Search for: All records

Abstract We introduced and applied a set of parameters to quantify surface modifications and pattern resolutions made by a Ga ion beam in a focused ion beam instrument using two material systems, Si and SrTiO3. A combination of top-view scanning electron microscopy and cross-sectional scanning transmission electron microscopy imaging and energy-dispersive X-ray spectroscopy was used to study the structure, composition and measure dimensions of the patterned lines. The total ion dose was identified as the key parameter governing the line characteristics, which can be controlled by the degree of overlap among adjacent spots, beam dwell time at each spot, and number of beam passes for given beam size and current. At higher ion doses (>1015 ions/cm2), the Ga ions remove part of the material in the exposed area creating “channels” surrounded with amorphized regions, whereas at lower ion doses only amorphization occurs, creating “ridges” on the wafer surface. To pattern lines with similar sizes, an order of magnitude different ion doses was required for Si and SrTiO3 indicating strong material dependence. Quantification revealed that lines as fine as 10 nm can be reproducibly patterned and characterized on the surfaces of materials. 

Abstract Exciton‐polaritons in organic microcavities are applied in devices including lasers, light‐emitting devices, and photodetectors, as well as in structures capable of tuning exciton kinetics and energy transfer. To enable a broader tailoring of polariton properties, it is important to develop means to better control molecular orientation and tune the intensity of the exciton–photon interaction. Vapor‐processed, glassy organic thin films are previously shown to have tunable molecular orientation as evidenced by phenomena including birefringence and transition dipole moment (TDM) alignment. Here, this tunability in TDM orientation with thin film processing conditions is exploited to continuously vary the interaction between the exciton and confined cavity photon mode. By embedding a thin film of 4,4′‐bis[(N‐carbazole)styryl]biphenyl (BSB‐Cz) in a metal‐reflector microcavity, ultrastrong coupling and hybridization of multiple electronic transitions of BSB‐Cz are demonstrated with a common cavity mode. Increasing the temperature during BSB‐Cz deposition tunes the TDM orientation from predominantly in‐plane to random to slightly vertical. This leads to a corresponding ≈30% variation in the associated Rabi splitting, consistent with theoretical predictions. This work demonstrates a means to continuously tune coupling strength from a materials perspective while also providing a handle to tune orientation disorder in thin film. 

Abstract Broader adoption of 4D ultrafast electron microscopy (UEM) for the study of chemical, materials, and quantum systems is being driven by development of new instruments as well as continuous improvement and characterization of existing technologies. Perhaps owing to the still‐high barrier to entry, the full range of capabilities of laser‐driven 4D UEM instruments has yet to be established, particularly when operated at extremely low beam currents (~fA). Accordingly, with an eye on beam stability, we have conducted particle tracing simulations of unconventional off‐axis photoemission geometries in a UEM equipped with a thermionic‐emission gun. Specifically, we have explored the impact of experimentally adjustable parameters on the time‐of‐flight (TOF), the collection efficiency (CE), and the temporal width of ultrashort photoelectron packets. The adjustable parameters include the Wehnelt aperture diameter (D_W), the cathode set‐back position (Z_tip), and the position of the femtosecond laser on the Wehnelt aperture surface relative to the optic axis (R_photo). Notable findings include significant sensitivity of TOF toD_WandZ_tip, as well as non‐intuitive responses of CE and temporal width to varyingR_photo. As a means to improve accessibility, practical implications and recommendations are emphasized wherever possible. 

Abstract Magnetic particle imaging (MPI) is a tracer-based tomographic imaging technique utilized in applications such as lung perfusion imaging, cancer diagnosis, stem cell tracking, etc. The goal of translating MPI to clinical use has prompted studies on further improving the spatial-temporal resolutions of MPI through various methods, including image reconstruction algorithm, scanning trajectory design, magnetic field profile design, and tracer design. Iron oxide magnetic nanoparticles (MNPs) are favored for MPI and magnetic resonance imaging (MRI) over other materials due to their high biocompatibility, low cost, and ease of preparation and surface modification. For core–shell MNPs, the tracers’ magnetic core size and non-magnetic coating layer characteristics can significantly affect MPI signals through dynamic magnetization relaxations. Most works to date have assumed an ensemble of MNP tracers with identical sizes, ignoring that artificially synthesized MNPs typically follow a log-normal size distribution, which can deviate theoretical results from experimental data. In this work, we first characterize the size distributions of four commercially available iron oxide MNP products and then model the collective magnetic responses of these MNPs for MPI applications. For an ensemble of MNP tracers with size standard deviations ofσ, we applied a stochastic Langevin model to study the effect of size distribution on MPI imaging performance. Under an alternating magnetic field (AMF), i.e., the excitation field in MPI, we collected the time domain dynamic magnetizations (M-t curves), magnetization-field hysteresis loops (M-H curves), point-spread functions (PSFs), and higher harmonics from these MNP tracers. The intrinsic MPI spatial resolution, which is related to the full width at half maximum (FWHM) of the PSF profile, along with the higher harmonics, serve as metrics to provide insights into how the size distribution of MNP tracers affects MPI performance. 

Abstract Despite their highly anisotropic complex-oxidic nature, certain delafossite compounds (e.g., PdCoO₂, PtCoO₂) are the most conductive oxides known, for reasons that remain poorly understood. Their room-temperature conductivity can exceed that of Au, while their low-temperature electronic mean-free-paths reach an astonishing 20 μm. It is widely accepted that these materials must be ultrapure to achieve this, although the methods for their growth (which produce only small crystals) are not typically capable of such. Here, we report a different approach to PdCoO₂crystal growth, using chemical vapor transport methods to achieve order-of-magnitude gains in size, the highest structural qualities yet reported, and record residual resistivity ratios ( > 440). Nevertheless, detailed mass spectrometry measurements on these materials reveal that they are not ultrapure in a general sense, typically harboring 100s-of-parts-per-million impurity levels. Through quantitative crystal-chemical analyses, we resolve this apparent dichotomy, showing that the vast majority of impurities are forced to reside in the Co-O octahedral layers, leaving the conductive Pd sheets highly pure (∼1 ppm impurity concentrations). These purities are shown to be in quantitative agreement with measured residual resistivities. We thus conclude that a sublattice purification mechanism is essential to the ultrahigh low-temperature conductivity and mean-free-path of metallic delafossites. 

Abstract We report the development of a small molecule‐based barcoding platform for pooled screening of nanoparticle delivery. Using aryl halide‐based tags (halocodes), we achieve high‐sensitivity detection via gas chromatography coupled with mass spectrometry or electron capture. This enables barcoding and tracking of nanoparticles with minimal halocode concentrations and without altering their physicochemical properties. To demonstrate the utility of our platform for pooled screening, we synthesized a halocoded library of polylactide‐co‐glycolide (PLGA) nanoparticles and quantified uptake in ovarian cancer cells in a pooled manner. Our findings correlate with conventional fluorescence‐based assays. Additionally, we demonstrate the potential of halocodes for spatial mapping of nanoparticles using mass spectrometry imaging (MSI). Halocoding presents an accessible and modular nanoparticle screening platform capable of quantifying delivery of pooled nanocarrier libraries in a range of biological settings. 

Abstract Na₂WO₄/SiO₂, a material known to catalyze alkane selective oxidation including the oxidative coupling of methane (OCM), is demonstrated to catalyze selective hydrogen combustion (SHC) with >97 % selectivity in mixtures with several hydrocarbons (CH₄, C₂H₆, C₂H₄, C₃H₆, C₆H₆) in the presence of gas‐phase dioxygen at 883–983 K. Hydrogen combustion rates exhibit a near‐first‐order dependence on H₂partial pressure and are zero‐order in H₂O and O₂partial pressures. Mechanistic studies at 923 K using isotopically‐labeled reagents demonstrate the kinetic relevance of H−H dissociation and absence of O‐atom recombination. In situ X‐ray diffraction (XRD) and W L_III‐edge X‐ray absorption spectroscopy (XAS) studies demonstrate, respectively, a loss of Na₂WO₄crystallinity and lack of second‐shell coordination with respect to W⁶⁺cations below 923 K; benchmark experiments show that alkali cations must be present for the material to be selective for hydrogen combustion, but that materials containing Na alone have much lower combustion rates (per gram Na) than those containing Na and W. These data suggest a synergy between Na and W in a disordered phase at temperatures below the bulk melting point of Na₂WO₄(971 K) during SHC catalysis. The Na₂WO₄/SiO₂SHC catalyst maintains stable combustion rates at temperatures ca. 100 K higher than redox‐active SHC catalysts and could potentially enable enhanced olefin yields in tandem operation of reactors combining alkane dehydrogenation with SHC processes. 

Abstract Polarization, as a fundamental property of light, plays a key role in many phenomena of near‐field coupling, namely the coupling of source's evanescent waves into some guided modes. As a typical example of the polarization‐locked phenomenon in the near‐field coupling, the Janus dipole has the orientation of its near‐field coupling face intrinsically determined by the polarization state of linearly‐polarized surface waves, specifically whether they are transverse‐magnetic (TM) or transverse‐electric (TE) surface waves. Here, a mechanism to achieve the directional near‐field coupling of Janus dipoles beyond polarization locking by leveraging hybrid TM‐TE surface waves is presented. These hybrid surface waves, as eigenmodes with both TM and TE wave components, can be supported by optical interfaces between different filling materials inside a parallel‐plate waveguide. Under the excitation of hybrid surface waves, it is found that the coupling and non‐coupling face of a Janus dipole may be switched, if the Janus dipole itself rotates in a plane parallel to the designed optical interface between different filling materials, without resorting to the change of surface‐wave polarization. The underlying mechanism is due to the capability of hybrid surface waves to extract both the source's TM and TE evanescent waves, which offers an alternative paradigm to regulate the interference in the near‐field coupling. 

Abstract Current potentiometric sensing methods are limited to detecting nitrate at parts-per-billion (sub-micromolar) concentrations, and there are no existing potentiometric chemical sensors with ultralow detection limits below the parts-per-trillion (picomolar) level. To address these challenges, we integrate interdigital graphene ion-sensitive field-effect transistors (ISFETs) with a nitrate ion-sensitive membrane (ISM). The work aims to maximize nitrate ion transport through the nitrate ISM, while achieving high device transconductance by evaluating graphene layer thickness, optimizing channel width-to-length ratio (R_WL), and enlarging total sensing area. The captured nitrate ions by the nitrate ISM induce surface potential changes that are transduced into electrical signals by graphene, manifested as the Dirac point shifts. The device exhibits Nernst response behavior under ultralow concentrations, achieving a sensitivity of 28 mV/decade and establishing a record low limit of detection of 0.041 ppt (4.8 × 10⁻¹³M). Additionally, the sensor showed a wide linear detection range from 0.1 ppt (1.2 × 10⁻¹²M) to 100 ppm (1.2 × 10⁻³M). Furthermore, successful detection of nitrate in tap and snow water was demonstrated with high accuracy, indicating promising applications to drinking water safety and environmental water quality control. 

Abstract Voltage‐Gated Spin‐Orbit‐Torque (VGSOT) Magnetic Random‐Access Memory (MRAM) is a promising candidate for reducing writing energy and improving writing speed in emerging memory and in‐memory computing applications. However, conventional Voltage Controlled Magnetic Anisotropy (VCMA) approaches are often inefficient due to the low VCMA coefficient at the CoFeB/MgO interface. Additionally, traditional heavy metal/perpendicular magnetic anisotropy (PMA) ferromagnet bilayers require an external magnetic field to overcome symmetry constraints and achieve deterministic SOT switching. Here, a novel and industry‐compatible SOT underlayer for next‐generation VGSOT MRAM by employing a composite heavy metal tri‐layer with a high work function is presented. This approach achieves a VCMA coefficient exceeding 100 fJ V⁻¹m⁻¹through electron depletion effects, which is ten times larger than that observed with a pure W underlayer. Furthermore, it is demonstrated that this composite heavy metal SOT underlayer facilitates the integration of VCMA with opposite spin Hall angles, enabling field‐free SOT switching in industry‐compatible PMA CoFeB/MgO systems.