Nonlinear Nano-Imaging of Interlayer Coupling in 2D Graphene-Semiconductor Heterostructures.

The emergent electronic, spin, and other quantum properties of 2D heterostructures of graphene and transition metal dichalcogenides are controlled by the underlying interlayer coupling and associated charge and energy transfer dynamics. However, these processes are sensitive to interlayer distance and crystallographic orientation, which are in turn affected by defects, grain boundaries, or other nanoscale heterogeneities. This obfuscates the distinction between interlayer charge and energy transfer. Here, nanoscale imaging in coherent four-wave mixing (FWM) and incoherent two-photon photoluminescence (2PPL) is combined with a tip distance-dependent coupled rate equation model to resolve the underlying intra- and inter-layer dynamics while avoiding the influence of structural heterogeneities in mono- to multi-layer graphene/WSe2 heterostructures. With selective insertion of hBN spacer layers, it is shown that energy, as opposed to charge transfer, dominates the interlayer-coupled optical response. From the distinct nano-FWM and -2PPL tip-sample distance-dependent modification of interlayer and intralayer relaxation by tip-induced enhancement and quenching, an interlayer energy transfer time of τ ET ≈ ( 0 . 35 - 0.15 + 0.65 ) $\tau _{\rm ET} \approx (0.35^{+0.65}_{-0.15})$  ps consistent with recent reports is derived. As a local probe technique, this approach highlights the ability to determine intrinsic sample properties even in the presence of large sample heterogeneity.

Subnanometer Visualization of Spatially Varying Local Field Resonances that Drive Tip-Enhanced Optical Spectroscopy.

Our knowledge of the electromagnetic fields that power modern nanoscale optical measurements, including (non)linear tip-enhanced Raman and photoluminescence, chiefly stems from numerical simulations. Aside from idealized in silico vs heterogeneous (nano)structures in the laboratory, challenges in quantitative descriptions of nanoscale light-matter interactions more generally stem from the very nature of the problem, which lies at the interface of classical and quantum theories. This is particularly the case in ultrahigh spatial resolution measurements that are sensitive to local optical field variations that take place on subnanometer length scales. This work approaches this challenge through extinction-based spectral nanoimaging experiments. We demonstrate <1 nm spatial resolution in hyperspectral extinction measurements that track spatially varying plasmon resonances. We describe the principles behind our experiments and highlight more general implications of our observations.

Ultrafast Nanoimaging of Electronic Coherence of Monolayer WSe2.

Transition-metal dichalcogenides (TMDs) have demonstrated a wide range of novel photonic, optoelectronic, and correlated electron phenomena for more than a decade. However, the coherent dynamics of their excitons, including possibly long dephasing times and their sensitivity to spatial heterogeneities, are still poorly understood. Here we implement adiabatic plasmonic nanofocused four-wave mixing (FWM) to image the coherent electron dynamics in monolayer WSe2. We observe nanoscale heterogeneities at room temperature with dephasing ranging from T2 ≲ 5 to T2 ≳ 60 fs on length scales of 50-100 nm. We further observe a counterintuitive anticorrelation between FWM intensity and T2, with the weakest FWM emission at locations of longest coherence. We interpret this behavior as a nonlocal nano-optical interplay between spatial coherence of the nonlinear polarization and disorder-induced scattering. The results highlight the challenges associated with heterogeneities in TMDs limiting their photophysical properties, yet also the potential of their novel nonlinear optical phenomena.

Nanoscopic Assessment of Anti-SARS-CoV-2 Spike Neutralizing Antibody Using High-Speed AFM.

Anti-spike neutralizing antibodies (S NAbs) have been developed for prevention and treatment against COVID-19. The nanoscopic characterization of the dynamic interaction between spike proteins and S NAbs remains difficult. By using high-speed atomic force microscopy (HS-AFM), we elucidate the molecular property of an S NAb and its interaction with spike proteins. The S NAb appeared as monomers with a Y conformation at low density and formed hexameric oligomers at high density. The dynamic S NAb-spike protein interaction at RBD induces neither RBD opening nor S1 subunit shedding. Furthermore, the interaction was stable at endosomal pH. These findings indicated that the S NAb could have a negligible risk of antibody-dependent enhancement. Dynamic movement of spike proteins on small extracellular vesicles (S sEV) resembled that on SARS-CoV-2. The sensitivity of variant S sEVs to S NAb could be evaluated using HS-AFM. Altogether, we demonstrate a nanoscopic assessment platform for evaluating the binding property of S NAbs.

Mid-Infrared Mapping of Four-Layer Graphene Polytypes Using Near-Field Microscopy.

The mid-infrared (MIR) spectral region attracts attention for accurate chemical analysis using photonic devices. Few-layer graphene (FLG) polytypes are promising platforms, due to their broad absorption in this range and gate-tunable optical properties. Among these polytypes, the noncentrosymmetric ABCB/ACAB structure is particularly interesting, due to its intrinsic bandgap (8.8 meV) and internal polarization. In this study, we utilize scattering-scanning near-field microscopy to measure the optical response of all three tetralayer graphene polytypes in the 8.5-11.5 µm range. We employ a finite dipole model to compare these results to the calculated optical conductivity for each polytype obtained from a tight-binding model. Our findings reveal a significant discrepancy in the MIR optical conductivity response of graphene between the different polytypes than what the tight-binding model suggests. This observation implies an increased potential for utilizing the distinct tetralayer polytypes in photonic devices operating within the MIR range for chemical sensing and infrared imaging.

Mechanistic Understanding of Oxygen Activation on Bulk Au(111) Surface Using Tip-Enhanced Raman Spectroscopy.

Gaining mechanistic understanding of oxygen activation on metal surfaces is a topical area of research in surface science. However, direct investigation of on-surface oxidation processes at the nanoscale and the empirical validation of oxygen activation pathways remain challenging for the conventional analytical tools. In this study, we applied tip-enhanced Raman spectroscopy (TERS) to gain mechanistic insights into oxygen activation on bulk Au(111) surface. Specifically, oxidation of 4-aminothiophenol (4-ATP) to 4-nitrothiophenol (4-NTP) on Au(111) surface was investigated using hyperspectral TERS imaging. Nanoscale TERS images revealed a markedly higher oxidation efficiency in disordered 4-ATP adlayers compared to the ordered adlayers signifying that the oxidation of 4-ATP molecules proceeds via interaction with the on-surface oxidative species. These results were further validated via direct oxidation of the 4-ATP adlayers with H2O2 solution. Finally, TERS measurements of oxidized 4-ATP adlayers in the presence of H2O18 provided the first empirical evidence for the generation of oxidative species on bulk Au(111) surface via water-mediated activation of molecular oxygen. This study expands our mechanistic understanding of oxidation chemistry on bulk Au surface by elucidating the oxygen activation pathway.

Counting on the future: fast charge-integrating detectors for X-ray nanoimaging.

A fast charge-integrating detector has been showcased for high-resolution X-ray ptychography. The advancement in developing detectors of this kind, with rapid framing capabilities, holds paramount significance in harnessing the full potential of emerging diffraction-limited synchrotron sources for X-ray nanoimaging.

Full-field hard X-ray nano-tomography at SSRF.

An in-house designed transmission X-ray microscopy (TXM) instrument has been developed and commissioned at beamline BL18B of the Shanghai Synchrotron Radiation Facility (SSRF). BL18B is a hard (5-14 keV) X-ray bending-magnet beamline recently built with sub-20 nm spatial resolution in TXM. There are two kinds of resolution mode: one based on using a high-resolution-based scintillator-lens-coupled camera, and the other on using a medium-resolution-based X-ray sCMOS camera. Here, a demonstration of full-field hard X-ray nano-tomography for high-Z material samples (e.g. Au particles, battery particles) and low-Z material samples (e.g. SiO2 powders) is presented for both resolution modes. Sub-50 nm to 100 nm resolution in three dimensions (3D) has been achieved. These results represent the ability of 3D non-destructive characterization with nano-scale spatial resolution for scientific applications in many research fields.

In-place molecular preservation of cellulose in 5,000-year-old archaeological textiles.

The understanding of fossilization mechanisms at the nanoscale remains extremely challenging despite its fundamental interest and its implications for paleontology, archaeology, geoscience, and environmental and material sciences. The mineralization mechanism by which cellulosic, keratinous, and silk tissues fossilize in the vicinity of archaeological metal artifacts offers the most exquisite preservation through a mechanism unexplored on the nanoscale. It is at the center of the vast majority of ancient textiles preserved under nonextreme conditions, known through extremely valuable fragments. Here we show the reconstruction of the nanoscale mechanism leading to the preservation of an exceptional collection of ancient cellulosic textiles recovered in the ancient Near East (4,000 to 5,000 years ago). We demonstrate that even the most mineralized fibers, which contain inorganic compounds throughout their histology, enclose preserved cellulosic remains in place. We evidence a process that combines the three steps of water transport of biocidal metal cations and soil solutes, degradation and loss of crystallinity of cellulosic polysaccharides, and silicification.

Revealing the Interaction of Charge Carrier-Phonon Coupling by Quantification of Electronic Properties at the SrTiO3/TiO2 Heterointerface.

Oxide heterointerfaces with high carrier density can interact strongly with the lattice phonons, generating considerable plasmon-phonon coupling and thereby perturbing the fascinating optical and electronic properties, such as two-dimensional electron gas, ferromagnetism, and superconductivity. Here we use infrared-spectroscopic nanoimaging based on scattering-type scanning near-field optical microscopy (s-SNOM) to quantify the interaction of electron-phonon coupling and the spatial distribution of local charge carriers at the SrTiO3/TiO2 interface. We found an increased high-frequency dielectric constant (ε∞ = 7.1-9.0) and charge carrier density (n = 6.5 × 1019 to 1.5 × 1020 cm-3) near the heterointerface. Moreover, quantitative information between the charge carrier density and extension thickness across the heterointerface has been extracted by monochromatic near-field imaging. A direct evaluation of the relationship between the thickness and the interaction of charge carrier-phonon coupling of the heterointerface would provide valuable information for the development of oxide-based electronic devices.

An anti-ANGPTL3/8 antibody decreases circulating triglycerides by binding to a LPL-inhibitory leucine zipper-like motif.

Triglycerides (TG) are required for fatty acid transport and storage and are essential for human health. Angiopoietin-like-protein 8 (ANGPTL8) has previously been shown to form a complex with ANGPTL3 that increases circulating TG by potently inhibiting LPL. We also recently showed that the TG-lowering apolipoprotein A5 (ApoA5) decreases TG levels by suppressing ANGPTL3/8-mediated LPL inhibition. To understand how LPL binds ANGPTL3/8 and ApoA5 blocks this interaction, we used hydrogen-deuterium exchange mass-spectrometry and molecular modeling to map binding sites of LPL and ApoA5 on ANGPTL3/8. Remarkably, we found that LPL and ApoA5 both bound a unique ANGPTL3/8 epitope consisting of N-terminal regions of ANGPTL3 and ANGPTL8 that are unmasked upon formation of the ANGPTL3/8 complex. We further used ANGPTL3/8 as an immunogen to develop an antibody targeting this same epitope. After refocusing on antibodies that bound ANGPTL3/8, as opposed to ANGPTL3 or ANGPTL8 alone, we utilized bio-layer interferometry to select an antibody exhibiting high-affinity binding to the desired epitope. We revealed an ANGPTL3/8 leucine zipper-like motif within the anti-ANGPTL3/8 epitope, the LPL-inhibitory region, and the ApoA5-interacting region, suggesting the mechanism by which ApoA5 lowers TG is via competition with LPL for the same ANGPTL3/8-binding site. Supporting this hypothesis, we demonstrate that the anti-ANGPTL3/8 antibody potently blocked ANGPTL3/8-mediated LPL inhibition in vitro and dramatically lowered TG levels in vivo. Together, these data show that an anti-ANGPTL3/8 antibody targeting the same leucine zipper-containing epitope recognized by LPL and ApoA5 markedly decreases TG by suppressing ANGPTL3/8-mediated LPL inhibition.

Non-Local Electrostatic Gating Effect in Graphene Revealed by Infrared Nano-Imaging.

Electrostatic gating lies in the heart of field effect transistor (FET) devices and modern integrated circuits. To achieve efficient gate tunability, the gate electrode has to be placed very close to the conduction channel, typically a few nanometers. Remote control of a FET device through a gate electrode located far away is highly desirable, because it not only reduces the complexity of device fabrication, but also enables the design of novel devices with new functionalities. Here, a non-local electrostatic gating effect in graphene devices using scanning near-field optical microscopy (SNOM)-a technique that can probe local charge density in graphene-is reported. Remarkably, the charge density of the graphene region tens of micrometers away from a local gate can be efficiently tuned. The observed non-local gating effect is initially driven by an in-plane electric field induced by the quantum capacitance of graphene, and further largely enhanced by adsorbed polarized water molecules. This study reveals a non-local phenomenon of Dirac electrons, provides a deep understanding of in-plane screening from Dirac electrons, and paves the way for designing novel electronic devices with remote gate control.

X-ray multiscale 3D neuroimaging to quantify cellular aging and neurodegeneration postmortem in a model of Alzheimer's disease.

PURPOSE: Modern neuroimaging lacks the tools necessary for whole-brain, anatomically dense neuronal damage screening. An ideal approach would include unbiased histopathologic identification of aging and neurodegenerative disease. METHODS: We report the postmortem application of multiscale X-ray phase-contrast computed tomography (X-PCI-CT) for the label-free and dissection-free organ-level to intracellular-level 3D visualization of distinct single neurons and glia. In deep neuronal populations in the brain of aged wild-type and of 3xTgAD mice (a triply-transgenic model of Alzheimer's disease), we quantified intracellular hyperdensity, a manifestation of aging or neurodegeneration. RESULTS: In 3xTgAD mice, the observed hyperdensity was identified as amyloid-ß and hyper-phosphorylated tau protein deposits with calcium and iron involvement, by correlating the X-PCI-CT data to immunohistochemistry, X-ray fluorescence microscopy, high-field MRI, and TEM. As a proof-of-concept, X-PCI-CT was used to analyze hippocampal and cortical brain regions of 3xTgAD mice treated with LY379268, selective agonist of group II metabotropic glutamate receptors (mGlu2/3 receptors). Chronic pharmacologic activation of mGlu2/3 receptors significantly reduced the hyperdensity particle load in the ventral cortical regions of 3xTgAD mice, suggesting a neuroprotective effect with locoregional efficacy. CONCLUSIONS: This multiscale micro-to-nano 3D imaging method based on X-PCI-CT enabled identification and quantification of cellular and sub-cellular aging and neurodegeneration in deep neuronal and glial cell populations in a transgenic model of Alzheimer's disease. This approach quantified the localized and intracellular neuroprotective effects of pharmacological activation of mGlu2/3 receptors.

Array atomic force microscopy for real-time multiparametric analysis.

Nanoscale multipoint structure-function analysis is essential for deciphering the complexity of multiscale biological and physical systems. Atomic force microscopy (AFM) allows nanoscale structure-function imaging in various operating environments and can be integrated seamlessly with disparate probe-based sensing and manipulation technologies. Conventional AFMs only permit sequential single-point analysis; widespread adoption of array AFMs for simultaneous multipoint study is challenging owing to the intrinsic limitations of existing technological approaches. Here, we describe a prototype dispersive optics-based array AFM capable of simultaneously monitoring multiple probe-sample interactions. A single supercontinuum laser beam is utilized to spatially and spectrally map multiple cantilevers, to isolate and record beam deflection from individual cantilevers using distinct wavelength selection. This design provides a remarkably simplified yet effective solution to overcome the optical cross-talk while maintaining subnanometer sensitivity and compatibility with probe-based sensors. We demonstrate the versatility and robustness of our system on parallel multiparametric imaging at multiscale levels ranging from surface morphology to hydrophobicity and electric potential mapping in both air and liquid, mechanical wave propagation in polymeric films, and the dynamics of living cells. This multiparametric, multiscale approach provides opportunities for studying the emergent properties of atomic-scale mechanical and physicochemical interactions in a wide range of physical and biological networks.

High-Quality All-Inorganic Perovskite CsPbBr3 Microsheet Crystals as Low-Loss Subwavelength Exciton-Polariton Waveguides.

Nanostructured all-inorganic metal halide perovskites have attracted considerable attention due to their outstanding photonic and optoelectronic properties. Particularly, they can exhibit room-temperature exciton-polaritons (EPs) capable of confining electromagnetic fields down to the subwavelength scale, enabling efficient light harvesting and guiding. However, a real-space nanoimaging study of the EPs in perovskite crystals is still absent. Additionally, few studies focused on the ambient-pressure and reliable fabrication of large-area CsPbBr3 microsheets. Here, CsPbBr3 orthorhombic microsheet single crystals were successfully synthesized under ambient pressure. Their EPs were examined using a real-space nanoimaging technique, which reveal EP waveguide modes spanning the visible to near-infrared spectral region. The EPs exhibit a sufficient long propagation length of over 16 µm and a very low propagation loss of less than 0.072 dB·µm-1. These results demonstrate the potential applications of CsPbBr3 microsheets as subwavelength waveguides in integrated optics.

Multidimensional Nano-Imaging of Structure, Coupling, and Disorder in Molecular Materials.

A hierarchy of intramolecular and intermolecular interactions controls the properties of biomedical, photophysical, and novel energy materials. However, multiscale heterogeneities often obfuscate the relationship between microscopic structure and emergent function, and they are generally difficult to access with conventional optical and electron microscopy techniques. Here, we combine vibrational exciton nanoimaging in variable-temperature near-field optical microscopy (IR s-SNOM) with four-dimensional scanning transmission electron microscopy (4D-STEM), and vibrational exciton modeling based on density functional theory (DFT), to link local microscopic molecular interactions to macroscopic three-dimensional order. In the application to poly(tetrafluoroethylene) (PTFE), large spatio-spectral heterogeneities with C-F vibrational energy shifts ranging from sub-cm-1 to ≳25 cm-1 serve as a molecular ruler of the degree of local crystallinity and disorder. Spatio-spectral-structural correlations reveal a previously invisible degree of highly variable local disorder in molecular coupling as the possible missing link between nanoscale morphology and associated electronic, photonic, and other functional properties of molecular materials.

Unraveling Charge-Separation Mechanisms in Photocatalyst Particles by Spatially Resolved Surface Photovoltage Techniques.

The photocatalytic conversion of solar energy offers a potential route to renewable energy, and its efficiency relies on effective charge separation in nanostructured photocatalysts. Understanding the charge-separation mechanism is key to improving the photocatalytic performance and this has now been enabled by advances in the spatially resolved surface photovoltage (SRSPV) method. In this Review we highlight progress made by SRSPV in mapping charge distributions at the nanoscale and determining the driving forces of charge separation in heterogeneous photocatalyst particles. We discuss how charge separation arising from a built-in electric field, diffusion, and trapping can be exploited and optimized through photocatalyst design. We also highlight the importance of asymmetric engineering of photocatalysts for effective charge separation. Finally, we provide an outlook on further opportunities that arise from leveraging these insights to guide the rational design of photocatalysts and advance the imaging technique to expand the knowledge of charge separation.

Roadmap of Terahertz Imaging 2021.

In this roadmap article, we have focused on the most recent advances in terahertz (THz) imaging with particular attention paid to the optimization and miniaturization of the THz imaging systems. Such systems entail enhanced functionality, reduced power consumption, and increased convenience, thus being geared toward the implementation of THz imaging systems in real operational conditions. The article will touch upon the advanced solid-state-based THz imaging systems, including room temperature THz sensors and arrays, as well as their on-chip integration with diffractive THz optical components. We will cover the current-state of compact room temperature THz emission sources, both optolectronic and electrically driven; particular emphasis is attributed to the beam-forming role in THz imaging, THz holography and spatial filtering, THz nano-imaging, and computational imaging. A number of advanced THz techniques, such as light-field THz imaging, homodyne spectroscopy, and phase sensitive spectrometry, THz modulated continuous wave imaging, room temperature THz frequency combs, and passive THz imaging, as well as the use of artificial intelligence in THz data processing and optics development, will be reviewed. This roadmap presents a structured snapshot of current advances in THz imaging as of 2021 and provides an opinion on contemporary scientific and technological challenges in this field, as well as extrapolations of possible further evolution in THz imaging.

Metallic Carbon Nanotube Nanocavities as Ultracompact and Low-loss Fabry-Perot Plasmonic Resonators.

Plasmonic resonators enable deep subwavelength manipulation of light matter interactions and have been intensively studied both in fundamental physics as well as for potential technological applications. While various metallic nanostructures have been proposed as plasmonic resonators, their performances are rather limited at mid- and far-infrared wavelengths. Recently, highly confined and low-loss Luttinger liquid plasmons in metallic single-walled carbon nanotubes (SWNTs) have been observed at infrared wavelengths. Here, we tailor metallic SWNTs into ultraclean nanocavities by advanced scanning probe lithography and investigate plasmon modes in these individual nanocavities by infrared nanoimaging. The dependence of mode evolutions on cavity length and excitation wavelength can be captured by a Fabry-Perot resonator model of a plasmon nanowaveguide terminated by highly reflective ends. Plasmonic resonators based on SWNT nanocavities approach the ultimate plasmon confinement limit and open the door to the strong light-matter coupling regime, which may enable various nanophotonic applications.

Logarithm Diameter Scaling and Carrier Density Independence of One-Dimensional Luttinger Liquid Plasmon.

Quantum-confined electrons in one-dimensional (1D) metals are described by a Luttinger liquid. The collective charge excitations (i.e., plasmons) in a Luttinger liquid can behave qualitatively different from their conventional counterparts. For example, the Luttinger liquid plasmon velocity is uniquely determined by the electron-electron interaction, which scales logarithmly with the diameter of the 1D material. In addition, the Luttinger liquid plasmon is predicted to be independent of the carrier concentration. Here, we report the observation of such unusual Luttinger liquid plasmon behaviors in metallic single-walled carbon nanotubes, a model system featuring strong electron quantum confinement. We systematically investigate the plasmon propagation in over 30 metallic carbon nanotubes of different diameters using infrared nanoscopy. We establish that the plasmon velocity has a weak logarithm dependence on the nanotube diameter, as predicted by the Luttinger liquid theory. We further study the plasmon excitation as a function of the carrier density in electrostatically gated metallic carbon nanotubes and demonstrate that the plasmon velocity is completely independent of the carrier density. These behaviors are in striking contrast to conventional plasmons in 1D metallic shells, where the plasmon dispersion changes dramatically with the metal electron density and the 1D diameter. The unusual behaviors of Luttinger liquid plasmon may enable novel nanophotonic applications based on carbon nanotubes.