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At least 307 records · Page 17

Unidirectional ray polaritons in twisted asymmetric stacks

Abstract The vast repository of van der Waals (vdW) materials supporting polaritons offers numerous possibilities to tailor electromagnetic waves at the nanoscale. The development of twistoptics—the modulation of the optical properties by twisting stacks of vdW materials—enables directional propagation of phonon polaritons (PhPs) along a single spatial direction, known as canalization. Here we demonstrate a complementary type of directional propagation of polaritons by reporting the visualization of unidirectional ray polaritons (URPs). They arise naturally in twisted hyperbolic stacks with very different thicknesses of their constituents, demonstrated for homostructures of$$\alpha$$ α -MoO 3 and heterostructures of$$\alpha$$ α -MoO 3 and$$\beta$$ β -Ga 2 O 3 . Importantly, their ray-like propagation, characterized by large momenta and constant phase, is tunable by both the twist angle and the illumination frequency. Apart from their fundamental importance, our findings introduce twisted asymmetric stacks as efficient platforms for nanoscale directional polariton propagation, opening the door for applications in nanoimaging, (bio)-sensing, or polaritonic thermal management.

Science & Technology - Other Topics↗

Hemicellulose Modulates Nanoscale Lignin Architecture in Synthetic Plant Cell Walls

Cellulose, hemicellulose, and lignin─the most abundant biopolymers on Earth─compose the structural matrix of plant biomass, providing renewable resources critical to bioenergy and sustainable materials. Despite their importance, the nanoscale mechanochemical processes underlying lignocellulose assembly during plant secondary cell wall formation remain poorly understood, hindering advancements in biomass conversion technologies. Here, in this study, we synthesize a biomimetic model system comprising cellulose–hemicellulose nanofibrils (CHN) to examine guaiacyl lignin polymerization in a physiologically relevant context. Using advanced nanocharacterization─scattering-type scanning near-field optical microscopy (s-SNOM) with infrared nanospectroscopy coupled to solid-state nuclear magnetic resonance (NMR)─we reveal that hemicellulose presence considerably modulates lignin deposition and alters its interunit bond distribution. Specifically, hemicellulose-rich environments dramatically reduce lignin deposition by approximately 50% and yield highly condensed lignin structures characterized by severely reduced β–O–4′ linkages (<2%) and suppressed β–β′ linkages. Conversely, cellulose-alone scaffolds support notably higher β–O–4′ content (∼10%), resulting in a more uniform nanoscale lignin coating. Our work helps explain how accessible hemicellulose sites, both sterically and chemically, direct radical coupling during lignification, fundamentally reshaping lignin’s nanoscale architecture. These findings deepen our mechanistic understanding of plant cell wall biosynthesis and inform strategies aimed at enhancing biomass deconstruction efficiency for sustainable bioenergy applications.

NMR↗

Synthesis‐Related Nanoscale Defects in Mo‐Based Janus Monolayers Revealed by Cross‐Correlated AFM and TERS Imaging

2D Janus transition metal dichalcogenides (TMDs) are promising candidates for various applications including non-linear optics, energy harvesting, and catalysis. These materials are usually synthesized via chemical conversion of pristine TMDs. Nanometer-scale characterization of the obtained Janus materials’ morphology and local composition is crucial for both the synthesis optimization and the future device applications. In this work, we present the results of cross-correlated atomic force microscopy (AFM) and tip-enhanced Raman spectroscopy (TERS) study of Janus monolayers synthesized by the hydrogen plasma-assisted chemical conversion of MoSe 2 and MoS 2 . We demonstrate that the choice of both the growth substrate and the starting TMD influences the residual strain, thereby shaping the nanoscale morphology of the resulting Janus material. Furthermore, by employing TERS imaging, we show the presence of nanoscale islands (≈20 nm across) of MoSe 2 - ${\mathrm{Mo}}_{{\mathrm{Se}}}^{\mathrm{S}}$ (MoS 2 -${\mathrm{Mo}}_{\mathrm{S}}^{{\mathrm{Se}}}$) vertical heterostructures originating from the bilayer nanoislands in the precursor monolayer crystals. The understanding of the origins of nanoscale defects in Janus TMDs revealed in this study can help with further optimization of the Janus conversion process towards uniform and wrinkle-/crack-free Janus materials. Moreover, this work shows that cross-correlated AFM and TERS imaging is a powerful and accessible method for studying nanoscale composition and defects in Janus TMD monolayers.

2D materials↗

Laser-Induced Enhancement of Acoustic Mode Quality Factor Revealed by Correlated Single-Particle Optical and Electron Microscopy

Acoustic modes in plasmonic nanostructures provide fundamental insights into their optomechanical behavior at the nanoscale, enabling emerging applications in plasmon-enhanced optomechanics, ultrasensitive sensing, and nanoscale energy transduction. Here we explore the modulation of acoustic phonon dynamics in lithographically fabricated gold nanodisks via laser-induced photothermal annealing. Using a correlated approach that utilizes both single-particle transient extinction spectroscopy and advanced electron microscopy, we directly link nanoscale structural transformations to changes in mechanical properties as probed through the coherence of the excited acoustic modes. Specifically, ultrafast pump–probe microscopy reveals an enhancement in the acoustic mode quality factor of annealed gold nanodisks, indicative of reduced damping and improved vibrational coherence. Structural characterization via scanning electron microscopy and electron backscatter diffraction confirms that photoinduced annealing results in smoother surface morphology and overall enhanced crystallinity. The improved crystalline order reduces defect and crystal boundary scattering, which we suggest as the reason underlying the lower quality factor before annealing. Furthermore, these findings demonstrate that targeted structural engineering at the nanoscale offers a powerful strategy for optimizing the optomechanical performance of plasmonic nanostructures, with broad implications for the design of next-generation nanophotonic and optomechanical systems.

Annealing (metallurgy)↗

Monolayer Films of Binary Metal Oxide Nanoparticles for Carbon Nanotube Synthesis

Binary metal oxide nanoparticles (biMO-NPs) combining transition and main-group metals with well-organized atomic architectures have unique potential as robust and economical heterogeneous catalysts. Herein, metal oxide nanoparticles (CoAlxOy) using cobalt and aluminum were synthesized, and their structure, morphology, and chemical composition were investigated using various characterization techniques. The biMO-NPs, which had a Gaussian-type size distribution (∼6 nm), were assembled on plain silicon substrates modified chemically with linker molecules bearing suitable end groups. Surface analysis revealed an ordered, uniform, close-packed arrangement of biMO-NPs forming a monolayer architecture with nanoscale thickness (∼12 nm), high surface uniformity, and negligible defects. The nanoparticle monolayer film (NP-MF) was employed as a catalyst to grow carbon nanotube (CNT) forests via the thermal chemical vapor deposition (CVD) method, similar to those grown from catalyst thin films deposited by physical vapor deposition. Structural characterization confirmed the growth of a dense, uniform, high-quality vertically aligned carbon nanotube (VA-CNT) forest with a length of ∼125 µm, which is comparable to the VA-CNTs grown from expensive thin films. Thus, CNT growth was successfully catalyzed by the biMO-NPs, highlighting a simple and inexpensive alternative for catalyst deposition. In this innovative wet-chemistry approach, the catalyst and catalyst support are combined within a single nanoparticle before NP-MF assembly. Interestingly, this approach provides a scalable and cost-effective pathway for CNT growth, eliminating the need for expensive thin deposition techniques.

Regmi, Bishow [University of Cincinnati]↗

Scattering-type Scanning Near-Field Optical Microscopy of Polymer-Coated Gold Nanoparticles

Scattering-type scanning near-field optical microscopy (s-SNOM) has emerged over the past years as a powerful characterization tool that can probe important properties of advanced materials and biological samples in a label-free manner, with spatial resolutions lying in the nanoscale realm. In this work, we explore such usefulness in relationship with an interesting class of materials: polymer-coated gold nanoparticles (NPs). As thoroughly discussed in recent works, the interplay between the Au core and the polymeric shell has been found to be important in many applications devoted to biomedicine. We investigate bare Au NPs next to polystyrenesulfonate (PSS) and poly(diallyldimethylammonium chloride) (PDDA) coated ones under 532 nm laser excitation, an wavelength matching the surface plasmon band of the custom-synthesized nanoparticles. We observe consistent s-SNOM phase signals in the case of bare and shallow-coated Au NPs, whereas for thicker shell instances, these signals fade. For all investigated samples, the s-SNOM amplitude signals were found to be very weak, which may be related to reduced scattering efficiency due to absorption of the incident beam. We consider these observations important, as they may facilitate studies and applications in nanomedicine and nanotechnology where the precise positioning of polymer-coated Au NPs with nanoscale resolution is needed besides their dielectric function and related intrinsic optical properties, which are also quantitatively available with s-SNOM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Image registration for in situ X-ray nano-imaging of a composite battery cathode with deformation

The structural and chemical evolution of battery electrodes at the nanoscale plays an important role in affecting the cell performance. Nano-resolution X-ray microscopy has been demonstrated as a powerful technique for characterizing the evolution of battery electrodes under operating conditions with sensitivity to their morphology, compositional distribution and redox heterogeneity. In real-world batteries, the electrode could deform upon battery operation, causing challenges for the image registration which is necessary for several experimental modalities, e.g. XANES imaging. To address this challenge, this work develops a deep-learning-based method for automatic particle identification and tracking. This approach was not only able to facilitate image registration with good robustness but also allowed quantification of the degree of sample deformation. The effectiveness of the method was first demonstrated using synthetic datasets with known ground truth. The method was then applied to an experimental dataset collected on an operating lithium battery cell, revealing a high degree of intra- and interparticle chemical complexity in operating batteries.

25 ENERGY STORAGE↗

A MEMS dynamic mechanical analyzer for in situ viscoelastic characterization of 3D printed nanostructures

Cellular metamaterial structures with sub-micron features have shown the ability to become excellent energy absorbing materials for impact mitigation due to the enhanced mechanical properties of materials at the nanoscale. However, in order to optimize the design of these energy absorbing metamaterial structures we need to be able to measure the dynamic properties of the sub-micron features such as storage and loss moduli and the loss factor. Therefore, at scale testing is required to capture the scale, temperature, and strain rate dependent material properties of these nanoscale materials. This study presents the design, fabrication, and calibration of a MEMS-based dynamic mechanical analyzer (DMA) that can be directly integrated with the two photon lithography (TPL) process commonly used to fabricate metamaterial structures with nanoscale features. The MEMS-based DMA consists of a chevron style thermal actuator used to generate a tensile load on the structure and two differential capacitive sensors on each side of the structure used to measure load and displacement. This design demonstrated 1.5 ± 0.75 nm displacement resolution and 104 ± 52 nN load resolution, respectively. Dynamic mechanical analysis was successfully conducted on a single nanowire feature printed between the load and displacement stages of the MEMS device with testing frequencies ranging between 0.01–10 Hz and testing temperatures ranging between 22 °C–47 °C. These initial tests on an exemplar TPL part demonstrate that the printed nanowire behaves as a viscoelastic material wherein the transition from glassy to viscous behavior has already set in at the room temperature.

42 ENGINEERING↗

Distribution of Copper States, Phases, and Defects across the Depth of a Cu-Doped CdTe Solar Cell

Copper has been used as a p-type dopant in cadmium telluride (CdTe) for decades. However, the density of Cu atoms in the finished device is much higher than that of holes, which means that most Cu atoms are not activated as acceptors during incorporation. Furthermore, studies have demonstrated that the distribution of copper (Cu) atoms across the device is highly inhomogeneous, with reports citing Cu substitution on Cd sites and segregation to grain boundaries. Fast diffusion along these boundaries and Cu accumulation at the CdTe/CdS interface have also been observed and validated computationally. These levels of inhomogeneity make it difficult to accurately characterize and correlate the performance with the nature of the Cu atomic species present. To address this challenge, we utilize X-ray microscopy and, specifically, nanoscale fluorescence-mode X-ray absorption near-edge structure to resolve the atomic Cu environment throughout the depth of the CdTe layer. Our results suggest that the majority of Cu atoms are in the form of Cu x Te phases (or similar local environments) near the ZnTe|CdTe interface, Cu x O phases in the CdTe absorber, and present in various oxidation states, including Cu 1+ and Cu 2+ , near the CdS/CdTe junction. Here this work also provides experimental evidence for the first time of the presence of CuS around the ZnTe|CdTe interface and the hypothesized Cu Cd -Cl i complex in the CdTe absorber.

14 SOLAR ENERGY↗

High Resolution Imaging and Analysis of Terrestrial Impact Glass: Amorphous Materials, Phyllosilicates and Everything in Between

Introduction: Impact cratering is one of the most ubiquitous geologic processes shaping the surface of all solid bodies in our solar system. Impacts are also a major source of clay minerals, poorly crystalline clay-like phases and amorphous (i.e., lacking long-range atomic order) materials on Earth and Mars. Phyllosilicates and amorphous materials have consistently formed a major component (~20-70 wt%) of every single drilled rock and soil sample in Gale Crater on Mars, as determined by the CheMin instrument on Curiosity. The origin of the amorphous component is speculative, but could be primary impact or volcanic-produced glass(es) deposited via aeolian or fluvial processes, secondary aqueous alteration products or chemical precipitates; it is likely to be a combination of all three possibilities. Efforts to determine the composition of these materials across the rover’s traverse through Gale Crater are ongoing. Naturally occurring amorphous phases are found in a variety of environments on Earth, and terrestrial analogue studies may help shed light on how they may have formed on Mars. Primary and altered impact glass are likely widespread on Mars and may have contributed to the amorphous component found throughout Gale Crater. In its pristine, unaltered state, impact glass (i.e., melt glass) is considered amorphous. However, truly unaltered glass is rarely preserved in crater fill impactites as it quickly alters in the post-impact environ-ment, commonly forming a mixture of hydrated aluminosilicate phases whose structures are not always discernable at the microscale (i.e., they may be amorphous or contain short-range order). These phases are part of an incredibly complex group of materials; differences in their composition and crystalline structure (or lack thereof) and genetic relationship to the more well-crystalline clay minerals are often only discernable at the nanoscale, beyond the resolution of traditional X-ray diffractometers (XRD) and scanning electron microscopes/microprobes (SEM/EPMA) alone. In this contribution, we summarize recent results from ongoing characterization of clay minerals, poorly crystalline clay-like phases, and amorphous materials preserved in altered terrestrial impact glass from the Chicxulub (~66 Ma) and Ries (~15 Ma) impact structures. This work has been performed using a combination of high-resolution transmission electron microscopy (HR-TEM), SEM, microprobe/EPMA, Raman spectroscopy and XRD.

Impact crater↗

NSUF Rad-AFM: Nanoscale Material Property Measurements of Radioactive Materials

Many advances in our understanding of radiation induced damage mechanisms are due to imaging techniques including transmission electron microscopy and scanning electron microscopy. However, the effect of these radiation induced defects characterized on the atomic to micrometer scale are often interpreted by changes in bulk material properties measured in the hundreds of microns to cm scale. In order to bridge this gap, additional tools need to be developed for use with radioactive materials. To this end a new Asylum Infinity multimodal atomic force microscope (AFM) has been added to the library of Nuclear Science User Facility (NSUF) instruments for use on radioactive materials. This instrument is housed in the Radiochemical Processing Laboratory (RPL) which is a Department of Energy Hazard Category II Non-Reactor Nuclear Facility operated by Battelle at Pacific Northwest National Laboratory. This allows for the handling, sample preparation, and characterization of highly radioactive materials providing a unique capability to understand fundamental properties of nuclear materials and the effects of radiation induced damage.

Riechers, Shawn L.↗

Janus Superiority of Membranes in Chemical Engineering and Beyond

Janus configurations, characterized by their inherent asymmetry, enable directional mass transfer in membrane materials that drive novel and energy-efficient chemical processes. This Janus superiority spans applications from nanoscale molecular and ionic transport to macro-scale separation systems with asymmetric spatial architectures. This review provides an analysis of the material foundations including design principles, structure regulation, and scalability challenges underlying Janus membranes. Here, we explore the physics that governs their unique behavior and examine their diverse applications across chemical engineering, including phase transfer, and molecular or ionic transport. Through a multiscale perspective, we provide a comprehensive understanding of the impact of Janus superiority in advancing chemical engineering technologies. Finally, we discuss the hurdles in translating theoretical advances into practical applications and propose promising avenues for future research to harness the full potential of Janus membranes and systems in addressing global challenges related to energy, sustainability, and beyond.

Yang, Hao‐Cheng [Zhejiang University, Hangzhou (Ch↗

Persistent and partially mobile oxygen vacancies in Li-rich layered oxides

Increasing the energy density of layered oxide battery electrodes is challenging as accessing high states of delithiation often triggers voltage degradation and oxygen release. Here we utilize transmission-based X-ray absorption spectromicroscopy and ptychography on mechanically cross-sectioned Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ electrodes to quantitatively profile the oxygen deficiency over cycling at the nanoscale. The oxygen deficiency penetrates into the bulk of individual primary particles (~200 nm) and is well-described by oxygen vacancy diffusion. Using an array of characterization techniques, we demonstrate that, surprisingly, bulk oxygen vacancies that persist within the native layered phase are indeed responsible for the observed spectroscopic changes. We additionally show that the arrangement of primary particles within secondary particles (~5 μm) causes considerable heterogeneity in the extent of oxygen release between primary particles. Finally, our work merges an ensemble of length-spanning characterization methods and informs promising approaches to mitigate the deleterious effects of oxygen release in lithium-ion battery electrodes.

25 ENERGY STORAGE↗

Recent experimental explorations of non-classical nucleation

Nucleation, the early stage of crystallization, is a key step in producing functional materials, but nucleation processes have yet to be understood in detail. Recent advanced characterization techniques, especially atomic force microscopy, liquid-cell transmission electron microscopy (TEM) and cryo-TEM, enable scientists to observe previously inaccessible nucleation details at the nanoscale. In this review, we summarize newly suggested non-classical nucleation models with respect to mechanistic understanding from experimental views, which highlight multi-step nucleation mechanisms. Different intermediated phases such as clusters at the pre-nucleation stage, liquid-like precursors, amorphous phases and even oligomers have been revealed, which play vital roles in nucleation and structure control. Moreover, these intermediated phases practically contribute in general to the structural variances of materials for nanoscience and nanotechnology. Overall, these studies ultimately enable us to control nucleation processes for materials synthesis.

Jin, Biao↗

Fabrication of single-crystalline YFeO3 films with large antiferromagnetic domains

The antiferromagnetic orthoferrite YFeO3 possesses fascinating magnetic properties for spintronics, such as terahertz spin dynamics, ultrafast domain wall motion, and long magnon decay length. YFeO3 belongs to a special family of antiferromagnets that show an unusually strong non-trivial Kerr response due to its weak ferromagnetism. The highly stable antiferromagnetic domains without any spontaneous spin rotation transitions below the 645 K Néel temperature may be useful for nanoscale device applications. We report the successful fabrication of high-quality twinning-free (110)-oriented YFeO3 films by pulsed laser deposition. Detailed structural and magnetic characterization revealed that the crystal structure and magnetic properties of the YFeO3 films are comparable to bulk single crystals. We show that the spin rotation under high magnetic fields follows the two-sublattice approximation model. The film surface is atomically flat with step-terrace surface morphology. A longitudinal magneto-optic Kerr (MOKE) rotation of 10 mdeg was observed at room temperature, which is consistent with earlier reports on bulk single crystals. The in-plane anisotropy of the Kerr response corresponds to the obtained magnetic anisotropy from the SQUID measurement. The large MOKE signal enables the imaging of antiferromagnetic domains and their reversal. The domain size was found to be larger than 100 μm. These high-quality YFeO3 thin films facilitate the fabrication of antiferromagnetic spintronic devices and provide a convenient platform for studying various spin-related phenomena in thin films and at interfaces.

Physics↗

Quantitative phase retrieval and characterization of magnetic nanostructures via Lorentz (scanning) transmission electron microscopy

Magnetic materials phase reconstruction using Lorentz transmission electron microscopy (LTEM) measurements have traditionally been achieved using longstanding methods such as off-axis holography (OAH) fast-Fourier transform technique and the transport-of-intensity equation (TIE). The increase in access to processing power alongside the development of advanced algorithms have allowed for phase retrieval of nanoscale magnetic materials with greater efficacy and resolution. Specifically, reverse-mode automatic differentiation (RMAD) and the extended electron ptychography iterative engine (ePIE) are two recent developments of phase retrieval that can be applied to analyzing micro-to-nano- scale magnetic materials. This work evaluates phase retrieval using TIE, RMAD, and ePIE in simulations of Permalloy (Ni 80 Fe 20 ) nanoscale islands, or nanomagnets. Extending beyond simulations, we demonstrate total phase retrieval and image reconstructions of a NiFe nanowire using OAH and RMAD in LTEM and ePIE in Lorentz-mode-4D scanning transmission electron microscopy experiments and determine the saturation magnetization through corroborations with micromagnetic modeling. Finally, we demonstrate the efficacy of these methods in retrieving the total phase and highlight its use in characterizing and analyzing the proximity effect of the magnetic nanostructures.

Lorentz transmission electron microscopy↗

Nanoscale Analysis of Space-Weathering Features in Soils from Itokawa

Space weathering alters the spectral properties of airless body surface materials by redden-ing and darkening their spectra and attenuating characteristic absorption bands, making it challenging to characterize them remotely [1,2]. It also causes a discrepency between laboratory analysis of meteorites and remotely sensed spectra from asteroids, making it difficult to associate meteorites with their parent bodies. The mechanisms driving space weathering include mi-crometeorite impacts and the interaction of surface materials with solar energetic ions, particularly the solar wind. These processes continuously alter the microchemical and structural characteristics of exposed grains on airless bodies. The change of these properties is caused predominantly by the vapor deposition of reduced Fe and FeS nanoparticles (npFe(sup 0) and npFeS respectively) onto the rims of surface grains [3]. Sample-based analysis of space weathering has tra-ditionally been limited to lunar soils and select asteroidal and lunar regolith breccias [3-5]. With the return of samples from the Hayabusa mission to asteroid Itoka-wa [6], for the first time we are able to compare space-weathering features on returned surface soils from a known asteroidal body. Analysis of these samples will contribute to a more comprehensive model for how space weathering varies across the inner solar system. Here we report detailed microchemical and microstructal analysis of surface grains from Itokawa.

Thompson, M. S.↗

Microstructural and chemical characterization of a purple pigment from a Faiyum mummy portrait

Results are presented from analyses that were conducted to explain the presence of chromium, detected noninvasively using energy dispersive X-ray fluorescence (XRF), in the unusually large (2-3mm diameter) rough gem-like purple pigment particles in the paint used for a Faiyum mummy portrait. An approximately 50 µm diameter particle of the chromium-containing purple pigment was extracted from the Portrait of a Bearded Man, dated to Roman Imperial Egypt in the second century, circa 170-180 CE, accession #32.6 in the Walters Art Museum collection. The particle was characterized using energy dispersive X-ray fluorescence analysis, electron microscopy, diffraction, and atom probe tomography. It is demonstrated that the purple pigment particle is a heterogeneous organic pigment, specifically, a lake pigment likely derived from either plant or insect matter, which contains minor percentages of both transition metals and alkali / alkali earth metals, with nanometer-scale crystallites of lead carbonates and sulfates. The analyses revealed for the first time the nanoscale microstructure and stratigraphy in an ancient lake pigment. Results suggest that similarities with respect to time-period and place of production may be developed among unprovenienced Faiyum mummy portraits to help localize workshops or artists, using analyses focused on lake pigments to characterize specifically metal-based mordants.

36 MATERIALS SCIENCE↗