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At least 73 records · Page 4

Structural Tolerance Factor Approach to Defect-Resistant I 2 -II-IV-X 4 Semiconductor Design

Recent work on quaternary semiconductors Cu 2 BaSn(S,Se) 4 and Ag 2 BaSnSe 4 for photovoltaic and thermoelectric applications, respectively, has shown the promise of exploring the broader family of defect-resistant I 2 -II-IV-X 4 materials (where I, II, and IV refer to the formal oxidation state of the metal cations and X is a chalcogen anion) with tetrahedrally coordinated I/IV cations and larger II cations (i.e., Sr, Ba, Pb, and Eu) for optoelectronic and energy-related applications. Chemical dissimilarity among the II and I/IV atoms represents an important design motivation because it presents a barrier to antisite formation, which otherwise may act as electronically harmful defects. We herein show how all 31 experimentally reported I 2 -II-IV-X 4 examples (with large II cations and tetrahedrally coordinated smaller I/IV cations), which form within five crystal structure types, are structurally linked. Based on these structural similarities, we derive a set of tolerance factors that serve as descriptors for phase stability within this family. Despite common usage in the well-studied perovskite system, Shannon ionic radii are found to be insufficient for predicting metal–chalcogen bond lengths, pointing to the need for experimentally derived correction factors as part of an empirically driven learning approach to structure prediction. Here, we use the tolerance factors as a predictive tool and demonstrate that four new I 2 -II-IV-X 4 compounds, Ag 2 BaSiS 4 , Ag 2 PbSiS 4 , Cu 2 PbGeS 4 , and Cu 2 SrSiS 4 , can be synthesized in correctly predicted phases. One of these compounds, Ag 2 PbSiS 4 , shows potentially promising optoelectronic properties for photovoltaic applications.

36 MATERIALS SCIENCE↗

Li x (C 5 H 5 N) y Fe 2– z Se 2 : A Defect-Resilient Expanded-Lattice High-Temperature Superconductor

Two-dimensional iron chalcogenide intercalates display a remarkable correlation of the interlayer spacing with enhancement of the superconducting critical temperature (T c ). In this work, synchrotron X-ray absorption (XAS; at the Fe and Se K-edges) and emission (XES; at the Fe Κβ) spectroscopies allow one to discuss how the important rise of T c (~44 K) in the molecule-intercalated Li x (C 5 H 5 N) y Fe 2-z Se 2 relates to the electronic and local structural changes felt by the inorganic host upon doping (x). XES shows that widely separated layers of edge-sharing FeSe 4 tetrahedra carry low-spin moieties, with a local Fe magnetic moment slightly reduced compared to the parent β-Fe 2-z Se 2 . Pre-edge XAS expresses the progressively reduced mixing of metal 3d-4p states upon lithiation. Doping-mediated local lattice modifications, probed by conventional T c optimization measures (cf. the anion height and FeSe 4 tetrahedra regularity), become less relevant when layers are spaced far away. On the basis of extended X-ray absorption fine structure, such distortions are compensated by a softer Fe network that relates to Fe-site vacancies, alleviating electron-lattice correlations and superconductivity. Density functional theory (DFT) guided modification of the isolated Fe 2-z Se 2 (z, vacant sites) planes, resembling the host layers, identify that Fe-site deficiency occurs at low energy cost, giving rise to stretched Fe sheets, in accordance with experiments. Here, the robust high-T c in Li x (C 5 H 5 N) y Fe 2-z Se 2 , arises from the interplay of electron-donating spacers and the iron selenide layer's tolerance to defect chemistry, a tool to favorably tune its Fermi surface properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hydrophobic Carbon Nanosheets as Passivation Layer for Perovskite Solar Cells with High Efficiency and Stability (Final Technical Report)

Hybrid organic-inorganic metal halide perovskites have continually demonstrated competitive advantages for photovoltaic applications due to their high light absorption coefficient, tunable bandgaps, ambipolar charge mobility and high tolerance of defects. However, there are many challenges yet to overcome to bring this technology to the market. For instance, bridging the ‘scaling gap’ and transitioning PSCs from a lab scale to an industrial scale is a serious challenge. This project developed a high stability and inexpensive perovskite solar cell (PSC) by incorporating hydrophobic carbon nanosheets as counter electrodes (CEs). We demonstrated that the hydrogenated carbon nanosheets with tunable hydrophobic properties as CEs can improve life-time stability of PSCs in operating conditions (i.e. humid air) while achieving impressive power conversion efficiency (PCE).

14 SOLAR ENERGY↗

Scalable and Quench-Free Processing of Metal Halide Perovskites in Ambient Conditions

With the rise of global warming and the growing energy crisis, scientists have pivoted from typical resources to look for new materials and technologies. Perovskite materials hold the potential for making high-efficiency, low-cost solar cells through solution processing of Earth-abundant materials; however, scalability, stability, and durability remain key challenges. In order to transition from small-scale processing in inert environments to higher throughput processing in ambient conditions, the fundamentals of perovskite crystallization must be understood. Classical nucleation theory, the LaMer relation, and nonclassical crystallization considerations are discussed to provide a mechanism by which a gellan gum (GG) additive—a nontoxic polymeric saccharide—has enabled researchers to produce quality halide perovskite thin-film blade coated in ambient conditions without a quench step. Furthermore, we report on the improved stability and durability properties inherent to these films, which feature improved morphologies and optoelectronic properties compared to films spin-coated in a glovebox with antisolvent. We tune the amount of GG in the perovskite precursor and study the interplay between GG concentration and processability, morphological control, and increased stability under humidity, heat, and mechanical testing. The simplicity of this approach and insensitivity to environmental conditions enable a wide process window for the production of low-defect, mechanically robust, and operationally stable perovskites with fracture energies among the highest obtained for perovskites.

14 SOLAR ENERGY↗

Design considerations for high entropy alloys in advanced nuclear applications

The demanding operating environments of advanced nuclear reactors require the development of new nuclear materials that can withstand their increased physical, chemical, thermal, and radiation-related challenges. High-entropy alloys (HEAs) have shown often-impressive mechanical, thermomechanical, and corrosion-resistant properties, and offer a massive, unexplored compositional space which allows for the targeted development of application-specific materials. Furthermore, although still in a nascent stage, research has shown that HEAs may exhibit unique irradiation tolerance, including reduced defect production and resistance to irradiation-induced swelling and hardening. The mechanisms behind this increased tolerance are not yet well-understood, although the HEA-specific attributes of a complex energy landscape, reduced thermal conductivity, and shift in defect migration energies and pathways provide promising explanations. Here this work assesses the current and future challenges faced by structural nuclear materials, identifying the specific applications in which HEAs may provide a competitive advantage compared to industry-standard materials with the aid of Ashby material selection maps. Considerations are provided for the design of future nuclear HEAs, including calculations of nuclear-relevant properties to assist in the initial down-selection of elements depending on application requirements (e.g., low neutron capture for in-core applications), narrowing the existing compositional space of HEAs to a manageable scope.

36 MATERIALS SCIENCE↗

Molecular-resolution imaging of ice crystallized from liquid water by cryogenic liquid-cell TEM

Despite the ubiquity of ice, a molecular-resolution image of nanoscopic defects or microstructures in ice crystallized from liquid water has never been obtained. This is mainly due to the difficulties in preparing and preserving crystalline ice samples that can survive under high-resolution imaging conditions. Here, we report the stabilization and Å-resolution electron imaging of ice Ih crystallized from liquid water by developing cryogenic liquid-cell transmission electron microscopy (CRYOLIC-TEM). We combine lattice mapping with molecular dynamics simulations to reveal that ice formation is highly tolerant to nanoscale defects such as misoriented subdomains and trapped gas bubbles, which are stabilized by molecular-scale structural motifs. Importantly, bubble surfaces adopt low-energy nanofacets and create negligible strain fields in the surrounding crystal. These bubbles can dynamically nucleate, grow, migrate, dissolve, and coalesce under electron irradiation and be monitored in situ near a steady state. This work improves our understanding of water crystallization behaviors at a molecular spatial resolution.

Materials science↗

Hole Trapping in Halide Perovskites Induces Phase Segregation

Metal halide perovskites have garnered a great deal of attention for their applications in photovoltaics, LEDs, and radiation detection. The ease of solution processing high-quality perovskite semiconductors with large absorption coefficients and tolerance to native defects is decidedly attractive. Additionally, the ability to precisely tune the band gap of halide perovskites through compositional alloying of the halide ion is of particular interest for a range of applications, especially for tandem solar cells. However, under steady state light irradiation, an initially homogeneous mixed halide perovskite (MHP) will form local domains that are rich in one halide ion (e.g., Br or I). This light-induced phase segregation in MHPs forms iodide-rich domains that act as charge carrier traps and lowers the efficiency of perovskite-based devices. Thus, phase segregation poses a serious challenge to the implementation of MHPs in real-world device settings. Interestingly, when a phase segregated MHP film is placed in the dark, entropic driving forces become dominant and the segregated perovskite remixes and returns to its initially homogeneous state. Several key mechanistic details of phase segregation have been elucidated over the years. However, there are still aspects of halide segregation that are not clear, and there is ongoing debate in the literature as to what are the key factors that contribute to the mechanism. This Account discusses recent results that point to the specific role of hole trapping in phase segregation. Interestingly, generation of holes through above-band-gap excitation or through electrochemical injection increases ion migration and leads to phase segregation. The thermodynamic and redox properties of halide perovskites provide a strong driving force for hole trapping and oxidation of iodide species in MHPs. However, mobile halide species within the perovskite lattice take time to migrate and generate halide-rich domains. When in contact with a nonpolar solvent, the migration of iodine species is further extended to expulsion of iodine from the perovskite film. Thus, the mobility of halides and their susceptibility to hole-induced oxidation play a crucial role in determining the long-term stability of metal halide perovskites. Strategies to gain kinetic control over ion migration to slow phase segregation are needed to overcome these hurdles and achieve stable mixed halide perovskites. Modification of the perovskite composition through introduction of different cations or halide ions, or introduction of low-dimensional perovskite phases may suppress phase segregation. Furthermore, in achieving stability and improving the efficiency of perovskite solar cells and light emitting devices with minimal impacts, suppression of segregation remains the key factor.

36 MATERIALS SCIENCE↗

Radiation Tolerance of Nanoporous Gadolinium Titanate

Defect sinks play a crucial role in reducing radiation-induced damage accumulation, but their effectiveness varies. This study directly compares the efficacy of grain boundaries and pores (free surfaces) in gadolinium titanate (Gd 2 Ti 2 O 7 ) using in situ ion irradiation transmission electron microscopy (TEM). A unique sample configuration is developed, where each of the three distinct regions, each containing only one primary sink of interest, is in the same TEM lamella for simultaneous irradiation. Regular assessments of crystallinity in each region via nanobeam electron diffraction show that, at both room temperature and 600°C, free surface (pore) defect sinks are more effective than grain boundaries in capturing radiation-induced defects and delaying the onset of amorphization. These findings have significant implications for further microstructural engineering and the design of radiation-resistant microstructures.

36 MATERIALS SCIENCE↗

Role of chemical disorder on radiation-induced defect production and damage evolution in NiFeCoCr

Understanding chemical disorder in many concentrated solid solution alloys (CSAs) at the levels of electrons and atoms has attracted increasing attention as a path forward to reveal and identify underlying mechanisms for extraordinary mechanical properties and improved radiation tolerance. Single-phase NiFeCoCr CSA is a common base for many high-entropy alloys (HEAs) that have shown improved mechanical strength and radiation tolerance. In this study, defect production and damage evolution in NiFeCoCr under ion irradiation at room temperature to dose over 20 dpa are determined using ion channeling technique along both <100> and <110> directions utilizing multiple probing beam energies. The results obtained from the multi-axial and multi-energy channeling analysis are compared with those previously obtained for Ni crystals irradiated under similar conditions. The influence of chemical complexity on defect production and clustering at early-stage under room temperature irradiation up to dose of 1 dpa is discussed based on positron annihilation spectroscopy results. Defect structure evaluation in Ni and NiFeCoCr is also discussed based on transmission electron microscopy results over a prolonged irradiation at both room and elevated temperatures. Compared with chemically complex NiFeCoCr, larger dislocation loops thus less lattice strain are expected to form in pure Ni. Moreover, the role of chemical disorder in this CSA is also investigated based on ab initio calculations using large supercells. Finally, to understand the impact of chemical complexity effect on defect structure evolution, this integrated research effort attempts to link the relatively large charge redistribution due to difference in valence electron counts resulting from alloying different 3d transition metal elements, moderate lattice distortion arising from similar adaptable atomic size, and notable suppressed or delayed damage evolution in NiFeCoCr.

36 MATERIALS SCIENCE↗

Microstructural Engineering of Cu-Rich Nanoprecipitate formation in NiCoFeCrCu0.12 High-Entropy Alloy via Severe Plastic Deformation for Enhanced Irradiation Tolerance

This study demonstrates a defect-engineering approach for controlling Cu-rich precipitates in FeNiCrCoCu0.2 high-entropy alloys (Cu-HEAs), delivering a novel pathway for next-generation nuclear reactor materials with superior irradiation resistance. This work establishes that severe plastic deformation (SPD) processing via Shear Assisted Processing and Extrusion (ShAPE) and Friction Stir Layer Deposition (FSLD) creates dense dislocation networks and subgrain boundaries that fundamentally alter precipitation behavior under identical thermal treatments. Atom probe tomography (APT) indicates that SPD produces a metastable, atomically homogeneous solid solution that, upon moderate heat treatment (500°C/10 hour), develops remarkedly stronger Cu clustering than the as-cast counterpart. High-temperature exposure (800°C/100 h) produces near-pure Cu precipitates (~90 at% Cu) with significantly enhanced defect-sink efficacy in SPD-processed alloys: precipitate sizes of 50-60 nm and number densities of 2.7-3.8 × 10¹7 m?³, compared to 89 nm and 0.44 × 10¹7 m?³ in as-cast materials. Collectively, the findings establish defect-mediated precipitation control as a scalable, high-impact route to tailor sink density and distribution in HEAs, enabling microstructures optimized for irradiation tolerance and mechanical robustness in nuclear reactor environments.

Meher, Subhashish↗

Molecular-Resolution Electron Imaging of Defects and Dynamics at the Ice-Water Interface

Water crystallization into hexagonal ice (type I h ) is one of the most critical processes relevant to the Earth’s environment and human activities. However, despite recent breakthroughs in imaging non-equilibrium condensed ice structures, the ice-water interface has never been imaged at a molecular resolution. This is primarily due to the low stability of the hydrogen bonds in ice under high-resolution microscopy conditions and a lack of methods to prepare compatible samples. Here, this presentation describes the first molecular-resolution imaging of ice crystallized from liquid water and the ice-water interface using high-resolution transmission electron microscopy (HRTEM). By encapsulating deionized (DI) water between two amorphous carbon (a-C) TEM grids and subsequently freezing it with liquid N 2 on a cryo sample stage, we generated two types of ice: non-equilibrium, condensed ice from the atmosphere and encapsulated ice from the DI water (Fig. 1A). Condensed ice usually shows irregular, spherulitic shapes (Fig. 1B). Selected area electron diffraction (SAED) shows that they are a mixture of cubic and hexagonal crystals (Fig. 1C). On the contrary, encapsulated ice forms thin films that contain large-area single-crystalline regions of hexagonal ice oriented along the [0001] zone axis (Fig. 1D). Differential electron energy-loss spectroscopy (EELS) confirmed the high purity of the encapsulated ice free from organic contaminations that are common in other encapsulation methods for HRTEM such as graphene liquid cells. These single-crystalline areas are robust under the electron beam up to ~100 e/Å 2 s. Aberration-corrected HRTEM imaging in these areas achieved a line resolution of ~1.3 Å (Fig. 1E and F). This platform allows us to study near-equilibrium ice structures and dynamics at an unprecedented spatial resolution (Fig. 2). For example, we discovered subdomain-rich regions near the defective crystal edges despite the structure appearing single-crystalline according to diffraction criteria. These subdomains connect via low-angle grain boundaries with flat energy landscapes as a function of tilt angles (according to simulations), showing the high tolerance of ice to defect structures. When we tuned the sample temperature and electron flux rate, we observed radiolysis-controlled bubble generation and dissolution in ice single crystals near a steady state of bubble dynamics. Furthermore, rich beam-induced melting and recrystallization dynamics were observed at the ice-water interface with lattice resolution. These data represent the first observation of the ice-water phase transformation at the sub-nanometer level. In summary, the methods developed in this work enabled molecular-resolution observations of ice and the ice-water interface and shed light on the microstructures and phase transformation pathways. Finer control on the temperature, electron irradiation profile, and imaging detector could eventually lead to real-time observation of ice nucleation in water and address long-standing questions in the nucleation pathways.

74 ATOMIC AND MOLECULAR PHYSICS↗

Defect-engineered GaN high electron mobility transistors for enhanced radiation tolerance

This study explores the radiation resilience of GaN high-electron-mobility transistors (HEMTs) under various preconditioning treatments—pristine, electro-pulsed, electrically overstressed, and 60 Co gamma-irradiated—with a focus on enhancing survivability in high-radiation environments. Key findings emphasize the gate region’s central role in radiation sensitivity, with increased defect concentrations leading to reduced sensitivity—as determined from reduced single-event transient intensities during pulsed-laser studies—and impacting charge-transport dynamics. Notably, the most sensitive region shifted as a function of bias state, with the drain side of the gate being most sensitive under negative gate bias and the source side under unbiased conditions due to two-dimensional electron gas disruptions. These insights clarify the mechanisms influencing radiation sensitivity in microelectronics and highlight the potential of defect and strain engineering to enhance the radiation hardness of GaN HEMTs across various operational states, providing valuable guidance for applications in space, defense, and other radiation-rich environments.

36 MATERIALS SCIENCE↗

Pixelated plastic scintillator array manufacturing using fast-, photo-curable resin

Pixelated plastic scintillator arrays can serve as high efficiency and high resolution neutron imaging detectors. Manufacturing these arrays is intensive in both time and labor. This article presents a fabrication method based on additive manufacturing for two-dimensional plastic organic scintillator arrays using a custom-built automated assembly machine and a custom photocurable resin that has significant non-aromatic acrylate oligomer content. The process involves two main stages: fully autonomous production of one-dimensional layered arrays, followed by semi-autonomous cutting and stacking to form two-dimensional pixel arrays. One-dimensional arrays were manufactured at a rate of around 4 layers per hour with minimal defects and tight dimensional tolerances, while two-dimensional arrays up to 7 x 7 pixels and 70 mm in length were completed in approximately 3.5 hours. Final arrays exhibited dimensional deviations of less than 0.5 mm. Two-dimensional arrays read out by a multi-anode photomultiplier tube demonstrated per-pixel position resolution and pulse-shape discrimination, enabling gamma–neutron interaction separation in mixed radiation environments.

36 MATERIALS SCIENCE↗

High Performance Circuit Pastes for Solid Oxide Fuel Cell Applications: Final Technical Report

Using a combination of in-plane electrical conductivity measurements, electrical contact resistance measurements, tensile fracture tests, double shear lap fracture tests, rapid thermal cycling adhesion tests, in situ wetting angle measurements, 3D X-ray tomography, reduction-oxidation (RedOx) cycling, scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDAX), Density Functional Theory (DFT) modeling, Molecular Dynamics (MD) modeling, and Phase Field modeling, this project determined that a new brazing technique developed by the PIs (specifically the use of nickel particles to direct the wetting and spreading of molten silver) could be used to produce well-adhered, >97% dense, electrically-conductive circuits, current collectors, and/or electrical contacts on a variety of ceramic and ceramic-coated substrates (specifically lanthanum strontium manganite, yttria stabilized zirconia, sapphire, Cr2O3-passivated stainless steel, and Al2O3-passivated stainless steel). Compared to other silver-based alternatives, Ag:Ni led to less manufacturing defects and was more tolerant of the extreme environments (isothermal high-temperature aging) and occasional abuse (rapid thermal cycling and RedOx cycling) encountered during Solid Oxide Fuel Cell and/or Solid Oxide Electrolysis Cell operation. Further, in some situations (such as when to produce Ag:Ni electrical contacts to Al2O3-protected stainless steel) the Ni particles also improved operation by acting as chemical getters that removed electrically-insulating, surface-segregating substrate impurities (i.e. by lowering the contact resistance with the underlying substrate).

36 MATERIALS SCIENCE↗

The integral spliceosomal component CWC15 is required for development in Arabidopsis

Efficient mRNA splicing is a prerequisite for protein biosynthesis and the eukaryotic splicing machinery is evolutionarily conserved among species of various phyla. At its catalytic core resides the activated splicing complex Bact consisting of the three small nuclear ribonucleoprotein complexes (snRNPs) U2, U5 and U6 and the so-called NineTeen complex (NTC) which is important for spliceosomal activation. CWC15 is an integral part of the NTC in humans and it is associated with the NTC in other species. Here we show the ubiquitous expression and developmental importance of the Arabidopsis ortholog of yeast CWC15. CWC15 associates with core components of the Arabidopsis NTC and its loss leads to inefficient splicing. Consistent with the central role of CWC15 in RNA splicing, cwc15 mutants are embryo lethal and additionally display strong defects in the female haploid phase. Interestingly, the haploid male gametophyte or pollen in Arabidopsis, on the other hand, can cope without functional CWC15, suggesting that developing pollen might be more tolerant to CWC15-mediated defects in splicing than either embryo or female gametophyte.

59 BASIC BIOLOGICAL SCIENCES↗

Carbon nanotube (CNT) metal composites exhibit greatly reduced radiation damage

Radiation damage of structural materials leads to mechanical property degradation, eventually inducing failure. Secondary-phase dispersoids or other radiation defect sinks are often added to materials to boost their radiation resistance. We demonstrate that a metal composite made by adding 1D carbon nanotubes (CNTs) to aluminum (Al) exhibits superior radiation resistance. In situ ion irradiation with transmission electron microscopy (TEM) and atomistic simulations together reveal the mechanisms of rapid defect migration to CNTs, facilitating defect recombination and enhancing radiation tolerance. The origin of this effect is an evolving stress gradient in the Al matrix resulting from CNT transformation under irradiation, and the stability of resulting carbides. Extreme value statistics of large defect behavior in our simulations highlight the role of CNTs in reducing accumulated damage. Furthermore, this approach to controlling defect migration represents a promising opportunity to enhance the radiation resistance of nuclear materials without detrimental effects.

36 MATERIALS SCIENCE↗

Revealing the Latent Atomic World Through Data-Driven Microscopy

Many emerging technologies depend on the precise design of materials structure, chemistry, and defects. As devices shrink, manufacturing tolerances tighten, and performance envelopes improve, we must increasingly measure and manipulate materials at or near the single atom level. Here we describe how transmission electron microscopy (TEM) underpins our ability to see and direct the latent atomic world. We review a selection of our recent high-resolution TEM studies of the synthesis of oxide-based nanomaterials and their evolution in extreme environments. We then discuss powerful new artificial intelligence (AI) and machine learning (ML) approaches we have developed for rich, reproducible, and scalable experimentation. Furthermore, we conclude by discussing future developments that will enable new materials for breakthrough technologies.

97 MATHEMATICS AND COMPUTING↗

In situ studies on heavy ion irradiation and partial oxidation induced stacking faults and nanograins in tungsten nanolaminates

Understanding the microstructural evolution of tungsten (W) under extreme irradiation environments is critical for its application as a plasma-facing material in future fusion reactors. Heavy ion irradiation study offers expedited damage accumulation and thus allows irradiation tolerance property prediction in a short period of time. In this study we explore in situ Kr ion irradiation of W nanolaminates at 800 °C and uncover a complex interplay of irradiation-induced transformations, including the emergence of stacking faults, nanograin formation, and generation of thickened grain boundaries defined as GB regions with the thickness of up to 15 nm. High-resolution transmission electron microscopy studies reveal the formation of extended planar faults and a metastable hexagonal close-packed (hcp) phase within the body-centered cubic (bcc) matrix. These structural transitions are facilitated by irradiation-induced shear. They are further stabilized by the presence of oxygen, which promotes stacking fault formation and vacancy trapping. Elevated temperatures enhance defect mobility, enabling dynamic recrystallization into ultrafine grains and the thickening of GBs due to defect absorption and impurity segregation. These findings unravel non-equilibrium phase transformation pathways in heavy ion irradiated W and highlight the critical role of impurity-mediated defect dynamics in governing its radiation tolerance properties.

Wazeer, Adil [Purdue University]↗