Two-dimensional chiral perovskites with large spin Hall angle and collinear spin Hall conductivity.

Two-dimensional hybrid organic-inorganic perovskites with chiral spin texture are emergent spin-optoelectronic materials. Despite the wealth of chiro-optical studies on these materials, their charge-to-spin conversion efficiency is unknown. We demonstrate highly efficient electrically driven charge-to-spin conversion in enantiopure chiral perovskites (R/S-MB)2(MA)3Pb4I13 (〈n〉 = 4), where MB is 2-methylbutylamine, MA is methylamine, Pb is lead, and I is iodine. Using scanning photovoltage microscopy, we measured a spin Hall angle θsh of 5% and a spin lifetime of ~75 picoseconds at room temperature in 〈n〉 = 4 chiral perovskites, which is much larger than its racemic counterpart as well as the lower 〈n〉 homologs. In addition to current-induced transverse spin current, the presence of a coexisting out-of-plane spin current confirms that both conventional and collinear spin Hall conductivities exist in these low-dimensional crystals.

Highly Confined Hybridized Polaritons in Scalable van der Waals Heterostructure Resonators.

The optimization of nanoscale optical devices and structures will enable the exquisite control of planar optical fields. Polariton manipulation is the primary strategy in play. In two-dimensional heterostructures, the ability to excite mixed optical modes offers an additional control in device design. Phonon polaritons in hexagonal boron nitride have been a common system explored for the control of near-infrared radiation. Their hybridization with graphene plasmons makes these mixed phonon polariton modes in hexagonal boron nitride more appealing in terms of enabling active control of electrodynamic properties with a reduction of propagation losses. Optical resonators can be added to confine these hybridized plasmon-phonon polaritons deeply into the subwavelength regime, with these structures featuring high quality factors. Here, we show a scalable approach for the design and fabrication of heterostructure nanodisc resonators patterned in chemical vapor deposition-grown monolayer graphene and h-BN sheets. Real-space mid-infrared nanoimaging reveals the nature of hybridized polaritons in the heterostructures. We simulate and experimentally demonstrate localized hybridized polariton modes in heterostructure nanodisc resonators and demonstrate that those nanodiscs can collectively couple to the waveguide. High quality factors for the nanodiscs are measured with nanoscale Fourier transform infrared spectroscopy. Our results offer practical strategies to realize scalable nanophotonic devices utilizing low-loss hybridized polaritons for applications such as on-chip optical components.

Giant Nonlinear Optical Response via Coherent Stacking of In-Plane Ferroelectric Layers.

Thin ferroelectric materials hold great promise for compact nonvolatile memory and nonlinear optical and optoelectronic devices. Herein, an ultrathin in-plane ferroelectric material that exhibits a giant nonlinear optical effect, group-IV monochalcogenide SnSe, is reported. Nanometer-scale ferroelectric domains with ≈90°/270° twin boundaries or ≈180° domain walls are revealed in physical-vapor-deposited SnSe by lateral piezoresponse force microscopy. Atomic structure characterization reveals both parallel and antiparallel stacking of neighboring van der Waals ferroelectric layers, leading to ferroelectric or antiferroelectric ordering. Ferroelectric domains exhibit giant nonlinear optical activity due to coherent enhancement of second-harmonic fields and the as-resulted second-harmonic generation was observed to be 100 times more intense than monolayer WS2 . This work demonstrates in-plane ferroelectric ordering and giant nonlinear optical activity in SnSe, which paves the way for applications in on-chip nonlinear optical components and nonvolatile memory devices.

Electrically switchable anisotropic polariton propagation in a ferroelectric van der Waals semiconductor.

Tailoring of the propagation dynamics of exciton-polaritons in two-dimensional quantum materials has shown extraordinary promise to enable nanoscale control of electromagnetic fields. Varying permittivities along crystal directions within layers of material systems, can lead to an in-plane anisotropic dispersion of polaritons. Exploiting this physics as a control strategy for manipulating the directional propagation of the polaritons is desired and remains elusive. Here we explore the in-plane anisotropic exciton-polariton propagation in SnSe, a group-IV monochalcogenide semiconductor that forms ferroelectric domains and shows room-temperature excitonic behaviour. Exciton-polaritons are launched in SnSe multilayer plates, and their propagation dynamics and dispersion are studied. This propagation of exciton-polaritons allows for nanoscale imaging of the in-plane ferroelectric domains. Finally, we demonstrate the electric switching of the exciton-polaritons in the ferroelectric domains of this complex van der Waals system. The study suggests that systems such as group-IV monochalcogenides could serve as excellent ferroic platforms for actively reconfigurable polaritonic optical devices.

Fructose and Uric Acid as Drivers of a Hyperactive Foraging Response: A Clue to Behavioral Disorders Associated with Impulsivity or Mania?

Several behavioral disorders, including attention deficit hyperactivity disorder (ADHD), bipolar disorder, and aggressive behaviors are linked with sugar intake and obesity. The reason(s) for this association has been unclear. Here we present a hypothesis supporting a role for fructose, a component of sugar and high fructose corn syrup (HFCS), and uric acid (a fructose metabolite), in increasing the risk for these behavioral disorders. Recent studies have shown that the reason fructose intake is strongly associated with development of metabolic syndrome is that fructose intake activates an evolutionary-based survival pathway that stimulates foraging behavior and the storage of energy as fat. While modest intake may aid animals that would like to store fat as a protective response from food shortage or starvation, we propose that high intake of sugar and HFCS causes a hyperactive foraging response that stimulates craving, impulsivity, risk taking and aggression that increases the risk for ADHD, bipolar disease and aggressive behavior. High glycemic carbohydrates and salty foods may also contribute as they can be converted to fructose in the body. Some studies suggest uric acid produced during fructose metabolism may mediate some of these effects. Chronic stimulation of the pathway could lead to desensitization of hedonic responses and induce depression. In conclusion, a hyperactive foraging response driven by high glycemic carbohydrates and sugars may contribute to affective disorders.

In situ nanoscale imaging of moiré superlattices in twisted van der Waals heterostructures.

Direct visualization of nanometer-scale properties of moiré superlattices in van der Waals heterostructure devices is a critically needed diagnostic tool for study of the electronic and optical phenomena induced by the periodic variation of atomic structure in these complex systems. Conventional imaging methods are destructive and insensitive to the buried device geometries, preventing practical inspection. Here we report a versatile scanning probe microscopy employing infrared light for imaging moiré superlattices of twisted bilayers graphene encapsulated by hexagonal boron nitride. We map the pattern using the scattering dynamics of phonon polaritons launched in hexagonal boron nitride capping layers via its interaction with the buried moiré superlattices. We explore the origin of the double-line features imaged and show the mechanism of the underlying effective phase change of the phonon polariton reflectance at domain walls. The nano-imaging tool developed provides a non-destructive analytical approach to elucidate the complex physics of moiré engineered heterostructures.

In Situ Photophysical Characterization of π-Conjugated Oligopeptides Assembled via Continuous Flow Processing.

Bioinspired materials have been developed with the aim of harnessing natural self-assembly for precisely engineered functionality. Microfluidics is poised to play a key role in the directed assembly of advanced materials with ordered nano and mesoscale features. More importantly, there is a strong need for understanding the kinetics of continuous assembly processes. In this work, we describe a continuous microfluidic system for the assembly and alignment of synthetic oligopeptides with π-conjugated cores using a three-dimensional (3D) flow focusing of inlet reactant streams. This system facilitates in situ confocal fluorescence microscopy and in situ fluorescence lifetime imaging microscopy (FLIM), which can be used in unprecedented capacity to characterize the integrity of peptides during the assembly process. To achieve continuous assembly, we integrate chevron patterns in the ceiling and floor of the microdevice to generate a 3D-focused sheath flow of the reactant peptide. Consequently, the peptide stream is directed toward an acidic triggering stream in a cross-slot geometry which mediates assembly into higher-order fiber-like structures. Using this approach, the focused peptide stream is assembled using a planar extensional flow, which ensures high degrees of microstructural alignment within the assembled material. We demonstrate the efficacy of this approach using three different synthetic oligopeptides, and in all cases, we observe the efficient and continuous assembly of oligopeptides. In addition, finite element simulations are used to guide device design and to validate 3D focusing. Overall, this approach presents an efficient and effective method for the continuous assembly and alignment of ordered materials using microfluidics.

A mid-infrared biaxial hyperbolic van der Waals crystal.

Hyperbolic media have attracted much attention in the photonics community due to their ability to confine light to arbitrarily small volumes and their potential applications to super-resolution technologies. The two-dimensional counterparts of these media can be achieved with hyperbolic metasurfaces that support in-plane hyperbolic guided modes upon nanopatterning, which, however, poses notable fabrication challenges and limits the achievable confinement. We show that thin flakes of a van der Waals crystal, α-MoO3, can support naturally in-plane hyperbolic polariton guided modes at mid-infrared frequencies without the need for patterning. This is possible because α-MoO3 is a biaxial hyperbolic crystal with three different Reststrahlen bands, each corresponding to a different crystalline axis. These findings can pave the way toward a new paradigm to manipulate and confine light in planar photonic devices.

Ultra-confined mid-infrared resonant phonon polaritons in van der Waals nanostructures.

Hexagonal boron nitride has been proposed as an excellent candidate to achieve subwavelength infrared light manipulation owing to its polar lattice structure, enabling excitation of low-loss phonon polaritons with hyperbolic dispersion. We show that strongly subwavelength hexagonal boron nitride planar nanostructures can exhibit ultra-confined resonances and local field enhancement. We investigate strong light-matter interaction in these nanoscale structures via photo-induced force microscopy, scattering-type scanning near-field optical microscopy, and Fourier transform infrared spectroscopy, with excellent agreement with numerical simulations. We design optical nano-dipole antennas and directly image the fields when bright- or dark-mode resonances are excited. These modes are deep subwavelength, and strikingly, they can be supported by arbitrarily small structures. We believe that phonon polaritons in hexagonal boron nitride can play for infrared light a role similar to that of plasmons in noble metals at visible frequency, paving the way for a new class of efficient and highly miniaturized nanophotonic devices.

Evidence for Prenucleated Fibrilogenesis of Acid-Mediated Self-Assembling Oligopeptides via Molecular Simulation and Fluorescence Correlation Spectroscopy.

An important step in controlling biomimetic amyloid systems is understanding the self-assembly reaction kinetics. We are interested in a family of such materials characterized by symmetric sequences of amino acids flanking a π-conjugated functional core. Many of these materials rapidly self-assemble into long fibers upon protonation in an acidic environment. Despite extensive investigation of these materials' properties, little is yet understood regarding their reaction kinetics. Based on previous studies, we have chosen DFAG-4T-GAFD as a representative system and conducted molecular dynamics simulations to show that although large-scale assembly is induced by lowering pH, some degree of assembly is thermodynamically favorable in high-pH nonprotonating environments. These results are consistent with findings for other systems such as DFAG-OPV-GAFD. The nonprotonated aggregation also appears to be concentration dependent, occurring at concentrations of 100 nM and above. Single molecule measurements using fluorescence correlation spectroscopy provide experimental support for these computational predictions. We find evidence of spontaneous aggregation in aqueous solutions of peptides with concentrations as low as 100 nM; however, 10 nM solutions appear to be largely homogeneous solutions of unassembled monomer. These results indicate that the simplest explanations for kinetics of acid-mediated assembly-protonation-induced nucleation by monomeric addition followed by subsequent stages of aggregation and elongation-are inappropriate in this system. In fact, the system only exists as pure monomer in very low concentrations, nucleation actually occurs in the absence of protonating elements at concentrations typically used for experiments, and pH triggered assembly proceeds from these preassembled aggregates. Accordingly, triggered assembly must be considered to operate outside the domain of nucleation-dependent models.

Sugar addiction: is it real? A narrative review.

In animal studies, sugar has been found to produce more symptoms than is required to be considered an addictive substance. Animal data has shown significant overlap between the consumption of added sugars and drug-like effects, including bingeing, craving, tolerance, withdrawal, cross-sensitisation, cross-tolerance, cross-dependence, reward and opioid effects. Sugar addiction seems to be dependence to the natural endogenous opioids that get released upon sugar intake. In both animals and humans, the evidence in the literature shows substantial parallels and overlap between drugs of abuse and sugar, from the standpoint of brain neurochemistry as well as behaviour.

Selective excitation and imaging of ultraslow phonon polaritons in thin hexagonal boron nitride crystals.

We selectively excite and study two new types of phonon-polariton guided modes that are found in hexagonal boron nitride thin flakes on a gold substrate. Such modes show substantially improved confinement and a group velocity that is hundreds of times slower than the speed of light, thereby providing a new way to create slow light in the mid-infrared range with a simple structure that does not require nano-patterning. One mode is the fundamental mode in the first Restrahlen band of hexagonal boron nitride thin crystals on a gold substrate; the other mode is equivalent to the second mode of the second Restrahlen band of hexagonal boron nitride flakes that are suspended in vacuum. The new modes also couple efficiently with incident light at the hexagonal boron nitride edges, as we demonstrate experimentally using photo-induced force microscopy and scanning near-field optical microscopy. The high confinement of these modes allows for Purcell factors that are on the order of tens of thousands directly above boron nitride and a wide band, with new perspectives for enhanced light-matter interaction. Our findings demonstrate a new approach to engineering the dispersion of polaritons in 2D materials to improve confinement and light-matter interaction, thereby paving the way for new applications in mid-infrared nano-optics.

Dynamics of Transformation from Platinum Icosahedral Nanoparticles to Larger FCC Crystal at Millisecond Time Resolution.

Atomic motion at grain boundaries is essential to microstructure development, growth and stability of catalysts and other nanostructured materials. However, boundary atomic motion is often too fast to observe in a conventional transmission electron microscope (TEM) and too slow for ultrafast electron microscopy. Here, we report on the entire transformation process of strained Pt icosahedral nanoparticles (ICNPs) into larger FCC crystals, captured at 2.5 ms time resolution using a fast electron camera. Results show slow diffusive dislocation motion at nm/s inside ICNPs and fast surface transformation at µm/s. By characterizing nanoparticle strain, we show that the fast transformation is driven by inhomogeneous surface stress. And interaction with pre-existing defects led to the slowdown of the transformation front inside the nanoparticles. Particle coalescence, assisted by oxygen-induced surface migration at T ≥ 300 °C, also played a critical role. Thus by studying transformation in the Pt ICNPs at high time and spatial resolution, we obtain critical insights into the transformation mechanisms in strained Pt nanoparticles.

Macroscopic Alignment and Assembly of π-Conjugated Oligopeptides Using Colloidal Microchannels.

One-dimensional (1-D) supramolecular self-assembly offers a powerful strategy to achieve long-range unidirectional ordering of organic semiconducting materials via noncovalent interactions. Using a hierarchical assembly, electronic and optoelectronic materials can be constructed for applications including organic conducting nanowires, organic field-effect transistors (OFETs), and organic light-emitting devices (OLEDs). Despite recent progress, it remains challenging to precisely align and assemble 1-D structures over large areas in a rapid and straightforward manner. In this work, we demonstrate a facile strategy to macroscopically align supramolecular fibers using a templating method based on sacrificial colloidal microchannels. Through use of this approach, colloidal microchannels are generated on a solid surface using a simple fabrication method, followed by the spontaneous self-assembly of π-conjugated oligopeptides inside large arrays of microchannels triggered by solvent evaporation. Following oligopeptide assembly and removal of sacrificial microchannels, the structural properties of oligopeptide fibers were characterized using atomic force microscopy (AFM), atomic force microscope-infrared spectroscopy (AFM-IR), photoinduced force microscopy (PiFM), fluorescence polarization microscopy, and electron microscopy. These results reveal the macroscopic alignment of oligopeptide fibers into ordered structures over millimeter length scales, facilitated by colloidal microchannel templating. In addition, the charge transport properties (I-V curves) of π-conjugated oligopeptides assembled using this method were determined under a wide range of applied voltages using interdigitated array electrodes and conductive AFM. Overall, this work illustrates a simple yet robust strategy to pattern 1-D supramolecular fibers over large areas, thereby offering new routes for assembling materials for organic electronics.

Concentration-Driven Assembly and Sol-Gel Transition of π-Conjugated Oligopeptides.

Advances in supramolecular assembly have enabled the design and synthesis of functional materials with well-defined structures across multiple length scales. Biopolymer-synthetic hybrid materials can assemble into supramolecular structures with a broad range of structural and functional diversity through precisely controlled noncovalent interactions between subunits. Despite recent progress, there is a need to understand the mechanisms underlying the assembly of biohybrid/synthetic molecular building blocks, which ultimately control the emergent properties of hierarchical assemblies. In this work, we study the concentration-driven self-assembly and gelation of π-conjugated synthetic oligopeptides containing different π-conjugated cores (quaterthiophene and perylene diimide) using a combination of particle tracking microrheology, confocal fluorescence microscopy, optical spectroscopy, and electron microscopy. Our results show that π-conjugated oligopeptides self-assemble into ß-sheet-rich fiber-like structures at neutral pH, even in the absence of electrostatic screening of charged residues. A critical fiber formation concentration cfiber and a critical gel concentration cgel are determined for fiber-forming π-conjugated oligopeptides, and the linear viscoelastic moduli (storage modulus G' and loss modulus G″) are determined across a wide range of peptide concentrations. These results suggest that the underlying chemical structure of the synthetic π-conjugated cores greatly influences the self-assembly process, such that oligopeptides appended to π-conjugated cores with greater torsional flexibility tend to form more robust fibers upon increasing peptide concentration compared to oligopeptides with sterically constrained cores. Overall, our work focuses on the molecular assembly of π-conjugated oligopeptides driven by concentration, which is controlled by a combination of enthalpic and entropic interactions between oligopeptide subunits.

Mechanical Detection and Imaging of Hyperbolic Phonon Polaritons in Hexagonal Boron Nitride.

Mid-infrared nanoimaging and spectroscopy of two-dimensional (2D) materials have been limited so far to scattering-type scanning near-field optical microscopy (s-SNOM) experiments, where light from the sample is scattered by a metallic-coated atomic force microscope (AFM) tip interacting with the material at the nanoscale. These experiments have recently allowed imaging of plasmon polaritons in graphene as well as hyperbolic phonon polaritons in hexagonal boron nitride (hBN). Here we show that the high mechanical sensitivity of an AFM cantilever can be exploited for imaging hyperbolic phonon polaritons in hBN. In our imaging process, the lattice vibrations of hBN micrometer-sized flakes are locally enhanced by the launched phonon polaritons. These enhanced vibrations are coupled to the AFM tip in contact with the sample surface and recorded during scanning. Imaging resolution of Δ/20 is shown (Δ being the polaritonic fringes' separation distance), comparable to the best resolution in s-SNOM. Importantly, this detection mechanism is free from light background, and it is in fact the first photonless detection of phonon polaritons.

Direct Electrical Probing of Periodic Modulation of Zinc-Dopant Distributions in Planar Gallium Arsenide Nanowires.

Selective lateral epitaxial (SLE) semiconductor nanowires (NWs), with their perfect in-plane epitaxial alignment, ability to form lateral complex p-n junctions in situ, and compatibility with planar processing, are a distinctive platform for next-generation device development. However, the incorporation and distribution of impurity dopants in these planar NWs via the vapor-liquid-solid growth mechanism remain relatively unexplored. Here, we present a detailed study of SLE planar GaAs NWs containing multiple alternating axial segments doped with Si and Zn impurities by metalorganic chemical vapor deposition. The dopant profile of the lateral multi-p-n junction GaAs NWs was imaged simultaneously with nanowire topography using scanning microwave impedance microscopy and correlated with infrared scattering-type near-field optical microscopy. Our results provide unambiguous evidence that Zn dopants in the periodically twinned and topologically corrugated p-type segments are preferentially segregated at twin plane boundaries, while Si impurity atoms are uniformly distributed within the n-type segments of the NWs. These results are further supported by microwave impedance modulation microscopy. The density functional theory based modeling shows that the presence of Zn dopant atoms reduces the formation energy of these twin planes, and the effect becomes significantly stronger with a slight increase of Zn concentration. This implies that the twin formation is expected to appear when a threshold planar concentration of Zn is achieved, making the onset and twin periodicity dependent on both Zn concentration and nanowire diameter, in perfect agreement with our experimental observations.

Nonequilibrium Self-Assembly of π-Conjugated Oligopeptides in Solution.

Supramolecular assembly is a powerful method that can be used to generate materials with well-defined structures across multiple length scales. Supramolecular assemblies consisting of biopolymer-synthetic polymer subunits are specifically known to exhibit exceptional structural and functional diversity as well as programmable control of noncovalent interactions through hydrogen bonding in biopolymer subunits. Despite recent progress, there is a need to control and quantitatively understand assembly under nonequilibrium conditions. In this work, we study the nonequilibrium self-assembly of π-conjugated synthetic oligopeptides using a combination of experiments and analytical modeling. By isolating an aqueous peptide solution droplet within an immiscible organic layer, the rate of peptide assembly in the aqueous solution can be controlled by tuning the transport rate of acid that is used to trigger assembly. Using this approach, peptides are guided to assemble under reaction-dominated and diffusion-dominated conditions, with results showing a transition from a diffusion-limited reaction front to spatially homogeneous assembly as the transport rate of acid decreases. Interestingly, our results show that the morphology of self-assembled peptide fibers is controlled by the assembly kinetics such that increasingly homogeneous structures of self-assembled synthetic oligopeptides were generally obtained using slower rates of assembly. We further developed an analytical reaction-diffusion model to describe oligopeptide assembly, and experimental results are compared to the reaction-diffusion model across a range of parameters. Overall, this work highlights the importance of molecular self-assembly under nonequilibrium conditions, specifically showing that oligopeptide assembly is governed by a delicate balance between reaction kinetics and transport processes.

Stain-free histopathology by programmable supercontinuum pulses.

The preparation, staining, visualization, and interpretation of histological images of tissue is well-accepted as the gold standard process for the diagnosis of disease. These methods were developed historically, and are used ubiquitously in pathology, despite being highly time and labor intensive. Here we introduce a unique optical imaging platform and methodology for label-free multimodal multiphoton microscopy that uses a novel photonic crystal fiber source to generate tailored chemical contrast based on programmable supercontinuum pulses. We demonstrate collection of optical signatures of the tumor microenvironment, including evidence of mesoscopic biological organization, tumor cell migration, and (lymph-)angiogenesis collected directly from fresh ex vivo mammary tissue. Acquisition of these optical signatures and other cellular or extracellular features, which are largely absent from histologically processed and stained tissue, combined with an adaptable platform for optical alignment-free programmable-contrast imaging, offers the potential to translate stain-free molecular histopathology into routine clinical use.

Scanning Probe Microwave Reflectivity of Aligned Single-Walled Carbon Nanotubes: Imaging of Electronic Structure and Quantum Behavior at the Nanoscale.

Single-walled carbon nanotubes (SWNTs) are 1-dimensional nanomaterials with unique electronic properties that make them excellent candidates for next-generation device technologies. While nanotube growth and processing methods have progressed steadily, significant opportunities remain in advanced methods for their characterization, inspection, and metrology. Microwave near-field imaging offers an extremely versatile "nondestructive" tool for nanomaterials characterization. Herein, we report the application of nanoscale microwave reflectivity to study SWNT electronic properties. Using microwave impedance microscopy (MIM) combined with microwave impedance modulation microscopy (MIM(2)), we imaged horizontal SWNT arrays, showing the microwave reflectivity from individual nanotubes is extremely sensitive to their electronic properties and dependent on the nanotube quantum capacitance under proper experimental conditions. It is shown experimentally that MIM can be a direct probe of the nanotube-free carrier density and the details of their electronic band structure. We demonstrate spatial mapping of local SWNT impedance (MIM), the density of states (MIM(2)), and the nanotube structural morphology (AFM) simultaneously and with lateral resolution down to <50 nm. Nanoscale microwave reflectivity could have tremendous impact, enabling optimization of enriched growth processes and postgrowth purification of SWNT arrays while aiding in the analysis of the quantum physics of these important 1D materials.