Molybdenum precursor delivery approaches in atomic layer deposition of α-MoO3.

In this research work, we present a study on time-sequenced plasma-enhanced atomic layer deposition (PE-ALD) processes towards the achievement of high-quality α-MoO3 thin films which are suitable for exfoliation. In particular, a conventional precursor injection method along with a boosted precursor delivery approach are discussed and analysed. In the latter, the proposed gas supply mechanism ensures a large number of deposited Mo atoms per unit of time, which, along with a proper thermal energy, leads to high-quality and oriented orthorhombic α-MoO3 films. The proposed boosted approach is also compared with post growth annealing steps, resulting in more effective achievement of a highly oriented orthorhombic α-MoO3 phase and less time consumption.

Surface Lattice Resonances in 3D Chiral Metacrystals for Plasmonic Sensing.

Chiral lattice modes are hybrid states arising from the chiral plasmonic particles assembled in ordered arrays with opportune periodicity. These resonances exhibit dependence on excitation handedness, and their observation in plasmonic lattices is strictly related to the chiroptical features of the fundamental plasmonic unit. Here, the emergence of chiral surface lattice resonances (c-SLRs) is shown in properly engineered arrays of nanohelices (NHs), fully three dimensional (3D) chiral nano-objects fabricated by focused ion beam processing. By tuning the relative weight of plasmonic and photonic components in the hybrid mode, the physical mechanism of strong diffractive coupling leading to the emergence of the lattice modes is analyzed, opening the way to the engineering of chiral plasmonic systems for sensing applications. In particular, a coupling regime is identified where the combination of a large intrinsic circular dichroism (CD) of the plasmonic resonance with a well-defined balance between the photonic quality factor (Q factor) and the plasmonic field enhancement (M) maximizes the capability of the system to discriminate refractive index (RI) changes in the surrounding medium. The results lay the foundation for exploiting CD in plasmonic lattices to high performance refractometric sensing.

Two-Channel Indirect-Gap Photoluminescence and Competition between the Conduction Band Valleys in Few-Layer MoS2.

MoS2 is a two-dimensional layered transition metal dichalcogenide with unique electronic and optical properties. The fabrication of ultrathin MoS2 is vitally important, since interlayer interactions in its ultrathin varieties will become thickness-dependent, providing thickness-governed tunability and diverse applications of those properties. Unlike with a number of studies that have reported detailed information on direct bandgap emission from MoS2 monolayers, reliable experimental evidence for thickness-induced evolution or transformation of the indirect bandgap remains scarce. Here, the sulfurization of MoO3 thin films with nominal thicknesses of 30 nm, 5 nm and 3 nm was performed. All sulfurized samples were examined at room temperature with spectroscopic ellipsometry and photoluminescence spectroscopy to obtain information about their dielectric function and edge emission spectra. This investigation unveiled an indirect-to-indirect crossover between the transitions, associated with two different Λ and K valleys of the MoS2 conduction band, by thinning its thickness down to a few layers.

Potential of CO2-laser processing of quartz for fast prototyping of microfluidic reactors and templates for 3D cell assembly over large scale.

Carbon dioxide (CO2)-laser processing of glasses is a versatile maskless writing technique to engrave micro-structures with flexible control on shape and size. In this study, we present the fabrication of hundreds of microns quartz micro-channels and micro-holes by pulsed CO2-laser ablation with a focus on the great potential of the technique in microfluidics and biomedical applications. After discussing the impact of the laser processing parameters on the design process, we illustrate specific applications. First, we demonstrate the use of a serpentine microfluidic reactor prepared by combining CO2-laser ablation and post-ablation wet etching to remove surface features stemming from laser-texturing that are undesirable for channel sealing. Then, cyclic olefin copolymer micro-pillars are fabricated using laser-processed micro-holes as molds with high detail replication. The hundreds of microns conical and square pyramidal shaped pillars are used as templates to drive 3D cell assembly. Human Umbilical Vein Endothelial Cells are found to assemble in a compact and wrapping way around the micro-pillars forming a tight junction network. These applications are interesting for both Lab-on-a-Chip and Organ-on-a-Chip devices.

Gallium chiral nanoshaping for circular polarization handling.

In this work we report the local growth of ordered arrays of 3D core-shell chiral nanohelices based on plasmonic gallium metal. The structures can be engineered in a single step using focused ion beam induced deposition, where a Ga+ ion source is used to shape the metallic nanohelix core, while the dielectric precursor is dissociated to create dielectric shells. The solubility of gallium in the different investigated dielectric matrices controls the core-shell thickness ratio of the nanohelices. The chiral plasmonic behaviour of these gallium-based nanostructures is experimentally measured by circularly polarized light transmission through nanostructure arrays and compared with numerical simulations. Large chiroptical effects in the visible range are demonstrated due to the plasmonic effects arising from gallium nanoclusters in the core.

Femtomolar Biodetection by a Compact Core-Shell 3D Chiral Metamaterial.

Advanced sensing tools, detecting extremely low concentrations of circulating biomarkers, can open unexplored routes toward early diagnostics and diseases progression monitoring. Here, we demonstrate the sensing capabilities of a chip-based metamaterial, combining 3D chiral geometry with a functional core-shell nanoarchitecture. The chiral metamaterial provides a circular polarization-dependent optical response, allowing analysis in a complex environment without significant background interferences. The functional nanoarchitecture, based on the conformal coating with a polymer shell, modifies the chiral metamaterial near- and far-field optical response because of the energy transfer between dielectric shell polarization charges and plasmonic core free electrons, leading to efficient interaction with biomolecules. The system sensitivity slope is 27 nm/pM, in the detection of TAR DNA-binding protein 43, clinically relevant for neurodegenerative diseases. Measurements were performed in spiked solution and in human serum with concentrations from 1 pM down to 10 fM, which is a range not accessible with common immunological assays, opening new perspectives for next-generation biomedical systems.

Near-field enhancement in oxidized close gap aluminum dimers.

Aluminum bowtie nanoantennas represent a possibility to confine and enhance electromagnetic (EM) field at optical frequencies in subwavelength regions by using an abundant and inexpensive metal. The native oxidation process of this metal is often viewed as a limitation for its application in plasmonics. Here, we show that in close gap configurations, the high refractive index of the native aluminum oxide helps in squeezing the plasmonic mode in extremely reduced size volumes, providing a higher EM near-field confinement and enhancement in the bowtie antenna gaps than achieved in the pure aluminum counterpart. Hence, the study provides new perspectives in the use of such a plasmonic antenna geometry within this aluminum system, which can be useful for improving plasmonics-enabled effects such as surface-enhanced Raman scattering- and light-matter interaction in strong coupling regime.

Focused Ion Beam Processing for 3D Chiral Photonics Nanostructures.

The focused ion beam (FIB) is a powerful piece of technology which has enabled scientific and technological advances in the realization and study of micro- and nano-systems in many research areas, such as nanotechnology, material science, and the microelectronic industry. Recently, its applications have been extended to the photonics field, owing to the possibility of developing systems with complex shapes, including 3D chiral shapes. Indeed, micro-/nano-structured elements with precise geometrical features at the nanoscale can be realized by FIB processing, with sizes that can be tailored in order to tune optical responses over a broad spectral region. In this review, we give an overview of recent efforts in this field which have involved FIB processing as a nanofabrication tool for photonics applications. In particular, we focus on FIB-induced deposition and FIB milling, employed to build 3D nanostructures and metasurfaces exhibiting intrinsic chirality. We describe the fabrication strategies present in the literature and the chiro-optical behavior of the developed structures. The achieved results pave the way for the creation of novel and advanced nanophotonic devices for many fields of application, ranging from polarization control to integration in photonic circuits to subwavelength imaging.

Symmetry Breaking in Oligomer Surface Plasmon Lattice Resonances.

We describe a novel plasmonic-mode engineering, enabled by the structural symmetry of a plasmonic crystal with a metallic oligomer as unit cell. We show how the oligomer symmetry can tailor the scattering directions to spatially overlap with the diffractive orders directions of a plasmonic array. Applied to the color generation field, the presented approach enables the challenging achievement of a broad spectrum of angle-dependent colors since smooth and continuous generation of transmitted vibrant colors, covering both the cyan-magenta-yellow and the red-green-blue color spaces, is demonstrated by scattering angle- and polarization-dependent optical response. The addition of a symmetry driven level of control multiplies the possibility of optical information storage, being of potential interest for secured optical information encoding but also for nanophotonic applications, from demultiplexers or signal processing devices to on-chip optical nanocircuitry.

Toward Cavity Quantum Electrodynamics with Hybrid Photon Gap-Plasmon States.

Combining localized surface plasmons (LSPs) and diffractive surface waves (DSWs) in metallic nanoparticle gratings leads to the emergence of collective hybrid plasmonic-photonic modes known as surface lattice resonances (SLRs). These show reduced losses and therefore a higher Q factor with respect to pure LSPs, at the price of larger volumes. Thus, they can constitute a flexible and efficient platform for light-matter interaction. However, it remains an open question if there is, in terms of the Q/V ratio, a sizable gain with respect to the uncoupled LSPs or DSWs. This is a fundamental point to shed light upon if such modes want to be exploited, for instance, for cavity quantum electrodynamic effects. Here, using aluminum nanoparticle square gratings with unit cells consisting of narrow-gap disk dimers-a geometry featuring a very small modal volume-we demonstrate that an enhancement of the Q/V ratio with respect to the pure LSP and DSW is obtained for SLRs with a well-defined degree of plasmon hybridization. Simultaneously, we report a 5× increase of the Q/V ratio for the gap-coupled LSP with respect to that of the single nanoparticle. These outcomes are experimentally probed against the Rabi splitting, resulting from the coupling between the SLR and a J-aggregated molecular dye, showing an increase of 80% with respect to the DSW-like SLR sustained by the disk LSP of the dimer. The results of this work open the way toward more efficient applications for the exploitation of excitonic nonlinearities in hybrid plasmonic platforms.

Programmable Extreme Chirality in the Visible by Helix-Shaped Metamaterial Platform.

The capability to fully control the chiro-optical properties of metamaterials in the visible range enables a number of applications from integrated photonics to life science. To achieve this goal, a simultaneous control over complex spatial and localized structuring as well as material composition at the nanoscale is required. Here, we demonstrate how circular dichroic bands and optical rotation can be effectively and independently tailored throughout the visible regime as a function of the fundamental meta-atoms properties and of their three dimensional architecture in a the helix-shaped metamaterials. The record chiro-optical effects obtained in the visible range are accompanied by an additional control over optical efficiency, even in the plasmonic context. These achievements pave the way toward fully integrated chiral photonic devices.

Exploiting Photo- and Electroluminescence Properties of FIrpic Organic Crystals.

In this work, we investigate the optical and structural properties of the well-known triplet emitter bis(4',6'-difluorophenylpyridinato)-iridium(III) picolinate (FIrpic), showing that its ability to pack in two different ordered crystal structures promotes attractive photophysical properties that are useful for solid-state lighting applications. This approach allows the detrimental effects of the nonradiative pathways on the luminescence performance in highly concentrated organic active materials to be weakened. The remarkable electro-optical behavior of sky-blue phosphorescent organic light-emitting diodes incorporating crystal domains of FIrpic, dispersed into an appropriate matrix as an active layer, has also been reported as well as the X-ray diffraction, nuclear magnetic resonance, electro-ionization mass spectrometry, and scanning electron microscopy analyses of the crystalline samples. We consider this result as a crucial starting point for further research aimed at the use of a crystal triplet emitter in optoelectronic devices to overcome the long-standing issue of luminescence self-quenching.

Tailoring chiro-optical effects by helical nanowire arrangement.

In this work, we experimentally investigate the chiro-optical properties of 3D metallic helical systems at optical frequencies. Both single and triple-nanowire geometries have been studied. In particular, we found that in single-helical nanostructures, the enhancement of chiro-optical effects achievable by geometrical design is limited, especially with respect to the operation wavelength and the circular polarization conversion purity. Conversely, in the triple-helical nanowire configuration, the dominant interaction is the coupling among the intertwined coaxial helices which is driven by a symmetric spatial arrangement. Consequently, a general improvement in the g-factor, extinction ratio and signal-to-noise-ratio is achieved in a broad spectral range. Moreover, while in single-helical nanowires a mixed linear and circular birefringence results in an optical activity strongly dependent on the sample orientation and wavelength, in the triple-helical nanowire configuration, the obtained purely circular birefringence leads to a large optical activity up to 8°, independent of the sample angle, and extending in a broad band of 500 nm in the visible range. These results demonstrate a strong correlation between the configurational internal interactions and the chiral feature designation, which can be effectively exploited for nanoscale chiral device engineering.

Exciton-Plasmon Coupling Enhancement via Metal Oxidation.

In this paper, we report on the effect of metal oxidation on strong coupling interactions between silver nanostructures and a J-aggregated cyanine dye. We show that metal oxidation can sensibly affect the plexcitonic system, inducing a change in the coupling strength. In particular, we demonstrate that the presence of oxide prevents the appearance of Rabi splitting in the extinction spectra for thick spacers. In contrast, below a threshold percentage, the oxide layer results in an higher coupling strength between the plasmon and the Frenkel exciton. Contrary to common belief, a thin oxide layer seems thus to act, under certain conditions, as a coupling mediator between an emitter and a localized surface plasmon excited in a metallic nanostructure. This suggests that metal oxidation can be exploited as a means to enhance light-matter interactions in strong coupling applications.

Triple-helical nanowires by tomographic rotatory growth for chiral photonics.

Three dimensional helical chiral metamaterials resulted in effective manipulation of circularly polarized light in the visible infrared for advanced nanophotonics. Their potentialities are severely limited by the lack of full rotational symmetry preventing broadband operation, high signal-to-noise ratio and inducing high optical activity sensitivity to structure orientation. Complex intertwined three dimensional structures such as multiple-helical nanowires could overcome these limitations, allowing the achievement of several chiro-optical effects combining chirality and isotropy. Here we report three dimensional triple-helical nanowires, engineered by the innovative tomographic rotatory growth, on the basis of focused ion beam-induced deposition. These three dimensional nanostructures show up to 37% of circular dichroism in a broad range (500-1,000 nm), with a high signal-to-noise ratio (up to 24 dB). Optical activity of up to 8° only due to the circular birefringence is also shown, tracing the way towards chiral photonic devices that can be integrated in optical nanocircuits to modulate the visible light polarization.

Silicon nanotubes from sacrificial silicon nanowires: fabrication and manipulation via embedding in flexible polymers.

In the present work we report a simple method to fabricate Si nanotubes (NTs) starting from the growth of self-assembled sacrificial Si nanowires that, at the same time, embeds them into a polyimide matrix, allowing a very easy manipulation of these nano-objects, including removal, transfer and positioning. Our all-silicon fabrication method is completely compatible with the Si technology platform and is therefore implementable using the existing technology. Transferred NTs show good electrical contact with underlying electrodes, and relatively low resistance values have been measured. All these features demonstrate the effectiveness of the transfer method and the potentiality of the NTs in electronics. Finally, optical reflectivity of the NTs has been measured in the near UV-near IR spectral range.

Optical reflectivity from highly disordered Si nanowire films.

In this work we present a study of the reflectivity from highly disordered silicon nanowire films as a function of the wire size. Arrays of Au-catalyzed Si wires with length and diameter ranging from 0.15-0.2 microm and 30-50 nm up to 20-25 microm and 200-250 nm, respectively, were grown on top of either SiO(2)(1 microm)/Si(100) or Si(100) substrates. The integrated total reflection was measured in the 190-2500 nm spectral range. The results show that, increasing the wire size, the optical behavior of the Si wire film can be gradually tuned from that of an optical coating characterized by a graded effective refractive index to that of an ensemble of diffuse optical reflectors. In addition, we show how the optical analysis provides some important indications concerning the structural properties of the nanowires.

Low-temperature, self-catalyzed growth of Si nanowires.

High densities of self-catalyzed Si nanowires have been grown at temperatures down to 320 degrees C on different Si substrates, whose surfaces have been roughened by simple physical or chemical treatments. The particular substrates are Si(110) cleavage planes, chemically etched Si(111) surfaces and microcrystalline Si obtained by laser annealing thin amorphous Si layers. The NW morphology depends on the growth surface. Transmission electron microscopy indicates that the NWs are made of pure Si with a crystalline core structure. Reflectivity measurements confirm this latter finding.