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.

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.

Biomolecular Sensing at the Interface between Chiral Metasurfaces and Hyperbolic Metamaterials.

In recent times, biomolecular sensing to recognize genetic fragments and proteins is spurring unprecedented interest as a diagnostic protocol for cancer and infectious diseases. Significant efforts have been made to design nanomaterials able to control the light-matter interaction at the single nanometer scale, where genes and proteins bind specifically to receptors. Here, we numerically show how the interface between a chiral metasurface and hyperbolic metamaterials can enable both high sensitivity and specificity for low-molecular-weight nucleic acids and proteins. As we have recently reported, hyperbolic dispersion metamaterials allow molecular biorecognition with extreme sensitivity because of coupled and highly confined plasmon polaritons. Specificity is almost exclusively achieved by receptor-ligand interaction at the in-plane sensing surface. Interestingly, an adapted out-of-plane chiral metasurface enables three key functionalities of the hyperbolic metamaterial sensor. Computational effort reveals that helicoidal metasurfaces can act as (i) efficient diffractive elements to excite surface and bulk plasmon polaritons; (ii) out-of-plane sensing branches to reduce the diffusion limit and increase the sensing surface; and (iii) biorecognition assay also via circular dichroism and chiral selectivity.

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.

First observation of the quantized exciton-polariton field and effect of interactions on a single polariton.

Polaritons are quasi-particles that originate from the coupling of light with matter and that demonstrate quantum phenomena at the many-particle mesoscopic level, such as Bose-Einstein condensation and superfluidity. A highly sought and long-time missing feature of polaritons is a genuine quantum manifestation of their dynamics at the single-particle level. Although they are conceptually perceived as entangled states and theoretical proposals abound for an explicit manifestation of their single-particle properties, so far their behavior has remained fully accounted for by classical and mean-field theories. We report the first experimental demonstration of a genuinely quantum state of the microcavity polariton field, by swapping a photon for a polariton in a two-photon entangled state generated by parametric downconversion. When bringing this single-polariton quantum state in contact with a polariton condensate, we observe a disentangling with the external photon. This manifestation of a polariton quantum state involving a single quantum unlocks new possibilities for quantum information processing with interacting bosons.

Hybrid polymeric-protein nano-carriers (HPPNC) for targeted delivery of TGFß inhibitors to hepatocellular carcinoma cells.

TGFß1 pathway antagonists have been considered promising therapies to attenuate TGFß downstream signals in cancer cells. Inhibiting peptides, as P-17 in this study, are bound to either TGFß1 or its receptors, blocking signal transduction. However, for efficient use of these TGFß1antagonist as target therapeutic tools, improvement in their delivery is required. Here, a plasmid carrying specific shDNA (SHT-DNA), small interfering RNA (siRNA), and the peptide (P-17) were loaded separately into folic acid (FA)-functionalized nano-carriers made of Bovine Serum Albumin (BSA). The two building blocks of the carrier, (BSA and FA) were used because of the high affinity of albumin for liver and for the overexpression of folate receptors on the membrane of hepatocellular carcinoma cells. The empty and the encapsulated carriers were thoroughly investigated to characterize their structure, to evaluate the colloidal stability and the surface functionalization. The entrapment of SHT-DNA, siRNA and P-17, respectively, was demonstrated by morphological and quantitative analysis. Finally, cellular studies were performed to assess the targeting efficiency of the hybrid carriers. These vectors were used because of the high affinity of albumin for liver and for the overexpression of folate receptors on the membrane hepatocellular carcinoma cells. The empty and the encapsulated carriers were thoroughly investigated to characterize their structure, to evaluate the colloidal stability and the surface functionalization. The entrapment of SHT-DNA, siRNA and P-17, respectively, was demonstrated by morphological and quantitative analysis. A novel fabrication of Hybrid Polymeric-Protein Nano-Carriers (HPPNC) for delivering TGF ß1 inhibitors to HCC cells has been developed. SHT-DNA, siRNA and P-17 have been successfully encapsulated. TGF ß1 inhibitors-loaded HPPNC were efficiently uptaken by HLF cells.

Precise detection of circular dichroism in a cluster of nano-helices by photoacoustic measurements.

Compact samples of nano-helices built by means of a focused ion beam technology with large bandwidth and high dichroism for circular polarization are promising for the construction of built-in-chip sensors, where the ideal transducer must be sufficiently confined without compromising its filtering ability. Direct all-optical measurements revealed the sample's dichroic character with insufficient details because of scattering and diffraction interference. On the other hand, photoacoustic measurements resulted to be a possible alternative investigation, since they directly deal with absorbed power and allow to get clear evidences of the differential selection for the two opposite polarization states. Multi-level numerical simulations confirmed the experimental results, proving once again the reliability of photoacoustic technique and the versatility of this class of dichroic artificial materials.

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.

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.

Tuning of polarization sensitivity in closely stacked trilayer InAs/GaAs quantum dots induced by overgrowth dynamics.

Tailoring of electronic and optical properties of self-assembled InAs quantum dots (QDs) is a critical limit for the design of several QD-based optoelectronic devices operating in the telecom frequency range. We describe how fine control of the strain-induced surface kinetics during the growth of vertically stacked multiple layers of QDs allows for the engineering of their self-organization process. Most noticeably, this study shows that the underlying strain field induced along a QD stack can be modulated and controlled by time-dependent intermixing and segregation effects occurring after capping with a GaAs spacer. This leads to a drastic increase of the TM/TE polarization ratio of emitted light, not accessible from conventional growth parameters. Our detailed experimental measurements, supported by comprehensive multi-million atom simulations of strain, electronic and optical properties, provide in-depth analysis of the grown QD samples allowing us to give a clear picture of the atomic scale phenomena affecting the proposed growth dynamics and consequent QD polarization response.

The polarization response in InAs quantum dots: theoretical correlation between composition and electronic properties.

III-V growth and surface conditions strongly influence the physical structure and resulting optical properties of self-assembled quantum dots (QDs). Beyond the design of a desired active optical wavelength, the polarization response of QDs is of particular interest for optical communications and quantum information science. Previous theoretical studies based on a pure InAs QD model failed to reproduce experimentally observed polarization properties. In this work, multi-million atom simulations are performed in an effort to understand the correlation between chemical composition and polarization properties of QDs. A systematic analysis of QD structural parameters leads us to propose a two-layer composition model, mimicking In segregation and In-Ga intermixing effects. This model, consistent with mostly accepted compositional findings, allows us to accurately fit the experimental PL spectra. The detailed study of QD morphology parameters presented here serves as a tool for using growth dynamics to engineer the strain field inside and around the QD structures, allowing tuning of the polarization response.