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DOE OSTI2020

Noninvasive Near‐Field Spectroscopy of Single Subwavelength Complementary Resonators

Abstract Subwavelength metallic resonators provide a route to achieving strong light–matter coupling by means of tight confinement of resonant electromagnetic fields. Investigation of such resonators however often presents experimental difficulties, particularly at terahertz (THz) frequencies. A single subwavelength resonator interacts weakly with THz beams, making it difficult to probe it using far‐field methods, whereas arrays of resonators exhibit inter‐resonator coupling, which affect the resonator spectral signature and field confinement. Here, traditional far‐field THz spectroscopy is systematically compared with aperture‐type THz near‐field microscopy for investigating complementary THz resonators. While the far‐field method proves impractical for measuring single resonators, the near‐field technique gives high signal‐to‐noise spectral information, only achievable in the far‐field with resonator arrays. At the same time, the near‐field technique allows to analyze single resonators without significant interaction with the near‐field probe. Furthermore, the near‐field technique allows highly confined fields and surface waves to be mapped in space and time. This information gives invaluable insight into spectral response in resonator arrays. This near‐field microscopy and spectroscopy method enables investigations of strong light–matter coupling at THz frequencies in the single‐resonator regime.

Hale, Lucy L.↗

DOE OSTI2021

Additive manufacturing and applications of nanomaterial-based sensors

Nanoscale materials possess distinct physical and chemical attributes including size-dependent properties, quantum confinement, high surface-to-volume ratio, and superior catalytic activity. These unique qualities enable sensors with high sensitivity, robustness, and fast time response. As the emergence of the Internet of Things (IoT) demands increased production of sensors, it also provides an impetus for concentrated nanomaterial-based sensor research. Meanwhile, additive manufacturing (AM) of nanomaterial-based sensors is critical to bridge the gap between one-off, lab-scale fabrication and cost-effective, industrial-scale production with high reproducibility. By applying the design flexibility and cost savings of AM techniques, a new generation of nanomaterial-based sensing platforms can be integrated with IoT devices in the consumer space. Furthermore, emergent research in human-machine interfaces, food safety, and point-of-care diagnostics will be expedited by the development of sensors that can be printed with irregular form factors. In this Review, the relative strengths and weaknesses of printed sensor systems based on zero-, one-, and two-dimensional nanomaterials are discussed. In addition, sensors enabled by printable soft nanomaterials, heterostructures, and nanocomposites are surveyed due to their synergistic advantages for wearable healthcare monitoring and soft robotics. Lastly, a roadmap for the next decade of research on this topic is provided.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Hierarchically structured MoO 2 /dopamine-derived carbon spheres as intercalation electrodes for lithium-ion batteries

A hydrogen peroxide initiated sol-gel process involving molybdenum transformation in the presence of dopamine (Dopa) hydrochloride excess produced the metastable precipitate composed of polydopamine (PDopa) spheres coated with Dopa preintercalated molybdenum oxide, (Dopa) x MoO y @PDopa. The hydrothermal treatment (HT) of the (Dopa) x MoO y @PDopa precursor resulted in the simultaneous carbonization of Dopa and molybdenum reduction generating MoO 2 nanoplatelets distributed and confined on the surface of the Dopa-derived carbon matrix (HT-MoO 2 /C). The consecutive annealing (An) of the HT-MoO 2 /C sample at 600 °C under Ar atmosphere led to the formation of MoO 2 with increased Mo oxidation state and improved structural stability (AnHT-MoO 2 /C). Annealing had also further facilitated interaction between the molybdenum-derived and Dopa-derived components resulting in the modification of the carbon matrix confirmed by Raman spectroscopy. Morphology of both materials is best described as Dopa-derived carbon spheres decorated with MoO 2 nanoplatelets. These integrated metal oxide and carbon structures were tested as electrodes for lithium-ion batteries in the potential window that corresponds to the intercalation mechanism of charge storage. The AnHT-MoO 2 /C electrode showed enhanced electrochemical activity, with an initial specific discharge capacity of 260 mAh/g and capacity retention of 67% after 50 cycles, compared to the HT-MoO 2 /C electrode which exhibited an initial specific discharge capacity of 235 mAh g –1 and capacity retention of 47% after 50 cycles. The rate capability experiments revealed that the capacity of 93 mAh/g and 120 mAh/g was delivered by the HT-MoO 2 /C and AnHT-MoO 2 /C electrodes, respectively, when the current density was increased to 100 mA/g. Here, the improved specific capacity, electrochemical stability, and rate capability achieved after annealing were attributed to higher crystallinity of MoO 2 , increased oxidation state of Mo, and formation of the tighter MoO 2 /carbon contact accompanied by the annealing assisted interaction between MoO 2 and Dopa-derived carbon.

25 ENERGY STORAGE↗

DOE OSTI2024

A Jacobian-free pseudo-arclength continuation method for phase transitions in inhomogeneous thermodynamic systems

Developing phase diagrams for inhomogeneous systems in thermodynamics is difficult, in part, due to the large phase space and the possibility of unstable and metastable solutions arising from first-order phase transitions. Pseudo-arclength continuation (PAC) is a method that allows one to trace out stable and unstable solutions of nonlinear systems. Typically, PAC utilizes the Jacobian in order to implement Newton (or quasi-Newton) steps. In this work, we present a Jacobian-free PAC method that is amenable to the usual workflows in inhomogeneous thermodynamics. We demonstrate our method in systems that have first-order phase transitions, including a novel example of polyelectrolyte complex coacervation in confinement, where multiple surface phase transitions occur and can overlap with one another.

Chemistry↗

DOE OSTI2021

Mechanisms of transport enhancement for self-propelled nanoswimmers in a porous matrix

Significance As with living microorganisms, many real-world applications of synthetic micro/nanoswimmers are likely to rely on transport in complex environments, a phenomenon that remains poorly understood. Here, we report anomalously rapid transport of self-propelled particles in a porous medium, where nanoswimmers escaped from cavities more than an order of magnitude faster than expected compared to corresponding Brownian particles. This phenomenon was determined to be due to nuanced effects associated with self-propulsion, including enhanced mobility in confinement, efficient surface-mediated searching for holes, and the abolition of barriers at cavity exits. These mechanisms are broadly generalizable, and the previously unknown transport efficiency of nanoswimmers in complex porous environments suggests tremendous opportunities in forward-looking applications, including drug delivery and environmental remediation.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Characterization of Natural Consolidated Halloysite Nanotube Structures

Halloysite is a unique 1:1 clay mineral frequently appearing with nanotubular morphology, and having surfaces of different polarity with interesting and important technological applications. HNTs can be consolidated naturally in the earth by pressure and thermal flows. In this study of natural consolidated HNTs, the strength and hardness of these materials were found to be dependent on the presence of impurities (gibbsite, alunite, quartz, and other silica minerals), which accounted for the increased stability of such samples. In the absence of impurities, the strength of consolidated HNTs was significantly lower. The first 3D mapping of the pore structure of natural consolidated HNT is provided. The contributions of the porosity within the nanotubes and between the nanotubes were delineated using a combination of non-invasive ultra-small and small-angle X-ray scattering (USAXS/SAXS) analyses, BET/BJH pore size analyses, and computed tomography studies. A total porosity of 40%, as determined by X-ray attenuation and He porosimetry, was found for the natural consolidated HNTs, of which about one-third was due to the inter-HNT porosity. Nano-X-ray computed tomography (nano-XCT) analyses also indicated that 76% of the inter-HNT pores were smaller than 150 nm in diameter. The intra-HNT pore size determined by combined USAXS/SAXS and BET/BJH was about 10 nm. This pore network information is essential for the utilization of natural consolidated HNTs as a model geomaterial to investigate the effects of surface characteristics on confined fluid flow.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Compact folded metasurface spectrometer

Compact optical devices such as spectrometers are realized with metasurfaces within a dielectric medium confined by reflective surfaces. The metasurfaces control the phase profiles of the reflected electromagnetic waves within the device. In a compact spectrometer, the metasurfaces within the device separate the electromagnetic waves in different wavelengths. The metasurfaces are designed according to their phase profile by varying the size of the array of scatterers.

Faraji-Dana, MohammadSadegh↗

DOE OSTI2020

Embedding PbS Quantum Dots (QDs) in Pb-Halide Perovskite Matrices: QD Surface Chemistry and Antisolvent Effects on QD Dispersion and Confinement Properties

Hybrid materials of metal chalcogenide colloidal quantum dots (QDs) embedded in metal halide perovskites (MHPs) have led to composites with synergistic properties. Here, we investigate how QD size, surface chemistry, and MHP film formation methods affect the resulting optoelectronic properties of QD/MHP “dot-in-matrix” systems. We monitor the QD absorption and photoluminescence throughout synthesis, ligand exchange, and transfer into the MHP ink, and we characterize the final QD/MHP films via electron microscopy and transient absorption. In addition, we are the first to globally map how PbS QDs are distributed on the micrometer scale within these dot-in-matrix systems, using three-dimensional (3D) tomography time-of-flight secondary ion mass spectrometry. The surface chemistry imparted during synthesis directly affects the optical properties of the dot-in-matrix composites. Pb-halide passivation leads to QD/MHP dot-in-matrix samples with optical properties that are well-described by a theoretical model, based on a Type I finite-barrier heterostructure between the PbS QD and the MHP matrix. Samples without Pb-halide passivation show complicated size-dependent behavior, indicating a transition from a Type I heterostructure between the PbS QD wells and MHP barriers for small-sized QDs to PbS QDs that are electronically decoupled from the MHP matrix for larger QDs. Furthermore, the choice in perovskite antisolvent crystallization method leads to a difference in the spatial QD distribution within the perovskite matrix, differences in carrier lifetime, and photoluminescence shifts of up to 180 meV for PbS in methylammonium lead iodide. This work establishes an understanding of such emerging synergistic systems relevant for technologies such as photovoltaics, infrared emitters and detectors, and other unexplored technological applications.

92 SC - Basic Energy Sciences (BES) (SC-22)↗

DOE OSTI2024

Surface-binding molecular multipods strengthen the halide perovskite lattice and boost luminescence

Reducing the size of perovskite crystals to confine excitons and passivating surface defects has fueled a significant advance in the luminescence efficiency of perovskite light-emitting diodes (LEDs). However, the persistent gap between the optical limit of electroluminescence efficiency and the photoluminescence efficiency of colloidal perovskite nanocrystals (PeNCs) suggests that defect passivation alone is not sufficient to achieve highly efficient colloidal PeNC-LEDs. Here, we present a materials approach to controlling the dynamic nature of the perovskite surface. Our experimental and theoretical studies reveal that conjugated molecular multipods (CMMs) adsorb onto the perovskite surface by multipodal hydrogen bonding and van der Waals interactions, strengthening the near-surface perovskite lattice and reducing ionic fluctuations which are related to nonradiative recombination. The CMM treatment strengthens the perovskite lattice and suppresses its dynamic disorder, resulting in a near-unity photoluminescence quantum yield of PeNC films and a high external quantum efficiency (26.1%) of PeNC-LED with pure green emission that matches the Rec.2020 color standard for next-generation vivid displays.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Surface Wave Based Non-conductor-contact Reflectometry Method for Insulation and Jacket Damage Detection in Multi-Conductor Cables

This paper presents a non-conductor-contact surface wave reflectometry technique to locate insulation and jacket damage on multi-conductor cables at a distant location from the sensor. Simulation studies were conducted using Ansys high frequency structure simulator (HFSS). A GHz range surface wave launcher was employed such that maximum surface wave energies were confined in the insulation layer while minimizing attenuation. The wave launcher can potentially be mounted on the outer surface of live cables or cable conduits and requires no physical connection to the conductors. Multiple simulations involving a 4 GHz wave launcher and a three-conductor cable with an 8 mm outer diameter were carried out demonstrating the efficacy of the proposed method. Water leak and different types of insulation/jacket damage were simulated and detected.

reflectometry, multi-conductor cable, frequency do↗

DOE OSTI2026

How Silica Surface Chemistry Modulates Interfacial Water: Insights from Machine Learning Molecular Dynamics

Controlling water structure and dynamics at silica interfaces are central to a wide range of technologies, including protective oxide layers for solar water splitting and nanoporous membranes. In this work, we develop a machine learning interatomic potential, trained via active learning, to achieve ab initio accuracy for water confined between hydroxylated silica surfaces over a range of silanol coverages and slit widths. We find that partially hydroxylated surfaces (50 and 75% OH) support stronger water−surface hydrogen bonding and more extended interfacial density profiles than fully hydroxylated (100% OH) surfaces, indicating that increasing OH coverage does not necessarily strengthen interfacial hydrogenbond networks. Translational diffusion decreases approximately linearly with slit width and OH coverage, whereas rotational dynamics respond nonlinearly. In particular, at the smallest slit width of 5 Å, 75% OH coverage produces an enhanced local tetrahedral ordered interfacial network that strongly suppresses reorientation, while 100% coverage yields a crowded, disordered interfacial layer that also hinders rotation. In contrast, the 50% OH coverage is sufficiently sparse that it does not markedly alter water structure or dynamics under confinement. These results show that coupled control of pore size and surface chemistry enables nonlinear tuning of interfacial water structure and transport, providing a design strategy for optimizing porous silica for either enhanced interfacial stability and controlled reactivity or rapid and selective transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

X-ray Induced Cycling of Rare-Earth Elements between Bulk and Interfacial Liquid

Reversible cycling of rare-earth elements between an aqueous electrolyte solution and its free surface is achieved by X-ray exposure. This exposure alters the competitive equilibrium between lanthanide ions bound to a chelating ligand, diethylenetriamine pentaacetic acid (DTPA), in the bulk solution and to insoluble monolayers of extractant di-hexadecyl phosphoric acid (DHDP) at its surface. Evidence for the exposure-induced temporal variations in the lanthanide surface density is provided by X-ray fluorescence near total reflection measurements. Comparison of results when X-rays are confined to the aqueous surface region to results when X-rays transmit into the bulk solution suggests the importance of aqueous radiolysis in the adsorption cycle. Amine binding sites in DTPA are identified as a likely target of radiolysis products. The molecules DTPA and DHDP are like those used in the separation of lanthanides from ores and in the reprocessing of nuclear fuel. Furthermore, these results suggest that an external source of X-rays can be used to drive rare-earth element separations. More generally, use of X-rays to controllably dose a liquid interface with lanthanides could trigger a range of interfacial processes, including enhanced metal ion extraction, catalysis, and materials synthesis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Delineating Confinement Regimes for Nafion Thin Films via Simultaneous QCM-D and Spectroscopic Ellipsometry

Proton-conducting ionomers used in electrodes of electrochemical devices form nanometer-scale films covering metallic catalyst surfaces, wherein they experience confinement and interfacial effects absent in the bulk polymer. This confinement alters the physical properties of the ionomer film, which is postulated to increase the density and is attributed to the transport limitations observed in fuel-cell electrodes. Despite studies showing reduced swelling, no systematic measurement has validated this phenomenon by demonstrating both densification and stiffening as the film gets thinner. Here, this study aims to fill this gap by reporting the humidity-driven changes in swelling, mass uptake, and density of Nafion ionomer films cast at varying thicknesses (10–320 nm) onto a gold-plated sensor. The films were simultaneously probed during humidification using spectroscopic ellipsometry (SE) and a quartz crystal microbalance with dissipation (QCM-D), which allowed for determination of the density and shear stiffness. The effects of confinement were prominently observed below ∼30 nm, with films showing increased density along with decreased swelling and mass uptake during hydration. In addition, the confined films show a negative excess volume upon initial water sorption, implying a larger proportion of absorbed water might bound to ionic groups in accord with notion of localized densification.

Espinet, Kevin B. [University of California, Berke↗

DOE OSTI2021

Traction-separation response of bilayer graphene interfaces: The role of an intercalated single atomic layer of water molecules and hydroxyl groups

Molecular dynamics simulations of the normal and shear traction-separation response of dry and wet bilayer graphene interfaces were performed. The influence of a single, atomic layer of water molecules sandwiched between graphene layers and hydroxyl functionalization on one or both layers were investigated. Hydroxyl groups provided a shielding effect during normal separation while favoring stick-slip friction under sliding conditions. The single, atomic layer of water molecules confined between hydrophilic and asymmetric hydrophobic/hydrophilic surfaces was found to ease sliding friction. The mechanisms arose from the balance between the attractive and repulsive graphene/water interactions through bridges of single water molecules between the two surfaces and the structure of the water monolayer under confinement for which an out-of-plane water/water hydrogen bond network could not be developed. The single, atomic layer of water molecules reduced the sliding friction the most when both surfaces were hydrophilic and lowered the sliding friction of the asymmetric hydrophobic/hydrophilic interfaces to that when both surfaces were hydrophobic. An optimal hydroxyl surface coverage of less than 10% may exist for efficient water lubrication, with diminishing effect with increasing number of hydroxyl groups. Finally, the findings offer a design strategy for assembling bilayer graphene interfaces with tailored friction and sliding contact properties.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Beyond Idealized Models of Nanoscale Metal Hydrides for Hydrogen Storage

Metal hydrides are attractive for compact, low-pressure hydrogen storage, yet a foundational understanding of factors governing their thermodynamics and kinetics is still lacking. Predictive modeling from the atomic to the microstructural scale plays a critical role in addressing these gaps, particularly for nanoscale materials, which promise improved performance but are difficult to probe. In this paper, we summarize strategies being developed within the Hydrogen Materials—Advanced Research Consortium (HyMARC) for going beyond conventional models to incorporate more complex physics, more realistic structures, and better approximation of operation conditions in simulations of nanoscale metal hydrides. We highlight four beyond-ideal factors that influence predicted performance: (1) surface anharmonic dynamics, (2) interface and surface energy penalties, (3) mechanical stress under confinement, and (4) the presence of native surface oxide. Approaches for addressing these factors are demonstrated on model materials representative of high-capacity hydrogen storage systems, and implications for understanding performance under operating conditions are discussed.

08 HYDROGEN↗

DOE OSTI2020

Surface immobilized copper(i) diimine photosensitizers as molecular probes for elucidating the effects of confinement at interfaces for solar energy conversion

Heteroleptic copper(I) bis(phenanthroline) complexes with surface anchoring carboxylate groups have been synthesized and immobilized on nanoporous metal oxide substrates. The species investigated are responsive to the external environment and this work provides a new strategy to control charge transfer processes for efficient solar energy conversion.

14 SOLAR ENERGY↗

DOE OSTI2023

Optical Processes behind Plasmonic Applications

Plasmonics is a revolutionary concept in nanophotonics that combines the properties of both photonics and electronics by confining light energy to a nanometer-scale oscillating field of free electrons, known as a surface plasmon. Generation, processing, routing, and amplification of optical signals at the nanoscale hold promise for optical communications, biophotonics, sensing, chemistry, and medical applications. Surface plasmons manifest themselves as confined oscillations, allowing for optical nanoantennas, ultra-compact optical detectors, state-of-the-art sensors, data storage, and energy harvesting designs. Surface plasmons facilitate both resonant characteristics of nanostructures and guiding and controlling light at the nanoscale. Plasmonics and metamaterials enable the advancement of many photonic designs with unparalleled capabilities, including subwavelength waveguides, optical nanoresonators, super- and hyper-lenses, and light concentrators. Alternative plasmonic materials have been developed to be incorporated in the nanostructures for low losses and controlled optical characteristics along with semiconductor-process compatibility. This review describes optical processes behind a range of plasmonic applications. It pays special attention to the topics of field enhancement and collective effects in nanostructures. The advances in these research topics are expected to transform the domain of nanoscale photonics, optical metamaterials, and their various applications.

2D materials↗

DOE OSTI2026

Surface Vacancy Engineering Re-Routes First-Cycle Redox for Stabilized Li-Rich Layered Cathodes

We demonstrate that atomic-scale surface disorder can control the first-cycle redox sequence of Li-rich layered oxides, eliminating the detrimental process of oxygen release and lattice collapse that degrades performance. In Li1.14Ni0.32Mn0.54O2 (LNMO), a simple chemical treatment introduces oxygen and transition metal (TM) vacancies confined to the particle surface while preserving the bulk layered framework. Multi-modal synchrotron analyses reveal that these vacancies trigger an early oxygen oxidation below 4.4 V, delay nickel oxidation to higher potential, and suppress the formation of covalent Ni4+─O states. This modified pathway prevents irreversible oxygen release, suppresses manganese dissolution, and maintains metal-oxygen coordination at high voltages. Consequently, the treated cathode delivers higher first-cycle Coulombic efficiency (CE), mitigated voltage fade, and superior capacity retention. By directly linking engineered surface disorder to redox reactions and associated structural transformations, this work establishes a general design principle for durable, high-energy-density cathodes.

Kang, Seongkoo↗