Search

Recently, there has been significant interest in using dielectric nanocavities for the controlled scattering of light, owing to the diverse electromagnetic modes that they support. For plasmonic systems, electron energy-loss spectroscopy (EELS) is now an established method enabling structure–optical property analysis at the scale of the nanostructure. Here, we instead test its potential for the near-field mapping of photonic eigenmodes supported in planar dielectric nanocavities, which are lithographically patterned from amorphous silicon according to standard photonic principles. By correlating results with finite element simulations, we demonstrate how many of the EELS excitations can be directly corresponded to various optical eigenmodes of interest for photonic engineering. The EELS maps present a high spatial definition, displaying intensity features that correlate precisely to the impact parameters giving the highest probability of modal excitation. Further, eigenmode characteristics translate into their EELS signatures, such as the spatially and energetically extended signal of the low Q-factor electric dipole and nodal intensity patterns emerging from excitation of toroidal and second-order magnetic modes within the nanocavity volumes. Overall, the spatial–spectral nature of the data, combined with our experimental–simulation toolbox, enables interpretation of subtle changes in the EELS response across a range of nanocavity dimensions and forms, with certain simulated resonances matching the excitation energies within ±0.01 eV. By connecting results to far-field simulations, perspectives are offered for tailoring the nanophotonic resonances via manipulating nanocavity size and shape.

The growth of MoS2 layers of desired dimensions at predefined locations is essential for fabricating opto-electronic devices based solely on MoS2 or on hetero-structures based on MoS2. Here we present a new route for patterned growth of MoS2 by combining radio frequency (RF) magnetron sputtering, stencil mask lithography and vapour phase sulfurization. The present method does not involve chemical etchants and organic photoresist and hence provides a simplified process of achieving MoS2 patterns. Here, the control over the number of layers (mono, few and bulk) of MoS2 is achieved by varying the thickness of Mo films. The statistical variation in thickness i.e., number of MoS2 layers within the individual patterns is investigated from Raman mappings which revealed the uniform growth of 3-4 MoS2 layers. From Kelvin probe force microscopy, the surface potential values of MoS2 patterns lie in the range -350 to -370 mV, which is consistent with 2D MoS2 layer with thickness of 3-4 layers. The surface potential analysis across individual patterns indicates weakly n-type doping of few layers MoS2 with Fermi level located ~0.83-0.85 eV below the conduction band edge.

International audience; The plasma membrane of living cells is compartmentalized at multiple spatial scales ranging from the nano-to the meso-scale. This non-random organization is crucial for a large number of cellular functions. At the nanoscale, cell membranes organize into dynamic nano-assemblies enriched by cholesterol, sphingolipids and certain types of proteins. Investigating these nano-assemblies known as lipid rafts is of paramount interest in fundamental cell biology. However, this goal requires simultaneous nanometer spatial precision and microsecond temporal resolution which is beyond the reach of common microscopes. Optical antennas based on metallic nanostructures efficiently enhance and confine light into nanometer dimensions, breaching the diffraction limit of light. In this Perspective, we discuss recent progress combining optical antennas with fluorescence correlation spectroscopy (FCS) to monitor microsecond dynamics at nanoscale spatial dimensions. These new developments offer numerous opportunities to investigate lipid and protein dynamics in both mimetic and native biological membranes.

Nanoscale color printing has recently emerged as a unique alternative to traditional pigments by providing record spatial resolution, angular independent, durable and single material colors. Widely based on plasmonic nanostructures, numerous efforts in the field have aimed at extending color range and saturation relying on a variety of designs and metals. Alternatively, silicon nanostructures support finely tunable electric and magnetic multipolar resonances, afford low absorption losses and benefit from well-established industrial fabrication processes, all features ideally suited to nanoscale color printing. Here we compare the properties of silicon nanodiscs with those of aluminum and silver plasmonic elements for the specific purpose of nanoscale color reproduction targeting the coverage of a broad and vivid color palette. We highlight the different properties of such metallic and dielectric resonators in various geometric and illumination conditions leading to the optimization of silicon nanodisc arr...

Two superposed layers of transparent cylindrical lenslet gratings create classical moiré fringes, when illuminated from behind. We rely on this observation to conceive special devices made of superposed lenslet gratings that produce animated moirés when they are tilted against the light. One-dimensional moirés can show a message moving back and forth along a given direction or radially expanding towards the exterior of a disk. These 1D moirés are conceived by fabricating two layers of micro-lenses on both sides of a transparent substrate. The top layer is a rectilinear grating of cylindrical lenslets and the bottom layer is an arrangement of smaller lenslets of different sizes and orientations that create a high contrast. Moirés created by superpositions of lenslets are visually striking and can be challenging to fabricate. Therefore they have a high potential for art, decoration, and document security.

The spatiotemporal architecture of the cell membrane and diffusion dynamics of its constituents (lipids and proteins) are critical for many cellular processes such as signaling, trafficking and cell adhesions. Sub-diffraction photonics based on plasmonics offer new opportunities to follow such events as they can confine electric fields in nanoscale hotspots with spatial dimensions comparable to single molecules (∼5 nm).

Predetermined and selective placement of nanoparticles onto large-area substrates with nanometre-scale precision is essential to harness the unique properties of nanoparticle assemblies, in particular for functional optical and electro-optical nanodevices. Unfortunately, such high spatial organization is currently beyond the reach of top-down nanofabrication techniques alone. Here, we demonstrate that topographic features comprising lithographed funnelled traps and auxiliary sidewalls on a solid substrate can deterministically direct the capillary assembly of Au nanorods to attain simultaneous control of position, orientation and interparticle distance at the nanometre level. We report up to 100% assembly yield over centimetre-scale substrates. We achieve this by optimizing the three sequential stages of capillary nanoparticle assembly: insertion of nanorods into the traps, resilience against the receding suspension front and drying of the residual solvent. Finally, using electron energy-loss spectroscopy we characterize the spectral response and near-field properties of spatially programmable Au nanorod dimers, highlighting the opportunities for precise tunability of the plasmonic modes in larger assemblies.

This letter reports on a novel fabrication method for 3D metal nanostructures using high-throughput nanostencil lithography. Aperture clogging, which occurs on the stencil membranes during physical vapor deposition, is leveraged to create complex topographies on the nanoscale. The precision of the 3D nanofabrication method is studied in terms of geometric parameters and material types. The versatility of the technique is demonstrated by various symmetric and chiral patterns made of Al and Au.

Two superposed layers of transparent cylindrical lenslet gratings create classical moiré fringes when illuminated from behind. We rely on this observation to conceive special devices made of superposed lenslet gratings that produce compelling beating shapes when tilted against the light. Level-line moirés are created by superposing gratings of cylindrical lenslets of the same period on both sides of a substrate and by locally shifting some of the cylindrical lenses according to the moiré theory. Depending on the illumination and the viewing conditions, constant light intensities or colors move across graphical elements or faces. Such level-line moiré samples have been fabricated and characterized to determine the optimal fabrication parameters. Thanks to their striking visual appeal and their relatively challenging fabrication, moirés created by superposition of lenslets have a high potential for document security, art, and decoration.

We present a novel blurring-free stencil lithography patterning technique for high-throughput fabrication of large-scale arrays of nanoaperture optical antennas. The approach relies on dry etching through nanostencils to achieve reproducible and uniform control of nanoantenna geometries at the nanoscale, over millimeter-sizes in a thin aluminum film. We demonstrate the fabrication of over 400 000 bowtie nanoaperture (BNA) antennas on biocompatible substrates, having gap sizes ranging from (80 ± 5) nm down to (20 ± 10) nm. To validate their applicability on live cell research, we used the antenna substrates as hotspots of localized illumination to excite fluorescently labeled lipids on living cell membranes. The high signal-to-background afforded by the BNA arrays allowed the recording of single fluorescent bursts corresponding to the passage of freely diffusing individual lipids through hotspot excitation regions as small as 20 nm. Statistical analysis of burst length and intensity together with simulations demonstrate that the measured signals arise from the ultraconfined excitation region of the antennas. Because these inexpensive antenna arrays are fully biocompatible and amenable to their integration in most fluorescence microscopes, we foresee a large number of applications including the investigation of the plasma membrane of living cells with nanoscale resolution at endogenous expression levels.

Resolving the various interactions of lipids and proteins in the plasma membrane of living cells with high spatiotemporal resolution is of upmost interest [1]. Here we introduce an innovative design of plasmonic nanogap antennas to monitor single-molecule events on model biological membranes at physiological relevant concentrations by means of fluorescence correlation spectroscopy. Our design involves the fabrication of in-plane plasmonic nanogap antennas arrays embedded in nanometric-size boxes to provide full surface accessibility of the hotspot-confined region. Using these antennas we recently reported fluorescence enhancement factors of 104-105 times on individual molecules diffusing in solution, together with nanoscale detection volumes in the zeptoliter range [2]. In principle, the planarity of these antennas should enable similar studies on biological membranes without unwanted membrane curvature effects. To show their applicability, we recorded the diffusion of individual molecules inserted in multi-component lipid bilayers as a simple mimetic system that recapitulates some of the most important features of cell membranes. We prepared membranes of different compositions: saturated phospholipids, sphingolipids and cholesterol and used antennas of different gap sizes (10-45 nm). The diffusion of individual molecules on membranes consisting of phospholipids and/or in a mixture with sphingolipids resulted Brownian, confirming homogenous lipid distribution. Interestingly, the strong confinement of antennas revealed the formation of transient (

Optical nanoantennas can efficiently confine light into nanoscopic hotspots, enabling single-molecule detection sensitivity at biological relevant conditions. This innovative approach to breach the diffraction limit offers a versatile platform to investigate the dynamics of individual biomolecules in living cell membranes and their partitioning into cholesterol-dependent lipid nanodomains. Here, we present optical nanoantenna arrays with accessible surface hotspots to study the characteristic diffusion dynamics of phosphoethanolamine (PE) and sphingomyelin (SM) in the plasma membrane of living cells at the nanoscale. Fluorescence burst analysis and fluorescence correlation spectroscopy performed on nanoantennas of different gap sizes show that, unlike PE, SM is transiently trapped in cholesterol-enriched nanodomains of 10 nm diameter with short characteristic times around 100 μs. The removal of cholesterol led to the free diffusion of SM, consistent with the dispersion of nanodomains. Our results are consistent with the existence of highly transient and fluctuating nanoscale assemblies enriched by cholesterol and sphingolipids in living cell membranes, also known as lipid rafts. Quantitative data on sphingolipids partitioning into lipid rafts is crucial to understand the spatiotemporal heterogeneous organization of transient molecular complexes on the membrane of living cells at the nanoscale. The proposed technique is fully biocompatible and thus provides various opportunities for biophysics and live cell research to reveal details that remain hidden in confocal diffraction-limited measurements.

To grow small molecule semiconductor thin films with domain size larger than modern-day device sizes, we evaporate the material through a dense array of small apertures, called a stencil nanosieve. The aperture size of 0.5 μm results in low nucleation density, whereas the aperture-to-aperture distance of 0.5 μm provides sufficient crosstalk between neighboring apertures through the diffusion of adsorbed molecules. By integrating the nanosieve in the channel area of a thin-film transistor mask, we show a route for patterning both the organic semiconductor and the metal contacts of thin-film transistors using one mask only and without mask realignment. ispartof: ACS Applied Materials and Interfaces vol:9 issue:28 pages:23314-23318 ispartof: location:United States status: published

Second harmonic generation (SHG) is an important tool for the study of plasmonic nanostructures and can open up important sensing applications since the second harmonic (SH) signal has an increased sensitivity to nanostructures shape and environment in comparison with the linear scattering [1,2]. SHG from plasmonic centrosymmetric nanostructures is controlled by two main properties. First, SHG is forbidden in the bulk of centrosymmetric structures in the dipolar approximation, meaning that nanostructures made of metals like gold and silver generate a SH signal coming mainly from their surfaces, where the symmetry is effectively broken. Second, because of the same symmetry reason, a dipolar excitation at the fundamental frequency induces SH modes with vanishing dipole moments [3]. In the case of plasmonic dimers, with the large intensity enhancement occurring in the gap, the SH emission is limited due to out-of-phase SH sources with destructive interferences in the far-field region. Consequently, new strategies must be developed to overcome this limitation.

While plasmonic antennas composed of building blocks made of the same material have been thoroughly studied, recent investigations have highlighted the unique opportunities enabled by making compositionally asymmetric plasmonic systems. So far, mainly heterostructures composed of nanospheres and nanodiscs have been investigated, revealing opportunities for the design of Fano resonant nanostructures, directional scattering, sensing and catalytic applications. In this article, an improved fabrication method is reported that enables precise tuning of the heterodimer geometry, with interparticle distances made down to a few nanometers between Au–Ag and Au–Al nanoparticles. A wide range of mode energy detuning and coupling conditions are observed by near field hyperspectral imaging performed with electron energy loss spectroscopy, supported by full wave analysis numerical simulations. These results provide direct insights into the mode hybridization of plasmonic heterodimers, pointing out the influence of each dimer constituent in the overall electromagnetic response. By relating the coupling of nondipolar modes and plasmon–interband interaction with the dimer geometry, this work facilitates the development of plasmonic heterostructures with tailored responses, beyond the possibilities offered by homodimers.

Optical nanoantennas have a great potential for enhancing light-matter interactions at the nanometer scale, yet fabrication accuracy and lack of scalability currently limit ultimate antenna performance and applications. In most designs, the region of maximum field localization and enhancement (i.e., hotspot) is not readily accessible to the sample since it is buried into the nanostructure. Moreover, current large-scale fabrication techniques lack reproducible geometrical control below 20 nm. Here, we describe a new nanofabrication technique that applies planarization, etch back and template stripping to expose the excitation hotspot at the surface, providing a major improvement over conventional electron beam lithography methods. We present large flat surface arrays of in-plane nanoantennas, featuring gaps as small as 10 nm with sharp edges, excellent reproducibility and full surface accessibility of the hotspot confined region. The novel fabrication approach drastically improves the optical performance of plasmonic nanoantennas to yield giant fluorescence enhancement factors up to 104-105 times, together with nanoscale detection volumes in the 20 zeptoliter range. The method is fully scalable and adaptable to a wide range of antenna designs. We foresee broad applications by the use of these in-plane antenna geometries ranging from large-scale ultra-sensitive sensor chips, to microfluidics and live cell membrane investigations.

Nanoscale membrane assemblies of sphingolipids, cholesterol, and certain proteins, also known as lipid rafts, play a crucial role in facilitating a broad range of important cell functions. Whereas on living cell membranes lipid rafts have been postulated to have nanoscopic dimensions and to be highly transient, the existence of a similar type of dynamic nanodomains in multicomponent lipid bilayers has been questioned. Here, we perform fluorescence correlation spectroscopy on planar plasmonic antenna arrays with different nanogap sizes to assess the dynamic nanoscale organization of mimetic biological membranes. Our approach takes advantage of the highly enhanced and confined excitation light provided by the nanoantennas together with their outstanding planarity to investigate membrane regions as small as 10 nm in size with microsecond time resolution. Our diffusion data are consistent with the coexistence of transient nanoscopic domains in both the liquid-ordered and the liquid-disordered microscopic phases of multicomponent lipid bilayers. These nanodomains have characteristic residence times between 30 and 150 μs and sizes around 10 nm, as inferred from the diffusion data. Thus, although microscale phase separation occurs on mimetic membranes, nanoscopic domains also coexist, suggesting that these transient assemblies might be similar to those occurring in living cells, which in the absence of raft-stabilizing proteins are poised to be short-lived. Importantly, our work underscores the high potential of photonic nanoantennas to interrogate the nanoscale heterogeneity of native biological membranes with ultrahigh spatiotemporal resolution.

Reference EPFL-ARTICLE-186993doi:10.1002/adom.201200017View record in Web of Science Record created on 2013-06-11, modified on 2017-05-10

Electron energy-loss spectroscopy (EELS) has become an experimental method of choice for the investigation of localized surface plasmon resonances, allowing the simultaneous mapping of the associated field distributions and their resonant energies with a nanoscale spatial resolution. The experimental observations have been well-supported by numerical models based on the computation of the Lorentz force acting on the impinging electrons by the scattered field. However, in this framework, the influence of the intrinsic properties of the plasmonic nanostructures studied with the electron energy-loss (EEL) measurements is somehow hidden in the global response. To overcome this limitation, we propose to go beyond this standard, and well-established, electron perspective and instead to interpret the EELS data using directly the intrinsic properties of the nanostructures, without regard to the force acting on the electron. The proposed method is particularly well-suited for the description of coupled plasmonic systems, because the role played by each individual nanoparticle in the observed EEL spectrum can be clearly disentangled, enabling a more subtle understanding of the underlying physical processes. As examples, we consider different plasmonic geometries in order to emphasize the benefits of this new conceptual approach for interpreting experimental EELS data. In particular, we use it to describe results from samples made by traditional thin film patterning and by arranging colloidal nanostructures.

Photocharge generation and formation of long-lived charge carriers are relevant in photosynthesis, photocatalysis, photovoltaics, and organic electronics. A better understanding of the factors that determine these processes in synthetic polymer semiconductors is crucial, but difficult due to their morphological inhomogeneity. Here, we report the formation of exceptionally long-lived photocharges in one-dimensional organic semiconductor nanostructures. These nanostructures consist of chiral oligopeptide-substituted thienothiophene-based chromophores and exhibit a well-defined helical arrangement of these chromophores at their core. The chromophores give rise to spectroscopic H-aggregates and show strong intermolecular excitonic coupling. We demonstrate that all of these parameters are the prerequisites required for the nanostructures to show the efficient formation of polaron-like photocharges upon irradiation with a low-power white light source. The observed charge carriers in the helical nanowires show an unusually long lifetime on the order of several hours and are formed at high concentrations of up to 3 mol % in the absence of any dedicated electron acceptor. They are observed in solution as well as in film and furthermore give rise to a light-induced increase of the macroscopic charge transport. By contrast, no such photocharge generation is observed either in non-aggregating reference systems of the same chromophores or in aggregated but non-helical systems that do not form one-dimensional nanostructures. Our results thus demonstrate a clear correlation between nanoscopic confinement and the generation of long-lived photocharges.

Plasmonic antennas have enabled a wealth of applications that exploit tailored near-fields and radiative properties, further endowed by the bespoke interactions of multiple resonant building blocks. Specifically, when the interparticle distances are reduced to a few nanometers, coupling may be greatly enhanced leading to ultimate near-field intensities and confinement along with a large energy splitting of resonant modes. While this concept is well-known, the fabrication and characterization of suitable multimers with controlled geometries and few-nanometer gaps remains highly challenging. In this article, we present the topographically templated assembly of single-crystal colloidal gold nanorods into trimers, with a dolmen geometry. This fabrication method enables the precise positioning of high-quality nanorods, with gaps as small as 1.5 nm, which permits a gradual and controlled symmetry breaking by tuning the arrangement of these strongly coupled nanostructures. To characterize the fabricated structures, we perform electron energy loss spectroscopy (EELS) near-field hyperspectral imaging and geometrically accurate EELS, plane wave, and eigenmode full-wave computations to reveal the principles governing the electromagnetic response of such nanostructures that have been extensively studied under plane wave excitation for their Fano resonant properties. These experiments track the evolution of the multipolar interactions with high accuracy as the antenna geometry varies. Our results provide new insights in strongly coupled single-crystal building blocks and open news opportunities for the design and fabrication of plasmonic systems.

Electron energy loss spectroscopy is a method of choice for the characterization of both the spatial and spectral properties of localized surface plasmon resonances. The energy lost by the impinging electrons is commonly explained by the Lorentz force acting on their motion. Here, we adopt another point of view to compute the electron energy loss spectra. Coupling the energy conservation law with full-wave electromagnetic computations based on a surface integral equation method, we derive the electron energy loss spectra directly from two dissipative processes, namely, absorption and scattering. This antenna-based approach is applied to nanostructures with different sizes and materials, showing an excellent agreement with experimental observation and computations based on the evaluation of the Lorentz force. This formalism permits the easy separation of absorption losses in the nanostructures forming a coupled system and reveals the subtle interplay between absorption and scattering, which are controlled by the materials, the nanostructure size, and the energy range.

In order to realize high-performance organic thin-film transistors (TFT), two parameters of the organic semiconducting layer are desired: single crystallinity for high mobility, and patterning for low off currents. High-quality single crystals can be fabricated using vapor techniques such as physical vapor transport (PVT) but they require high temperatures close to thermodynamic equilibrium, for example, 240°C for pentacene. Such high temperatures are not ideal for TFT fabrication on plastic substrates and limit the use of PVT in flexible electronics applications. In this work arrays of pentacene single crystals were directly deposited at low temperature of 40°C by vacuum thermal evaporation through micro-fabricated stencil masks (stencil lithography). By decreasing the stencil aperture size down to 1 µm x 1 µm, we were able to limit the nucleation area until only one grain per aperture is nucleated and grown. We studied systematically scaling effects for large singe crystal growth and discuss details of the growth morphology. We found for instance that the formed pentacene crystals are one monolayer thick and the crystal area is much larger than the aperture size. This can be explained by the diffusion of adsorbed molecules on the surface laterally under the shadow mask, where they are protected from other impinging molecules The diffusion away from the impinging area under the aperture affects the nucleation density inside this area and was used to calculate the diffusion length to nucleation λN = 0.66 ± 0.11 µm of pentacene on SiO2 at 40°C. Our diffusion-driven growth of organic single crystals by stencil lithography is a direct method to grow patterned arrays of single crystalline organic thin-film semiconductor layers. ispartof: Crystal Growth & Design vol:16 issue:8 pages:4694-4700 status: published