in these chambers were fertilized with sperm diluted in sea water and fixed with concentrated fixatives for final fixation in formaldehyde, taxol, EGTA, and MgCl2(exp -6)H2O for 1 cell to 16 cell stages to preserve cytoskeletal structures for simultaneous analysis with light, immunofluorescence, and electron microscopy, and 1.5 percent glutaraldehyde and 0.4 percent formaldehyde for blastula and plueus stages. The fixed samples wre maintained in chambers without degradation for up to two weeks after which the specimens were processed and analyzed with routine methods. Since complex manipulations are not possible in the closed chambers, the fertilization coat was removed from fixation using 0.5 percent freshly prepared sodium thioglycolate solution at pH 10.0 which provided reliable immunofluorescence staining for microtubules. Sperm/egg fusion, mitosis, cytokinesis, and calcium deposition during spicule formatin in early embryogenesis were found to be without artificial alterations when compared to cells fixed fresh and processed with conventional methods.

Chakrabarti, Amitabha↗
DOE OSTI2021

An explicitly solvable energy-conserving algorithm for pitch-angle scattering in magnetized plasmas

In this work, we develop an Explicitly Solvable Energy-Conserving (ESEC) algorithm for the Stochastic Differential Equation (SDE) describing the pitch-angle scattering process in magnetized plasmas. The Cayley transform is used to calculate both the deterministic gyromotion and stochastic scattering, affording the algorithm to be explicitly solvable and exactly energy conserving. An unusual property of the SDE for pitch-angle scattering is that its coefficients diverge at the zero velocity and do not satisfy the global Lipschitz condition. Consequently, when standard numerical methods, such as the Euler-Maruyama (EM), are applied, numerical convergence is difficult to establish. For the proposed ESEC algorithm, its energy-preserving property enables us to overcome this obstacle. We rigorously prove that the ESEC algorithm is order 1/2 strongly convergent. This result is confirmed by detailed numerical studies. For the case of pitch-angle scattering in a magnetized plasma with a constant magnetic field, the numerical solution is benchmarked against the analytical solution, and excellent agreements are found.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Single-Particle Insights Into the Electronic Structure and Enhanced Stability of CsPbBr 3 /FAPbBr 3 Core/Crown Nanoplatelets at the Nanometer Scale

Colloidal perovskite nanoplatelets (NPLs), despite their exceptional optoelectronic properties, face significant challenges due to their intrinsic instability and trap-assisted non-radiative recombination. Although many studies employing surface engineering, such as selecting ligands or coating to passivate defects, have demonstrated improved optoelectronic properties, these enhancements are typically inferred from bulk-ensemble measurements; the effects at the single-particle level remain elusive. Here, we conduct single-particle-level studies using scanning tunneling spectroscopy (STS) on a unique core–crown system, CsPbBr 3 @FAPbBr 3 NPLs, where the lateral surfaces of the CsPbBr 3 core are coated with an FAPbBr 3 crown. Experimental density-of-states (DOS) analysis reveals a 47% reduction in deep-trap states in core-crown NPLs compared to core-only NPLs, consistent with nearly two-fold enhancements in photoluminescence quantum yields. Progressive I–V sweep measurements demonstrate superior electrical stability in core-crown NPLs, preserving band structure with minimal degradation, while core-only NPLs exhibit rapid bandgap shrinkage and trap formation. Density functional theory (DFT) calculations indicate that FA incorporation distorts Pb octahedral lattice, widening the bandgap. This study elucidates how surface engineering modulates charge localization, passivates defects, and enhances stability at the single-particle level. Moreover, by uncovering bias-induced trap states in single unpassivated NPLs, this study establishes a precise, robust approach for characterizing emerging perovskite nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Bidentate Lewis Base Ligand-Mediated Surface Stabilization and Modulation of the Electronic Structure of CsPbBr 3 Perovskite Nanocrystals

The desorption of conventional ligands from the surface of halide perovskite nanocrystals (NCs) often causes their structural instability and the deterioration of the optoelectronic properties. To address this challenge, we present an approach of using a bidentate Lewis base ligand, namely, 1,4-bis(diphenylphosphino)butane (DBPP), for the synthesis of CsPbBr 3 NCs. The phosphine group of DBPP has a strong interaction with PbBr 2 precursor, forming a highly crystalline intermediate complex during the reaction. In the presence of oleic acid, the uncoordinated phosphine group of DBPP is converted into the phosphonium cation, which strongly binds with the surface bromide of the formed CsPbBr 3 NCs through hydrogen bonding. Density functional theory calculations suggest that DBPP can strongly bind to the undercoordinated lead and surface bromide ions of CsPbBr 3 NCs through its unprotonated and protonated phosphine groups, respectively. The robust binding of DBPP with the surface of perovskite NCs helps to preserve their structural integrity under various environmental stresses. Moreover, the electron density and energy levels are regulated in DBPP-capped CsPbBr 3 NCs via the efficient transfer of electrons from the ligands to the NCs, resulting in their improved photocatalytic CO 2 reduction performance. Furthermore, our study highlights the potential of using bidentate ligands to stabilize the surface of perovskite NCs and modulate their optical and electronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗