Ultra-Narrow Linewidth Photo-Emitters in Polymorphic Selenium Nanoflakes.

Photoluminescence (PL) in state-of-the-art 2D materials suffers from narrow spectral coverage, relatively broad linewidths, and poor room-temperature (RT) functionality. The authors report ultra-narrow linewidth photo-emitters (ULPs) across the visible to near-infrared wavelength at RT in polymorphic selenium nanoflakes (SeNFs), synthesized via a hot-pressing strategy. Photo-emitters in NIR exhibit full width at half maximum (Γ) of 330 ± 90 µeV, an order of magnitude narrower than the reported ULPs in 2D materials at 300 K, and decrease to 82 ± 70 µeV at 100 K, with coherence time (τc ) of 21.3 ps. The capping substrate enforced spatial confinement during thermal expansion at 250 °C is believed to trigger a localized crystal symmetry breaking in SeNFs, causing a polymorphic transition from the semiconducting trigonal (t) to quasi-metallic orthorhombic (orth) phase. Fine structure splitting in orth-Se causes degeneracy in defect-associated bright excitons, resulting in ultra-sharp emission. Combined theoretical and experimental findings, an optimal biaxial compressive strain of -0.45% cm-1 in t-Se is uncovered, induced by the coefficient of thermal expansion mismatch at the selenium/sapphire interface, resulting in bandgap widening from 1.74 to 2.23 ± 0.1 eV. This report underpins the underlying correlation between crystal symmetry breaking induced polymorphism and RT ULPs in SeNFs, and their phase change characteristics.

Shape and deposition angle control of silver film-over-nanosphere SERS substrates.

Thin metallic films on dielectric nanospheres are demonstrated to have a high potential for the fabrication of cost-effective SERS substrates. In addition to the morphological advantages that nanospheres offer for attaining a high density of hot spots, possessing shape adjustability by uncomplicated thermal treatment makes them an attractive platform for tuneable SERS substrates. Furthermore, when combined with the oblique angle metal deposition technique, adjustable gaps at a high density and adjustable shape of metal films, such as Ag films, can be achieved on nanospheres. Applying small changes in deposition angle can provide means for fine adjustment of the Raman enhancement factor (EF), resulting in EF up to 108measured using crystal violet dye molecule as a Raman analyte. This practice paves the way for the fabrication of high EF SERS substrates at a reasonable cost using a monolayer of self-organized nanosphere patterns. An ultra-thin Ag film coated at 5° tilt is shown to be an excellent substitute for a film deposited at 0° with double the thickness. There is a strong agreement between the experimental results and finite-elements-method-based Maxwell simulations exhibiting expected field enhancements up to 109at a tilt angle of 5°.

Facile preparation of nanoparticle based SERS substrates for trace molecule detection.

In this work, we demonstrate that a polished Si wafer surface can be converted to possess strong surface-enhanced Raman scattering (SERS) activity by spray coating of polyol synthesized colloidal silver nanoparticles (AgNPs) at as low as 1% surface coverage. The SERS activity assays of substrate surfaces prepared with different production procedures (spray and spin coating) at different surface coverages are realized using population statistics. The resulting Raman enhancement factors (EFs) are discussed with the help of distance-dependent electromagnetic simulations for single particles and dimers. Statistics on the SERS effect and the corresponding EF calculations show that polyol synthesized AgNPs exhibit extremely strong SERS activity with EFs up to 108 at as low as 1% surface coverage. We discuss in this work that this is possible due to the distinct properties of polyol synthesized AgNPs such as atomically flat surfaces, sharp edges and corners naturally occurring in this synthesis method, which favor strong plasmonic activity. The method can be generalized to convert virtually any surface into a SERS substrate.

In vivo distribution of ß2 glycoprotein I under various pathophysiologic conditions.

In vitro studies have documented ß2 glycoprotein I (ß2GPI) binding to endothelial cells (ECs) and trophoblast using antiphospholipid antibodies. The in vivo binding of ß2GPI to these cells and the conditions that favor their interaction have not been investigated. We analyzed the in vivo distribution of cyanine 5.5-labeled ß2GPI in mice and evaluated the effect of pregnancy and circulating antibodies on its tissue localization. The signal was detected in the liver by whole body scan and ex vivo analysis. The ß2GPI failed to bind to the vascular endothelium and reacted only with the ECs of uterine vessels. In pregnant mice the protein was localized on ECs and trophoblast at the embryo implantation sites. Immunized mice showed a similar ß2GPI biodistribution to naive mice but the immunized pregnant animals exhibited a significant increase in fetal loss associated with C3 and C9 deposition at the implantation sites. Treatment of mice with LPS after ß2GPI-Cy5.5 injection promoted protein localization on gut and brain ECs associated with IgG, C1q, and C9 deposition in immunized mice. These findings indicate that ß2GPI binding to EC requires priming with pro-inflammatory factors which is not needed for uterine and placental localization probably dependent on hormonal changes.

Effect of surface type on structural and optical properties of Ag nanoparticles formed by dewetting.

Integration of an array of Ag nanoparticles in solar cells is expected to increase light trapping through field enhancement and plasmonic scattering. Requirement of Ag nanoparticle decoration of cell surfaces or interfaces at the macro-scale, calls for a self-organized fabrication method such as thermal dewetting. Optical properties of a 2D array of Ag nanoparticles are known to be very sensitive to their shape and size. We show that these parameters depend on the type of the substrate used. We observe that the average nanoparticle size decreases with increasing substrate thermal conductivity and nanoparticle size distribution broadens with increasing surface roughness.

Understanding the plasmonic properties of dewetting formed Ag nanoparticles for large area solar cell applications.

The effects of substrates with technological interest for solar cell industry are examined on the plasmonic properties of Ag nanoparticles fabricated by dewetting technique. Both surface matching (boundary element) and propagator (finite difference time domain) methods are used in numerical simulations to describe plasmonic properties and to interpret experimental data. The uncertainty on the locations of nanoparticles by the substrate in experiment is explained by the simulations of various Ag nanoparticle configurations. The change in plasmon resonance due to the location of nanoparticles with respect to the substrate, interactions among them, their shapes, and sizes as well as dielectric properties of substrate are discussed theoretically and implications of these for the experiment are deliberated.

A revertible, autonomous, self-assembled DNA-origami nanoactuator.

A DNA-origami actuator capable of autonomous internal motion in accord to an external chemical signal was designed, built, operated and imaged. The functional DNA nanostructure consists of a disk connected to an external ring in two, diametrically opposite points. A single stranded DNA, named probe, was connected to two edges of the disk perpendicularly to the axis of constrain. In the presence of a hybridizing target molecule, the probe coiled into a double helix that stretched the inner disk forcing the edges to move toward each other. The addition of a third single stranded molecule that displaced the target from the probe restored the initial state of the origami. Operation, dimension and shape were carefully characterized by combining microscopy and fluorescence techniques.

Tip enhanced Raman scattering with adiabatic plasmon focusing tips.

Tip-Enhanced Raman spectroscopy (TERS) is a promising microscopy technique which combines, in principle, outstanding spatial resolution with a detailed chemical analysis of the sample. However, as yet, it is not routinely used although an increasing number of research groups are becoming more actively involved in the field. Among the several reasons which can explain the relatively low usage of TERS, the lack of reproducibility of tips as field enhancers is probably the most critical. Here we propose and demonstrate a TERS microscope which uses photonic engineered tips. These tips are based on standard silicon nitride atomic force microscope (AFM) cantilevers. A photonic crystal together with a plasmonic waveguide focuses the Raman excitation laser to the apex of the waveguide, enabling a photon confinement equivalent to the radius of curvature of the nanofabricated tip. These tips were successfully applied here in both AFM imaging and high resolution Raman spectroscopy. The new tips produced AFM imaging performances comparable with the best AFM commercial tips. Moreover, we demonstrate that the photonic crystal combined with the plasmonic waveguide acts effectively as a localized near field emitter.

Improvement of Laser-Crystallized Silicon Film Quality via Intermediate Dielectric Layers on a Glass Substrate.

The laser crystallization (LC) of amorphous silicon thin films into polycrystalline silicon (pc-Si) thin films on glass substrates is an active field of research in the fabrication of Si-based thin film transistors and thin film solar cells. Efforts have been, in particular, focused on the improvement of LC technique. Adhesion promoters of the crystallized Si thin films at the glass interface play a crucial role in the stability and device performance of fabricated structures. The crystalline Si thin films are required to be produced free of contamination risks arising from impurity diffusion from the glass substrate. Moreover, it is preferable to fabricate pc-Si thin films at temperatures as close as possible to the ambient temperature for an effective cost reduction. In this work, we demonstrate the successful use of a commercially available nanosecond pulsed laser marker at 1064 nm wavelength for Si crystallization at ambient conditions compared to the common method of pre-elevated substrate temperatures used in continuous wave laser irradiation technique. As a result, our technique results in a better energy balance than that in previous works. The second main purpose of this study is to enhance the crystallinity of Si thin films and to determine the best choice of an intermediate dielectric layer (IDL) comparatively among four thin buffer layers, namely, SiN x , SiO2, ZnO, and TiO2, for the sake of obtaining improved adhesion and larger crystalline domains as compared to that on a direct Si-glass interface. The crystalline qualities of samples containing IDLs of SiN x , SiO2, ZnO, and TiO2 were compared via Raman spectroscopy analysis and electron backscatter diffraction method against the direct Si-glass interface reference. The analyses quantitatively showed that both the crystallinity and the domain sizes can be increased via IDLs.

97 percent light absorption in an ultrabroadband frequency range utilizing an ultrathin metal layer: randomly oriented, densely packed dielectric nanowires as an excellent light trapping scaffold.

In this paper, we propose a facile and large scale compatible design to obtain perfect ultrabroadband light absorption using metal-dielectric core-shell nanowires. The design consists of atomic layer deposited (ALD) Pt metal uniformly wrapped around hydrothermally grown titanium dioxide (TiO2) nanowires. It is found that the randomly oriented dense TiO2 nanowires can impose excellent light trapping properties where the existence of an ultrathin Pt layer (with a thickness of 10 nm) can absorb the light in an ultrabroadband frequency range with an amount near unity. Throughout this study, we first investigate the formation of resonant modes in the metallic nanowires. Our findings prove that a nanowire structure can support multiple longitudinal localized surface plasmons (LSPs) along its axis together with transverse resonance modes. Our investigations showed that the spectral position of these resonance peaks can be tuned with the length, radius, and orientation of the nanowire. Therefore, TiO2 random nanowires can contain all of these features simultaneously in which the superposition of responses for these different geometries leads to a flat perfect light absorption. The obtained results demonstrate that taking unique advantages of the ALD method, together with excellent light trapping of chemically synthesized nanowires, a perfect, bifacial, wide angle, and large scale compatible absorber can be made where an excellent performance is achieved while using less materials.

In-chip microstructures and photonic devices fabricated by nonlinear laser lithography deep inside silicon.

Silicon is an excellent material for microelectronics and integrated photonics1-3 with untapped potential for mid-IR optics4. Despite broad recognition of the importance of the third dimension5,6, current lithography methods do not allow fabrication of photonic devices and functional microelements directly inside silicon chips. Even relatively simple curved geometries cannot be realised with techniques like reactive ion etching. Embedded optical elements, like in glass7, electronic devices, and better electronic-photonic integration are lacking8. Here, we demonstrate laser-based fabrication of complex 3D structures deep inside silicon using 1 µm-sized dots and rod-like structures of adjustable length as basic building blocks. The laser-modified Si has a different optical index than unmodified parts, which enables numerous photonic devices. Optionally, these parts are chemically etched to produce desired 3D shapes. We exemplify a plethora of subsurface, i.e., "in-chip" microstructures for microfluidic cooling of chips, vias, MEMS, photovoltaic applications and photonic devices that match or surpass the corresponding state-of-the-art device performances.

Infrared microspectroscopy: a multiple-screening platform for investigating single-cell biochemical perturbations upon prion infection.

Prion diseases are a group of fatal neurodegenerative disorders characterized by the accumulation of prions in the central nervous system. The pathogenic prion (PrP(Sc)) possesses the capability to convert the host-encoded cellular isoform of the prion protein, PrP(C), into nascent PrP(Sc). The present work aims at providing novel insight into cellular response upon prion infection evidenced by synchrotron radiation infrared microspectroscopy (SR-IRMS). This non-invasive, label-free analytical technique was employed to investigate the biochemical perturbations undergone by prion infected mouse hypothalamic GT1-1 cells at the cellular and subcellular level. A decrement in total cellular protein content upon prion infection was identified by infrared (IR) whole-cell spectra and validated by bicinchoninic acid assay and single-cell volume analysis by atomic force microscopy (AFM). Hierarchical cluster analysis (HCA) of IR data discriminated between infected and uninfected cells and allowed to deduce an increment of lysosomal bodies within the cytoplasm of infected GT1-1 cells, a hypothesis further confirmed by SR-IRMS at subcellular spatial resolution and fluorescent microscopy. The purpose of this work, therefore, consists of proposing IRMS as a powerful multiscreening platform, drawing on the synergy with conventional biological assays and microscopy techniques in order to increase the accuracy of investigations performed at the single-cell level.

Nanoscale chemical mapping using three-dimensional adiabatic compression of surface plasmon polaritons.

The fields of plasmonics, Raman spectroscopy and atomic force microscopy have recently undergone considerable development, but independently of one another. By combining these techniques, a range of complementary information could be simultaneously obtained at a single molecule level. Here, we report the design, fabrication and application of a photonic-plasmonic device that is fully compatible with atomic force microscopy and Raman spectroscopy. Our approach relies on the generation and localization of surface plasmon polaritons by means of adiabatic compression through a metallic tapered waveguide to create strongly enhanced Raman excitation in a region just a few nanometres across. The tapered waveguide can also be used as an atomic force microscope tip. Using the device, topographic, chemical and structural information about silicon nanocrystals may be obtained with a spatial resolution of 7 nm.

Modulation of alpha-synuclein aggregation by dopamine analogs.

The action of dopamine on the aggregation of the unstructured alpha-synuclein (alpha-syn) protein may be linked to the pathogenesis of Parkinson's disease. Dopamine and its oxidation derivatives may inhibit alpha-syn aggregation by non-covalent binding. Exploiting this fact, we applied an integrated computational and experimental approach to find alternative ligands that might modulate the fibrillization of alpha-syn. Ligands structurally and electrostatically similar to dopamine were screened from an established library. Five analogs were selected for in vitro experimentation from the similarity ranked list of analogs. Molecular dynamics simulations showed they were, like dopamine, binding non-covalently to alpha-syn and, although much weaker than dopamine, they shared some of its binding properties. In vitro fibrillization assays were performed on these five dopamine analogs. Consistent with our predictions, analyses by atomic force and transmission electron microscopy revealed that all of the selected ligands affected the aggregation process, albeit to a varying and lesser extent than dopamine, used as the control ligand. The in silico/in vitro approach presented here emerges as a possible strategy for identifying ligands interfering with such a complex process as the fibrillization of an unstructured protein.

Structural insights into alternate aggregated prion protein forms.

The conversion of the cellular form of the prion protein (PrP(C)) to an abnormal, alternatively folded isoform (PrP(Sc)) is the central event in prion diseases or transmissible spongiform encephalopathies. Recent studies have demonstrated de novo generation of murine prions from recombinant prion protein (recPrP) after inoculation into transgenic and wild-type mice. These so-called synthetic prions lead to novel prion diseases with unique neuropathological and biochemical features. Moreover, the use of recPrP in an amyloid seeding assay can specifically detect and amplify various strains of prions. We employed this assay in our experiments and analyzed in detail the morphology of aggregate structures produced under defined chemical constraints. Our results suggest that changes in the concentration of guanidine hydrochloride can lead to different kinetic traces in a typical thioflavin T(ThT) assay. Morphological and structural analysis of these aggregates by atomic force microscopy indicates a variation in the structure of the PrP molecular assemblies. In particular, ThT positive PrP aggregates produced from rec mouse PrP residues 89 to 230 lead to mostly oligomeric structures at low concentrations of guanidine hydrochloride, while more amyloidal structures were observed at higher concentrations of the denaturant. These findings highlight the presence of numerous and complex pathways in deciphering prion constraints for infectivity and toxicity.

Fluorescence enhancement in hot spots of AFM-designed gold nanoparticle sandwiches.

We observe an enhancement of fluorescence from a single fluorescent sphere, which is sandwiched between two individual gold nanoparticles, forming a hot spot of strong field enhancement. The fluorescence enhancing hot spot is custom-designed by the deliberate assembly of gold nanoparticles with an atomic force microscope cantilever. The fluorescence intensity is monitored while the separation between the two gold nanoparticles is reduced by gradually pushing the gold nanoparticles closer to the fluorescent sphere. The fluorescence enhancement is maximal when the distance between the two gold nanoparticles is smallest, when the excitation polarization is parallel to the axis of the sandwich, and when the fluorescent sphere is positioned exactly on the axis connecting the two gold nanoparticles.

Nanocrystal-encoded fluorescent microbeads for proteomics: antibody profiling and diagnostics of autoimmune diseases.

The first application of nanocrystal (NC)-encoded microbeads to clinical proteomics is demonstrated by multiplexed detection of circulating autoantibodies, markers of systemic sclerosis. Two-color complexes, consisting of NC-encoded, antigen-covered beads, anti-antigen antibody or clinical serum samples, and dye-tagged detecting antibodies, were observed using flow cytometry assays and on the surface of single beads. The results of flow cytometry assays correlated with the ELISA technique and provided clear discrimination between the sera samples of healthy donors and patients with autoimmune disease. Microbead fluorescence signals exhibited narrow distribution regardless of their surface antigen staining, without the need of any fluorescence compensation-a parameter determining the limit of sensitivity of flow cytometry assays. In single bead measurements, less than 30 dye-labeled antibodies interacting with the topoI-specific antibodies at the surface of a bead have been detected by the emission of dye excited through the FRET from NCs. In this format, the antibody-bead interaction reaction turns specifically the fluorescence signal from dye label off and on, additionally increasing autoantibody detection sensitivity.