Sample induced intensity variations of localized surface plasmon resonance in tip-enhanced Raman spectroscopy.

Tip-enhanced spectroscopy techniques, in particular tip-enhanced Raman spectroscopy (TERS), rely on a localized surface plasmon resonance (LSPR). This LSPR depends on the near field antenna, its material and shape, and the surrounding medium with respect to its relative permittivity and the volume fraction of the optical near field occupied by the sample. Here, we investigate the effects of the surface composition and topography on the change of the LSPR intensity in tip-enhanced spectroscopy on SrTiO3 nanoislands by monitoring the LSPR enhanced luminescence of gold tips. Our experimental results and analytical estimates indicate that by affecting the effective permittivity of the dielectric environment at the tip apex, the material composition as well as topography of the studied sample induce a change in LSPR intensity. This result significantly helps the understanding of the evolution or origin of the LSPR intensity during a typical TERS measurement, which in turn leads to a more accurate assessment of the relative intensity of different Raman modes in TERS.

Topography-induced variations of localized surface plasmon resonance in tip-enhanced Raman configuration.

We report on topography-induced changes of the localized surface plasmon resonance (LSPR) enhanced luminescence of gold tip on SrTiO3 nanostructures with apertureless scanning near-field optical microscopy (aSNOM) in tip-enhanced Raman spectroscopy (TERS) configuration. Our experimental and simulated results indicate that the averaged refractive index of the dielectric environment of the tip apex containing both air and SrTiO3 in variable volume ratios, is dependent on the topography of the sample. This reveals that the local topography has to be taken into consideration as an additional contribution to the position of the LSPR.

Plasmonic Enhancement of Two-Photon Excitation Fluorescence by Colloidal Assemblies of Very Small AuNPs Templated on M13 Phage.

In this study, an engineered M13 bacteriophage was examined as a biological template to create a well-defined spacing between very small gold nanoparticles (AuNPs 3-13 nm). The effect of the AuNP particle size on the enhancement of the nonlinear process of two-photon excitation fluorescence (2PEF) was investigated. Compared to conventional (one-photon) microscopy techniques, such nonlinear processes are less susceptible to scattering given that the density of background-scattered photons is too low to generate a detectable signal. Besides this, the use of very small AuNPs in 2PEF microscopy becomes more advantageous because individual "isolated" AuNPs of this size do not sufficiently enhance 2PEF to produce a detectable signal, resulting in even less background signal. To investigate the 2PEF of the AuNP-M13 assemblies, a variety of sample preparation approaches are tested, and surface-enhanced Raman spectroscopy (SERS) is employed to study the strength of plasmon coupling within the gaps of AuNPs assembled on the M13 template. Results indicate that assemblies prepared with 9-13 nm AuNP were able to clearly label Escherichia coli cells and produce a 2PEF signal that was orders of magnitude higher than the isolated AuNP (below the threshold of detection). This study thus provides a better understanding of the opportunities and limitations relevant to the use of such small AuNPs within colloidal plasmonic assemblies, for applications in biodetection or as imaging contrast agents.

Ultrastructures and Mechanics of Annealed Nephila clavipes Major Ampullate Silk.

The semicrystalline protein structure and impressive mechanical properties of major ampullate (MA) spider silk make it a promising natural alternative to polyacrylonitrile (PAN) fibers for carbon fiber manufacture. However, when annealed using a similar procedure to carbon fiber production, the tensile strength and Young's modulus of MA silk decrease. Despite this, MA silk fibers annealed at 600 °C remain stronger and tougher than similarly annealed PAN but have a lower Young's modulus. Although MA silk and PAN graphitize to similar extents, annealing disrupts the hydrogen bonding that controls crystal alignment within MA silk. Consequently, unaligned graphite crystals form in annealed MA silk, causing it to weaken, while graphite crystals in PAN maintain alignment along the fiber axis, strengthening the fibers. These shortcomings of spider silk when annealed provide insights into the selection and design of future alternative carbon fiber precursors.

Contrast Enhancement for the Recovery of Obliterated Serial Numbers in Different Polymers by Correlated Raman Imaging of Strain, Phonon Lifetime, and Strain-Induced Anisotropy.

In the field of forensic science, we have recently introduced Raman imaging as a promising nondestructive technique to efficiently recover obliterated serial numbers in polycarbonate. The present study is extending the investigation toward different polymers for the reconstruction of abraded information by Raman spectroscopy. Samples of polyethylene, nylon, and nylatron, which are mainly used in items such as firearms, banknotes, and package materials, are investigated by monitoring the vibrational modes which are most susceptible to peak shifts and changes in the full width at half-maximum (fwhm) and peak intensity ratios. In all cases, the most affected peak depends on the polymer's 3D structure and displays a ∼1 cm-1 shift and a broadening above ∼2 cm-1, as well as a relative intensity change of over 50%, more than enough for a successful recovery through confocal imaging. Depending on the polymer's structural arrangement, any of the three contributions prevails for the strongest contrast. The propagation of the plastic deformations is mainly affected by the Young's modulus of the material, due to a change in its elasticity. The shift, the width, and the relative intensity of the Raman peaks being three independent parameters, they can be correlated to enhance the contrast and thus to accelerate the image acquisition or to enhance statistical significance.

Extreme temperature stability of thermally insulating graphene-mesoporous-silicon nanocomposite.

We demonstrate the thermal stability and thermal insulation of graphene-mesoporous-silicon nanocomposites (GPSNC). By comparing the morphology of GPSNC carbonized at 650 °C as-formed to that after annealing, we show that this nanocomposite remains stable at temperatures as high as 1050 °C due to the presence of a few monolayers of graphene coating on the pore walls. This does not only make this material compatible with most thermal processes but also suggests applications in harsh high temperature environments. The thermal conductivity of GPSNCs carbonized at temperatures in the 500 °C-800 °C range is determined through Raman spectroscopy measurements. They indicate that the thermal conductivity of the composite is lower than that of silicon, with a value of 13 ± 1 W mK-1 at room temperature, and not affected by the thin graphene layer, suggesting a role of the high concentration of carbon related-defects as indicated by the high intensity of the D-band compared to G-band of the Raman spectra. This morphological stability at high temperature combined with a high thermal insulation make GPSNC a promising candidate for a broad range of applications including microelectromechanical systems and thermal effect microsystems such as flow sensors or IR detectors. Finally, at 120 °C, the thermal conductivity remains equal to that at room temperature, attesting to the potential of using our nanocomposite in devices that operate at high temperatures such as microreactors for distributed chemical conversion, solid oxide fuel cells, thermoelectric devices or thermal micromotors.

Reconstruction of Obliterated Characters in Polycarbonate through Spectral Imaging.

In forensic sciences, there is an increasing demand for nondestructive and reliable methods to retrieve obliterated information in polymers. This study demonstrates a case study for the potential of Raman spectroscopy to reconstruct abraded serial numbers. Residual strain and local variations in the structural arrangement are nondestructively imaged through peak shifts and variations of the full width at half-maximum of specific Raman lines, respectively. We qualitatively validate our approach by successfully recovering an obliterated letter stamped with a pressure of ∼170 MPa in a polycarbonate sample, with a subsequent quantitative statistical analysis. The detection threshold is estimated from the propagation depth of plastic deformations to a value of ∼750-800 µm, substantially larger than typical obliteration depths, 200 µm in our case for an initial profile depth of 120 µm.

Graphene-Mesoporous Si Nanocomposite as a Compliant Substrate for Heteroepitaxy.

The ultimate performance of a solid state device is limited by the restricted number of crystalline substrates that are available for epitaxial growth. As a result, only a small fraction of semiconductors are usable. This study describes a novel concept for a tunable compliant substrate for epitaxy, based on a graphene-porous silicon nanocomposite, which extends the range of available lattice constants for epitaxial semiconductor alloys. The presence of graphene and its effect on the strain of the porous layer lattice parameter are discussed in detail and new remarkable properties are demonstrated. These include thermal stability up to 900 °C, lattice tuning up to 0.9 % mismatch, and compliance under stress for virtual substrate thicknesses of several micrometers. A theoretical model is proposed to define the compliant substrate design rules. These advances lay the foundation for the fabrication of a compliant substrate that could unlock the lattice constant restrictions for defect-free new epitaxial semiconductor alloys and devices.

Effect of the gold crystallinity on the enhanced luminescence signal of scanning probe tips in apertureless near-field optical microscopy.

The effect of gold tip crystallinity on their spectral amplification characteristics, monitored through the luminescence enhanced by surface plasmon resonance (SPR), is investigated experimentally. As the tip radius increases, the grains composing polycrystalline tips become larger, resulting in a blueshift of the emission while a redshift of the SPR was predicted for monocrystalline gold. This reveals that the effect of the grain size, a parameter that has not been considered so far, is dominant over that of the tip radius. This study is significant to apertureless scanning near-field optical microscopy, where the gold tip emission defines the spectral antenna range.

Integration of 3D nanographene into mesoporous germanium.

Graphene is a key material of interest for the modification of physicochemical surface properties. However, its flat surface is a limitation for applications requiring a high specific surface area. This restriction may be overcome by integrating 2D materials in a 3D structure. Here, a strategy for the controlled synthesis of Graphene-Mesoporous Germanium (Gr-MP-Ge) nanomaterials is presented. Bipolar electrochemical etching and chemical vapor infiltration were employed, respectively, for the nanostructuration of Ge substrate and subsequent 3D nanographene coating. While Raman spectroscopy reveals a tunable domain size of nanographene with the treatment temperature, transmission electron microscopy data confirm that the crystallinity of Gr-MP-Ge is preserved. X-ray photoelectron spectroscopy indicates the non-covalent bonding of carbon to Ge for Gr-MP-Ge. State-of-the-art molecular dynamics modeling provides a deeper understanding of the synthesis process through the presence of radicals. The successful synthesis of these nanomaterials offers the integration of nanographene into a 3D structure with a high aspect ratio and light weight, thereby opening avenues to a variety of applications for this versatile nanomaterial.

Latent Fingermark Imaging by Single-Metal Deposition of Gold Nanoparticles and Surface Enhanced Raman Spectroscopy.

In forensic science, there is a high demand for a technique that allows the revelation of fingermarks invisible to the naked eye as well as the chemical information they contain. Here, we present a feasibility study consisting of using both the luminescence enhanced by surface plasmon of gold nanoparticles, and the surface enhanced Raman spectroscopy signal of fingermark chemical components to image latent fingermarks. A latent fingermark deposited on a transparent glass substrate was visually revealed using single-metal deposition employing gold nanoparticles. The resulting enhanced luminescence was monitored over a developed area of the latent fingermark, displaying light regions of 200-400 µm, corresponding to the fingermark ridges. The Raman signal of the fingermark's chemical components was enhanced into a measurable signal. Imaging those Raman peaks revealed the ridges pattern, attesting to the potential of our method. Since SMD is an end-of-sequence revelation technique for which further enhancement techniques do not exist, this work aims at demonstrating the feasibility of the technique in order to apply it on different systems, able to illuminate a complete surface of a few cm, and thus capable of both detecting contaminants in LFM and imaging features of the size of a complete LFM.

Optical near-field mapping of plasmonic nanostructures prepared by nanosphere lithography.

We introduce a simple, fast, efficient and non-destructive method to study the optical near-field properties of plasmonic nanotriangles prepared by nanosphere lithography. Using a rectangular Fourier filter on the blurred signal together with filtering of the lower spatial frequencies to remove the far-field contribution, the pure near-field contributions of the optical images were extracted. We performed measurements using two excitation wavelengths (532.1 nm and 632.8 nm) and two different polarizations. After the processing of the optical images, the distribution of hot spots can be correlated with the topography of the structures, as indicated by the presence of brighter spots at the apexes of the nanostructures. This technique is validated by comparison of the results to numerical simulations, where agreement is obtained, thereby confirming the near-field nature of the images. Our approach does not require any advanced equipment and we suggest that it could be applied to any type of sample, while keeping the measurement times reasonably short.

A Complementary Metal Oxide Semiconductor Process-Compatible Ferroelectric Tunnel Junction.

In recent years, experimental demonstration of ferroelectric tunnel junctions (FTJ) based on perovskite tunnel barriers has been reported. However, integrating these perovskite materials into conventional silicon memory technology remains challenging due to their lack of compatibility with the complementary metal oxide semiconductor process (CMOS). This communication reports the fabrication of an FTJ based on a CMOS-compatible tunnel barrier Hf0.5Zr0.5O2 (6 unit cells thick) on an equally CMOS-compatible TiN electrode. Analysis of the FTJ by grazing angle incidence X-ray diffraction confirmed the formation of the noncentrosymmetric orthorhombic phase (Pbc21, ferroelectric phase). The FTJ characterization is followed by the reconstruction of the electrostatic potential profile in the as-grown TiN/Hf0.5Zr0.5O2/Pt heterostructure. A direct tunneling current model across a trapezoidal barrier was used to correlate the electronic and electrical properties of our FTJ devices. The good agreement between the experimental and theoretical model attests to the tunneling electroresistance effect (TER) in our FTJ device. A TER ratio of ∼15 was calculated for the present FTJ device at low read voltage (+0.2 V). This study suggests that Hf0.5Zr0.5O2 is a promising candidate for integration into conventional Si memory technology.