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Cover page of Complexions at the iron-magnetite interface.

Complexions at the iron-magnetite interface.

(2025)

Synthesizing distinct phases and controlling crystalline defects are key concepts in materials design. These approaches are often decoupled, with the former grounded in equilibrium thermodynamics and the latter in nonequilibrium kinetics. By unifying them through defect phase diagrams, we can apply phase equilibrium models to thermodynamically evaluate defects-including dislocations, grain boundaries, and phase boundaries-establishing a theoretical framework linking material imperfections to properties. Using scanning transmission electron microscopy (STEM) with differential phase contrast (DPC) imaging, we achieve the simultaneous imaging of heavy Fe and light O atoms, precisely mapping the atomic structure and chemical composition at the iron-magnetite (Fe/Fe3O4) interface. We identify a well-ordered two-layer interface-stabilized phase state (referred to as complexion) at the Fe[001]/Fe3O4[001] interface. Using density-functional theory (DFT), we explain the observed complexion and map out various interface-stabilized phases as a function of the O chemical potential. The formation of complexions increases interface adhesion by 20% and alters charge transfer between adjacent materials, impacting transport properties. Our findings highlight the potential of tunable defect-stabilized phase states as a degree of freedom in materials design, enabling optimized corrosion protection, catalysis, and redox-driven phase transitions, with applications in materials sustainability, efficient energy conversion, and green steel production.

Cover page of Direct Observation of Phase Change Accommodating Hydrogen Uptake in Bimetallic Nanoparticles.

Direct Observation of Phase Change Accommodating Hydrogen Uptake in Bimetallic Nanoparticles.

(2025)

Hydrogen holds great promise as a cleaner alternative to fossil fuels, but its efficient and affordable storage remains a significant challenge. Bimetallic systems, such as Pd and Ni, present a promising option for storing hydrogen. In this study, using the combination of different cutting-edge X-ray and electron techniques, we observed the transformations of Pd-Ni nanoparticles, which initially consist of a NiO-rich shell surrounding a Pd-rich core but undergo a major transformation when they interact with hydrogen. During hydrogen exposure, the Pd core breaks into smaller pockets, dramatically increasing its surface area and enhancing the hydrogen storage capacity, especially in nanoparticles with lower Pd content. The findings provide a deep understanding of the morphological changes at the atomic level during hydrogen storage and contribute to designing cost-effective hydrogen storage using multimetallic systems.

Cover page of Humidity Disrupts Structural and Chiroptical Properties of Chiral 2D Perovskites

Humidity Disrupts Structural and Chiroptical Properties of Chiral 2D Perovskites

(2025)

Chiral two-dimensional (2D) hybrid organic-inorganic metal halide perovskite semiconductors have emerged as an exceptional material platform with many design opportunities for spintronic applications. However, a comprehensive understanding of changes to the crystal structure and chiroptical properties upon exposure to atmospheric humidity has not been established. We demonstrate phase degradation to the 1D (MBA)PbI3 (MBA = methylbenzylammonium) and the hypothetical (MBA)3PbI5·H2O hydrate phases, accompanied by a reduction and disappearance of the chiroptical response. First-principle simulations show that water molecules preferentially locate at the interface between the organic cations and the inorganic framework, thereby disrupting the hydrogen bonding, impacting both the structural chirality and stability of the material. These findings provide critical insights into phase degradation mechanisms and their impact on chiroptical activity in chiral 2D perovskites.

Cover page of Harnessing Cation Disorder for Enhancing Ionic Conductivity in Lithium Inverse Spinel Halides.

Harnessing Cation Disorder for Enhancing Ionic Conductivity in Lithium Inverse Spinel Halides.

(2025)

Halides are promising solid-state electrolytes for all-solid-state lithium batteries due to their exceptional oxidation stability, high Li-ion conductivity, and mechanical deformability. However, their practicality is limited by the reliance on rare and expensive metals. This study investigates the Li2MgCl4 inverse spinel system as a cost-effective alternative. Molecular dynamics simulations reveal that lithium disordering at elevated temperatures significantly reduces the activation energy in Li2MgCl4. To stabilize this disorder at lower temperatures, we experimentally explored the Li x Zr1-x/2Mg x/2Cl4 system and found that Zr doping induces both Zr and Li disorder at the 16c site at room temperature (RT). This leads to a 2 order-of-magnitude increase in ionic conductivity for the Li1.25Zr0.375Mg0.625Cl4 composition, achieving 1.4 × 10-5 S cm-1 at RT, compared to pristine Li2MgCl4. By deconvoluting the role of lithium vacancies and dopants, we reveal that cation disordering to the 16c site predominantly enhances ionic conductivity, whereas lithium vacancy concentration has a very limited effect.

Cover page of Dynamics and structure of the B2→B19’ phase transformation in NiTi revealed through in situ 4D-STEM

Dynamics and structure of the B2→B19’ phase transformation in NiTi revealed through in situ 4D-STEM

(2025)

The structural evolution of NiTi during the B2→B19’ martensitic phase transformation via thermal cycling is investigated using in situ four dimensional scanning transmission electron microscopy (4D-STEM). With 4D-STEM, we can directly visualize and quantify the nanoscale evolution of the martensitic structure on thermal cycling and also investigate the origin of diffuse scattering of NiTi in the pre-transitional state. Mapping of the martensite orientation and strain visualizes the progression of the transformation front and self-accommodation of the B19’ structure. Diffuse streaking and strain are measured in the pre-transitional austenite (B2) phase and demonstrate no localization or preferential directionality hinting that long-range homogeneous instability rather than nanoscale heterogeneities may be the origin of the pre-transitional anomalies in NiTi. Finally, it is revealed that NiTi does not reform the same martensite nanostructure on thermal cycling but does express similar features. This small variation is likely owing to transformation-induced dislocations.

Spatially Enhanced Electrostatic Doping in Graphene Realized via Heterointerfacial Precipitated Metals

(2025)

Abstract: Forming heavily‐doped regions in 2D materials, like graphene, is a steppingstone to the design of emergent devices and heterostructures. Here, a selective‐area approach is presented to tune the work‐function and carrier density in monolayer graphene by spatially synthesizing sub‐monolayer gallium beneath the 2D‐solid. The localized metallic gallium is formed via precipitation from an underlying diamond‐like carbon (DLC) film that is spatially implanted with gallium‐ions. By controlling the interfacial precipitation process with annealing temperature, spatially precise ambipolar tuning of the graphene work‐function is achieved, and the tunning effect preserved upon cooling to ambient conditions. Consequently, charge carrier densities from ≈1.8 × 1010 cm−2 (hole‐doped) to ≈7 × 1013 cm−2 (electron‐doped) are realized, confirmed by in situ and ex situ measurements. The theoretical studies corroborated the role of gallium at the heterointerface on charge transfer and electrostatic doping of the graphene overlayer. Specifically, sub‐monolayer gallium facilitates heavy n‐doping in graphene. Extending this doping strategy to other implantable elements in DLC provides a new means of exploring the physics and chemistry of highly‐doped 2D materials.

Cover page of Degradation Mechanism of Phosphate‐Based Li‐NASICON Conductors in Alkaline Environment

Degradation Mechanism of Phosphate‐Based Li‐NASICON Conductors in Alkaline Environment

(2025)

NASICON-type Li conductors (Li-NASICON) have traditionally been regarded as promising candidates for solid-state Li-air battery applications because of their stability in water and ambient air. However, the presence of water in the cathode of a Li-air battery can induce a highly alkaline environment by modifying the discharge product from Li2O2 to LiOH which can potentially degrade cathode and separator materials. This study investigates the alkaline stability of common Li-NASICON chemistries through a systematic experimental study of LiTixGe2-x(PO4)3 (LTGP) with varying x = 0–2.0. Density functional theory calculations are combined to gain a mechanistic understanding of the alkaline instability. It is demonstrated that the instability of LTGP in an alkaline environment is mainly driven by the dissolution of PO43– groups, which subsequently precipitate as Li3PO4. The introduction of Ti facilitates the formation of a Ti-rich compound on the surface that eventually passivates the material, but only after significant bulk degradation. Consequently, phosphate-based Li-NASICON materials exhibit limited alkaline stability, raising concerns about their viability in humid Li-air batteries.

Cover page of ASb3Mn9O19 (A = K or Rb): New Mn‐Based 2D Magnetoplumbites with Geometric and Magnetic Frustration

ASb3Mn9O19 (A = K or Rb): New Mn‐Based 2D Magnetoplumbites with Geometric and Magnetic Frustration

(2025)

Magnetoplumbites are one of the most broadly studied families of hexagonal ferrites, typically with high magnetic ordering temperatures, making them excellent candidates for permanent magnets. However, magnetic frustration is rarely observed in magnetoplumbites. Herein, the discovery, synthesis, and characterization of the first Mn-based magnetoplumbite, as well as the first magnetoplumbite involving pnictogens (Sb), ASb3Mn9O19 (A = K or Rb) are reported. The Mn3+ (S = 2) cations, further confirmed by DC magnetic susceptibility and X-ray photoelectron spectroscopy, construct three geometrically frustrated sublattices, including Kagome, triangular, and puckered honeycomb lattices. Magnetic properties measurements revealed strong antiferromagnetic spin-spin coupling as well as multiple low-temperature magnetic features. Heat capacity data does not show any prominent λ-anomaly, suggesting minimal associated magnetic entropy. Moreover, neutron powder diffraction (NPD) implied the absence of long-range magnetic ordering in KSb3Mn9O19 down to 3 K. However, several magnetic peaks are observed in RbSb3Mn9O19 at 3 K, corresponding to an incommensurate magnetic structure. Interestingly, strong diffuse scattering is seen in the NPD patterns of both compounds at low angles and is analyzed by reverse Monte Carlo refinements, indicating short-range spin ordering related to frustrated magnetism as well as 2D magnetic correlations in ASb3Mn9O19 (A = K or Rb).

Cover page of Absence of Long-Range Magnetic Ordering in a Trirutile High-Entropy Oxide (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)Ta1.92O6-δ.

Absence of Long-Range Magnetic Ordering in a Trirutile High-Entropy Oxide (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)Ta1.92O6-δ.

(2025)

Functionalities of solid-state materials are usually considered to be dependent on their crystal structures. The limited structural types observed in the emerging high-entropy oxides put constraints on the exploration of their physical properties and potential applications. Herein, we synthesized the first high-entropy oxide in a trirutile structure, (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)Ta1.92O6-δ, and investigated its magnetism. The phase purity and high-entropy nature were confirmed by powder X-ray diffraction and energy-dispersive spectroscopy, respectively. X-ray photoelectron spectroscopy indicated divalent Mn, Co, Ni, and Cu along with trivalent Fe. Magnetic property measurements showed antiferromagnetic coupling and potential short-range magnetic ordering below ∼4 K. The temperature-dependent heat capacity data measured under zero and high magnetic fields confirmed the lack of long-range magnetic ordering and a possible low-temperature phonon excitation. The discovery of the first trirutile high-entropy oxide opens a new pathway for studying the relationship between the highly disordered atomic arrangement and magnetic interaction. Furthermore, it provides a new direction for exploring the functionalities of high-entropy oxides.

Cover page of Streaming Large-Scale Microscopy Data to a Supercomputing Facility

Streaming Large-Scale Microscopy Data to a Supercomputing Facility

(2025)

Data management is a critical component of modern experimental workflows. As data generation rates increase, transferring data from acquisition servers to processing servers via conventional file-based methods is becoming increasingly impractical. The 4D Camera at the National Center for Electron Microscopy generates data at a nominal rate of 480 Gbit s-1 (87,000 frames s-1), producing a 700 GB dataset in 15 s. To address the challenges associated with storing and processing such quantities of data, we developed a streaming workflow that utilizes a high-speed network to connect the 4D Camera's data acquisition system to supercomputing nodes at the National Energy Research Scientific Computing Center, bypassing intermediate file storage entirely. In this work, we demonstrate the effectiveness of our streaming pipeline in a production setting through an hour-long experiment that generated over 10 TB of raw data, yielding high-quality datasets suitable for advanced analyses. Additionally, we compare the efficacy of this streaming workflow against the conventional file-transfer workflow by conducting a postmortem analysis on historical data from experiments performed by real users. Our findings show that the streaming workflow significantly improves data turnaround time, enables real-time decision-making, and minimizes the potential for human error by eliminating manual user interactions.