CMOS-compatible Hf0.5Zr0.5O2-based ferroelectric memory crosspoints fabricated with damascene process.

We report the fabrication of Hf0.5Zr0.5O2(HZO) based ferroelectric memory crosspoints using a CMOS-compatible damascene process. In this work, we compared 12 and 56 µm² crosspoint devices with the 0.02 mm² round devices commonly used as a benchmark. For all devices, a 9 nm thick ferroelectric thin film was deposited by plasma-enhanced atomic layer deposition (PEALD) on planarized bottom electrodes (BE). The wake-up appeared to be longer for the crosspoint memories compared to 0.02 mm² benchmark, while all the devices reached a 2Prvalue of ~ 50 µC/cm² after 105cycles with 3 V/10 µs squared pulses. The crosspoints stand out for their superior endurance, which was increased by an order of magnitude. Nucleation limited switching (NLS) experiments were performed, revealing a switching time < 170 ns for our 12 and 56 µm² devices, while it remained in the µs range for the larger round devices. The downscaled devices demonstrate notable advantages with a rise in endurance and switching speed.

Unraveling the Heterointegration of 3D Semiconductors on Graphene by Anchor Point Nucleation.

The heterointegration of graphene with semiconductor materials and the development of graphene-based hybrid functional devices are heavily bound to the control of surface energy. Although remote epitaxy offers one of the most appealing techniques for implementing 3D/2D heterostructures, it is only suitable for polar materials and is hugely dependent on the graphene interface quality. Here, the growth of defect-free single-crystalline germanium (Ge) layers on a graphene-coated Ge substrate is demonstrated by introducing a new approach named anchor point nucleation (APN). This powerful approach based on graphene surface engineering enables the growth of semiconductors on any type of substrate covered by graphene. Through plasma treatment, defects such as dangling bonds and nanoholes, which act as preferential nucleation sites, are introduced in the graphene layer. These experimental data unravel the nature of those defects, their role in nucleation, and the mechanisms governing this technique. Additionally, high-resolution transmission microscopy combined with geometrical phase analysis established that the as-grown layers are perfectly single-crystalline, stress-free, and oriented by the substrate underneath the engineered graphene layer. These findings provide new insights into graphene engineering by plasma and open up a universal pathway for the heterointegration of high-quality 3D semiconductors on graphene for disruptive hybrid devices.

Raman spectroscopy investigation of magnesium oxide nanoparticles.

We investigate Raman spectra (100 cm-1 to 3900 cm-1) of magnesium oxide nanoparticles with nominal sizes of 10 nm, 20 nm, 40 nm, 50 nm, and 300 nm. The crystal structure of MgO prohibits first-order modes and yet, there are numerous reports of relatively intense peaks throughout the literature. Raman signals at approximately 278 cm-1 and 445 cm-1 that were attributed to MgO nanoparticles by previous authors are shown to belong to layers of Mg(OH)2 formed on the surface of MgO nanoparticles. Through an annealing process at 400 °C in an O2 atmosphere, we observe that modes in the 3700 cm-1 spectral region, which are a signature of OH groups, disappear together with modes at 278 cm-1 and 445 cm-1, thus establishing a necessary criterion to associate all of these peaks to the presence of OH groups on the surface.

In Operando Photoswitching of Cu Oxidation States in Cu-Based Plasmonic Heterogeneous Photocatalysis for Efficient H2 Evolution.

Metal nanoparticles (NP) supported on TiO2 are known to be efficient photocatalysts for solar-to-chemical energy conversion. While TiO2 decorated with copper NPs has the potential to become an attractive system, the poor oxidative stability of Cu severely limits its applicability. In this work, we demonstrate that, when Cu NPs supported on TiO2 nanobelts (NBs) are engaged in the photocatalytic generation of H2 from water under light illumination, Cu is not only oxidized in CuO but also dissolved under the form of Cu+/Cu2+ ions, leading to a continuous reconstruction of nanoparticles via Ostwald ripening. By nanoencapsulating the CuOx (Cu/CuO/Cu2O) NPs by a few layers of carbon supported on TiO2 (TC@C), Ostwald ripening can be suppressed. Simultaneously, the resulting CuOx@C NPs are photoreduced under light illumination to generate Cu@C NPs. This photoswitching strategy allows the preparation of a Cu plasmonic photocatalyst with enhanced activity for H2 production. Remarkably, the photocatalyst is even active when illuminated with visible light, indicating a clear plasmonic enhancement of photocatalytic activity from the surface plasmonic resonance (SPR) effect of Cu NPs. Three-dimensional electromagnetic wave-frequency domain (3D-EWFD) simulations were conducted to confirm the SPR enhancement. This advance bodes for the development of scalable multifunctional Cu-based plasmonic photocatalysts for solar energy transfer.

Phonon confinement and particle size effect on the low-frequency Raman mode of aurivillius phase Bi4Ti3O12 powders.

We report the systematic measurements in bismuth titanate powders of Raman frequency shift, ω and full width at half maximum (FWHM), Γ of optical phonons at q = 0 obtained between ∼300 K and 673 K in air. Both the particle size and phonon confinement effects are reasonably satisfactory to explain the Raman peak shift and asymmetric broadening observed in the ferroelectric soft phonon mode at 42 cm-1. It is shown that the lattice parameter varies as particle size x, and its contribution to size-dependent Raman shift and broadening of linewidth follows ω ∝ x -0.73 and Γ âˆ x -0.38 law, respectively. Moreover, a single phonon coupling term corresponding to a three-phonon anharmonic process is sufficient to describe the phonon coupling decay culminating from the softening of this strongly overdamped phonon mode.

Catalytic Applications of Non-Centrosymmetric Oxide Nanomaterials.

Noble-metal-free catalytic nanoparticles hold the promise being abundant, low-cost materials having a small environmental footprint and excellent performance, albeit inferior to that of noble metal counterparts. Several materials have a long-standing history of success in photocatalysis, in particular titanium dioxide, and in recent years more complex oxides and added functionality have emerged with enhanced performance. We will discuss different approaches related to the use of non-centrosymmetric and polar oxide nanoparticles and how the bulk photovoltaic effect, piezoelectricity, and pyroelectricity add to photocatalysis and tribocatalysis. We pay special attention to discriminate between the role of free versus that of bound charges within the catalyst, which is crucial to disentangle the different contributions to the catalytic reaction for the benefit of the overall enhanced catalytic performance in e.g. wastewater treatment and ultimately water-splitting.

In situ evaluation of plasmonic enhancement of gold tips for plasmon-enhanced imaging techniques.

Plasmonic nanoantennas are at the core of various optical near-field scanning techniques such as tip-enhanced Raman spectroscopy as they provide the amplification and confinement of the electromagnetic field, which ultimately provides sensitivity and spatial resolution. With a cornucopia of different fabrication methods available, the actual performance of a nanoantenna is often only assessed by whether or not near-field imaging is possible, implying the complete alignment and landing procedure of the scanning probe. We present a semi-quantitative approach to assess the plasmonic enhancement of gold tips via localized surface plasmon resonance (LSPR) enhancement of intrinsic gold photoluminescence without the need for interaction with the sample. As the intensity of the plasmon at the apex decreases, a significant change in the shape of the tip signal spectrum is observed, reflecting itself as a decrease in the R2 value (fit quality) for numerical fitting with a Lorentzian, which also provides an approximation for the LSPR wavelength. Our findings suggest that the potential of a tip to perform well as an optical near field antenna may already be assessed in an early stage of the experiment.

Effect of Extrinsic Disorder on the Magnetoresistance Response of Gated Single-Layer Graphene Devices.

Analogous to the case of classical metal oxide semiconductor field-effect transistors, transport properties of graphene-based devices are determined by scattering from adventitious charged impurities that are invariably present. The presence of charged impurities renders experimental graphene samples "extrinsic" in that their electrical performances also depend on the environment in which graphene operates. While the role of such an extrinsic disorder component has been studied for conventional charge transport in graphene, its impact on the magnetotransport remains unexplored. Here, we show that single-layer graphene transistors with a low density of extrinsic disorder feature a larger magnetoresistance (MR) than those with a high density. Importantly, in gated single-layer devices with a low density of charged impurities, we find that MR peaks at gate voltage values far from the charge neutrality point not only at a low temperature but also at room temperature; in particular, MR approaches 800% at room temperature and 1400% at 50 K in such devices. In addition, dynamic measurements of MR on devices with a low degree of extrinsic disorder lead to stable and reliable single-layer graphene magnetosensors endowed with an ultralow power consumption of 2.5 nW. Our work indicates that the initial value of the minimum conductivity σ0 at room temperature along with carrier mobility must be looked at to select the most promising devices for magnetosensing.

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.

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.

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.

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.

Smooth pyroelectric luminescence in LiNbO3 single crystals.

We investigate the phenomenon of pyroelectric luminescence in LiNbO3 single crystals. This faint emission of light due to temperature-induced changes of permanent polarization is induced by different types of charge carrier recombination, outside and inside the crystal. With decreasing atmospheric pressure, the external discharge mechanism transitions from sparse intense gas discharge pulses at ambient pressure, to frequent faint discharges close to 1 mbar, to a continuous emission which is referred to as smooth pyroelectric luminescence. Our experimental setup exposes the crystal to constant positive and negative temperature changes in the range of 360-450 K under high vacuum while simultaneously measuring the surface charge density and the emitted intensity. A microscopic model of the luminescence allows the description of the time-dependent pyroelectric luminescence, in particular the determination of deep trap potentials that are otherwise inaccessible to thermal ionization. Using this model, we show that the behavior of this emission in LiNbO3 crystals is consistent with the release of trapped electrons by the Poole-Frenkel effect from a Dirac-well potential, while the commonly assumed coulombic trap shape is in clear disagreement with both the temporal evolution of the emission as well as the magnitude of the electric field obtained in our measurements.

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.

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.

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.