Unique orientation of 1D and 2D nanoparticle assemblies confined in smectic topological defects.

New collective optical properties have emerged recently from organized and oriented arrays of closely packed semiconducting and metallic nanoparticles (NPs). However, it is still challenging to obtain NP assemblies which are similar everywhere on a given sample and, most importantly, share a unique common orientation that would guarantee a unique behavior everywhere on the sample. In this context, by combining optical microscopy, fluorescence microscopy and synchrotron-based grazing incidence X-ray scattering (GISAXS) of assemblies of gold nanospheres and of fluorescent nanorods, we study the interactions between NPs and liquid crystal smectic topological defects that can ultimately lead to unique NP orientations. We demonstrate that arrays of one-dimensional - 1D (dislocations) and two-dimensional - 2D (grain boundaries) topological defects oriented along one single direction confine and organize NPs in closely packed networks but also orient both single nanorods and NP networks along the same direction. Through the comparison between smectic films associated with different kinds of topological defects, we highlight that the coupling between the NP ligands and the smectic layers below the grain boundaries may be necessary to allow for fixed NP orientation. This is in contrast with 1D defects, where the induced orientation of the NPs is intrinsically induced by the confinement independently of the ligand nature. We thus succeeded in achieving the fixed polarization of assemblies of single photon emitters in defects. For gold nanospheres confined in grain boundaries, a strict orientation of hexagonal networks has been obtained with the 〈10〉 direction strictly parallel to the defects. With such closely packed and oriented NPs, new collective properties are now foreseen.

From Chains to Monolayers: Nanoparticle Assembly Driven by Smectic Topological Defects.

In this Letter, we show how advanced hierarchical structures of topological defects in the so-called smectic oily streaks can be used to sequentially transfer their geometrical features to gold nanospheres. We use two kinds of topological defects, 1D dislocations and 2D ribbon-like topological defects. The large trapping efficiency of the smectic dislocation cores not only surpasses that of the elastically distorted zones around the cores but also surpasses the one of the 2D ribbon-like topological defect. This enables the formation of a large number of aligned NP chains within the dislocation cores that can be quasi-fully filled without any significant aggregation outside of the cores. When the NP concentration is large enough to entirely fill the dislocation cores, the LC confinement varies from 1D to 2D. We demonstrate that the 2D topological defect cores induce a confinement that leads to planar hexagonal networks of NPs. We then draw the phase diagram driven by NP concentration, associated with the sequential confinements induced by these two kinds of topological defects. Owing to the excellent large-scale order of these defect cores, not only the NP chains but also the NP hexagonal networks can be oriented along the desired direction, suggesting a possible new route for the creation of either 1D or 2D highly anisotropic NP networks. In addition, these results open rich perspectives based on the possible creation of coexisting NP assemblies of different kinds, localized in different confining areas of a same smectic film that would thus interact thanks to their proximity but also would interact via the surrounding soft matter matrix.

In Situ Study of the Interface-Mediated Solid-State Reactions during Growth and Postgrowth Annealing of Pd/a-Ge Bilayers.

Ohmic or Schottky contacts in micro- and nanoelectronic devices are formed by metal-semiconductor bilayer systems, based on elemental metals or thermally more stable metallic compounds (germanides, silicides). The control of their electronic properties remains challenging as their structure formation is not yet fully understood. We have studied the phase and microstructure evolution during sputter deposition and postgrowth annealing of Pd/a-Ge bilayer systems with different Pd/Ge ratios (Pd:Ge, 2Pd:Ge, and 4Pd:Ge). The room-temperature deposition of up to 30 nm Pd was monitored by simultaneous, in situ synchrotron X-ray diffraction, X-ray reflectivity, and optical stress measurements. With this portfolio of complementary real-time methods, we could identify the microstructural origins of the resistivity evolution during contact formation: Real-time X-ray diffraction measurements indicate a coherent, epitaxial growth of Pd(111) on the individual crystallites of the initially forming, polycrystalline Pd2Ge[111] layer. The crystallization of the Pd2Ge interfacial layer causes a characteristic change in the real-time wafer curvature (tensile peak), and a significant drop of the resistivity after 1.5 nm Pd deposition. In addition, we could confirm the isostructural interface formation of Pd/a-Ge and Pd/a-Si. Subtle differences between both interfaces originate from the lattice mismatch at the interface between compound and metal. The solid-state reaction during subsequent annealing was studied by real-time X-ray diffraction and complementary UHV surface analysis. We could establish the link between phase and microstructure formation during deposition and annealing-induced solid-state reaction: The thermally induced reaction between Pd and a-Ge proceeds via diffusion-controlled growth of the Pd2Ge seed crystallites. The second-phase (PdGe) formation is nucleation-controlled and takes place only when a sufficient Ge reservoir exists. The real-time access to structure and electronic properties on the nanoscale opens new paths for the knowledge-based formation of ultrathin metal/semiconductor contacts.

Linear chains of Ag nanoparticles embedded in dielectric films for SERS applications in analytical chemistry.

In line with the approach known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), in which Raman signal amplification of analytes is provided by metallic nanoparticles with an ultrathin silica or alumina shell, we report here on a Surface-Enhanced Raman Spectroscopy (SERS) substrate consisting of periodic lines of Ag nanoparticles embedded in dielectric surfaces for enhancing Raman signals. This paper demonstrates the possibility to use these so-called 'PLANEDSERS' substrates as washable and reusable chemical sensors with a good level of repeatability. Large-area Ag nanoparticle arrays are produced by glancing-angle ion-beam sputtering deposition on nanorippled patterns and are protected from the chemical environment (atmospheric or liquid solutions) by a robust and functionalizable thin dielectric layer of alumina or silicon nitride. Our results show that linear assemblies of ellipsoidal nanoparticles (size ∼15 nm) separated by interparticle gaps of approximately 5 nm generate enough near-field intensity enhancement to give rise to significant SERS signals of non-Raman-resonant bipyridine molecules without chemical contact between molecules and Ag nanoparticles. Moreover, the optical dichroic response of these plasmonic assemblies allows for the possibility of tuning the excitation wavelength of the Raman spectra over a wide spectral range. This study is a first step towards designing a substrate-platform without chemical specificity to enhance in equal manner all the weak Raman signals of usual organic molecules and to avoid loss of balance in favour of only one species as usual in SERS experiments. The quantitative detection ranges for bipyridine used as a probe test molecule are around between 10-3 to 10-6 M.

Structure of glancing incidence deposited TiO(2) thin films as revealed by grazing incidence small-angle X-ray scattering.

For the first time, grazing incidence small-angle X-ray scattering (GISAXS) analysis is used to characterize the morphology of TiO(2) thin films grown by glancing angle physical vapor deposition (GLAD). According to cross-section scanning electron microscopy (SEM) images, the films consist of near isotilted TiO(2) columns of different length and width depending on film thickness. The obtained GISAXS patterns show a characteristic asymmetry with respect to the incidence plane, which is associated with the tilted geometry of the TiO(2) columns. The patterns also show the existence of two populations of columns in these GLAD-TiO(2) films. The population of the thinnest columns appears related to the first grown layer and is common for all the films investigated, while the second population of columns grows with the thickness of the films and has been related to wider columns formed by shadowing at the expense of the initially formed columns.

Full reciprocal-space mapping up to 2000†K under controlled atmosphere: the multipurpose QMAX furnace.

A furnace that covers the temperature range from room temperature up to 2000 K has been designed, built and implemented on the D2AM beamline at the ESRF. The QMAX furnace is devoted to the full exploration of the reciprocal hemispace located above the sample surface. It is well suited for symmetric and asymmetric 3D reciprocal space mapping. Owing to the hemispherical design of the furnace, 3D grazing-incidence small- and wide-angle scattering and diffraction measurements are possible. Inert and reactive experiments can be performed at atmospheric pressure under controlled gas flux. It is demonstrated that the QMAX furnace allows monitoring of structural phase transitions as well as microstructural evolution at the nanoscale, such as self-organization processes, crystal growth and strain relaxation. A time-resolved in situ oxidation experiment illustrates the capability to probe the high-temperature reactivity of materials.

Spectral and Color Changes of Ag/TiO2 Photochromic Films Deposited on Diffusing Paper and Transparent Flexible Plastic Substrates.

Giving paper and polymer photochromic properties under laser irradiation is challenging due to the low resistance of these materials to heat, their flexibility, and their possibly irregular structure. However, we could successfully deposit TiO2/Ag/TiO2 layers stacking on flexible white glossy paper and transparent polyethylene terephalate (PET) substrates using a reactive magnetron sputtering technique, and tailor coloration changes after laser irradiation, alternating visible and ultraviolet (UV) wavelengths. The sample colors are characterized by a panel of chromas depending on the irradiation conditions. We demonstrate that these chroma changes are due to morphological changes of Ag nanoparticles (NPs) after visible laser irradiation of the colored as-deposited sample. The process exhibits a good reversibility after subsequent UV irradiation due to the growth of new metallic Ag NPs. The colors displayed in diffuse reflection by the paper samples are more saturated than the ones displayed in regular transmission by PET samples. We demonstrate the efficiency of the photochromic process on such support by printing high resolution patterns exhibiting different colors depending on the observation conditions.

Self-organized ultrathin FePt nanowires produced by glancing-angle ion-beam codeposition on rippled alumina surfaces.

Ultradense macroscopic arrays of ferromagnetic alloy nanowires exhibit unique properties that make them attractive both for basic physics studies and for prospective nanodevice applications in various areas. We report here on the production of self-organized equiatomic FePt nanowires produced by glancing-angle ion-beam codeposition on alumina nanoripple patterns at room temperature and subsequent annealing at 600 °C. This study demonstrates that periodically aligned FePt nanowires with tunable size (∼10-20 nm width and ∼0.5-10 nm height) can be successfully grown as a consequence of shadowing effects and low mobility of Fe and Pt on the rippled alumina surface. Moreover, the structure and magnetic properties of the FePt nanowires, which undergo a phase transition from a disordered A1 (soft) structure to a partially ordered L10 (hard) structure, can be modified upon annealing. We show that this behavior can be further exploited to change the effective uniaxial anisotropy of the system, which is determined by a strong interplay between the shape and magnetocrystalline anisotropies of the nanowires.

Tailoring Anisotropic Interactions between Soft Nanospheres Using Dense Arrays of Smectic Liquid Crystal Edge Dislocations.

We investigated composite films of gold nanoparticles (NPs)/liquid crystal (LC) defects as a model system to understand the key parameters, which allow for an accurate control of NP anisotropic self-assemblies using soft templates. We combined spectrophotometry, Raman spectroscopy, and grazing incidence small-angle X-ray scattering with calculations of dipole coupling models and soft sphere interactions. We demonstrate that dense arrays of elementary edge dislocations can strongly localize small NPs along the defect cores, resulting in formation of parallel chains of NPs. Furthermore, we show that within the dislocation cores the inter-NP distances can be tuned. This phenomenon appears to be driven by the competition between "soft (nano)sphere" attraction and LC-induced repulsion. We evidence two extreme regimes controlled by the solvent evaporation: (i) when the solvent evaporates abruptly, the spacing between neighboring NPs in the chains is dominated by van der Waals interactions between interdigitated capping ligands, leading to chains of close-packed NPs; (ii) when the solvent evaporates slowly, strong interdigitation between the is avoided, leading to a dominating LC-induced repulsion between NPs associated with the replacement of disordered cores by NPs. The templating of NPs by topological defects, beyond the technological inquiries, may enable creation, investigation, and manipulation of unique collective features for a wide range of nanomaterials.

Optical and structural properties of Ag-Si3N4 nanocermets prepared by means of ion-beam sputtering in alternate and codeposition modes.

Ion-beam sputtering deposition has been used in two ways, as granular multilayers and as cosputtered film, to elaborate Ag-Si3N4 nanocermets. Multilayer deposition creates slightly oblate clusters, and cosputtering produces two cluster families: elongated clusters within the Si3N4 matrix and larger ones at the film surface. The transmittance spectra of these nanocermets are characterized by a surface plasmon resonance. In the reported research the position of this resonance is related to the morphological properties of silver nanoclusters, which are studied by transmission-electron microscopy, grazing-incidence small-angle x-ray scattering, and atomic-force microscopy.