Valentina Robbiano

Fluorescent polystyrene photonic crystals self-assembled with water-soluble conjugated polyrotaxanes

We demonstrate control of the photoluminescence spectra and decay rates of water-soluble green-emitting conjugated polyrotaxanes by incorporating them in polystyrene opals with a stop-band spectrally tuned on the rotaxane emission (405–650 nm). We observe a suppression of the luminescence within the photonic stop-band and a corresponding enhancement of the high-energy edge (405–447 nm). Time-resolved measurements reveal a wavelength-dependent modification of the emission lifetime, which is shortened at the high-energy edge (by ∼11%, in the range 405–447 nm), but elongated within the stop-band (by ∼13%, in the range 448–482 nm). We assign both effects to the modification of the density of photonic states induced by the photonic crystal band structure. We propose the growth of fluorescent composite photonic crystals from blends of “solvent-compatible” non-covalently bonded nanosphere-polymer systems as a general method for achieving a uniform distribution of polymeric dopants in three-dimensional self-assem...

Measurement of the circular dichroism in the second harmonic optical signal produced by Au covered self ordered dielectric nanospheres

Here we present the measurements of the second harmonic generation (SHG) signal raised by self ordered dielectric nanospheres partially covered by thin (10nm) Au layer. The measurement were performed by studying the SHG efficiency in different polarization states of the light. In particular measurement performed with circular polarized light show the presence of chiral response of the nanospheres that is induced by the particular geometry of the metasurface.

Flexible Polydimethylsiloxane Foams Decorated with Multiwalled Carbon Nanotubes Enable Unprecedented Detection of Ultralow Strain and Pressure Coupled with a Large Working Range

Low-cost piezoresistive strain/pressure sensors with large working range, at the same time able to reliably detect ultralow strain (≤0.1%) and pressure (≤1 Pa), are one of the challenges that have still to be overcome for flexible piezoresistive materials toward personalized health-monitoring applications. In this work, we report on unprecedented, simultaneous detection of ultrasmall strain (0.1%, i.e., 10 μm displacement over 10 mm) and subtle pressure (20 Pa, i.e., a force of only 2 mN over an area of 1 cm2) in compression mode, coupled with a large working range (i.e., up to 60% for strain-6 mm in displacement-and 50 kPa for pressure) using piezoresistive, flexible three-dimensional (3D) macroporous polydimethylsiloxane (pPDMS) foams decorated with pristine multiwalled carbon nanotubes (CNTs). pPDMS/CNT foams with pore size up to 500 μm (i.e., twice the size of those of commonly used foams, at least) and porosity of 77%, decorated with a nanostructured surface network of CNTs at densities ranging from 7.5 to 37 mg/cm3 are prepared using a low-cost and scalable process, through replica molding of sacrificial sugar templates and subsequent drop-casting of CNT ink. A thorough characterization shows that piezoresistive properties of the foams can be finely tuned by controlling the CNT density and reach an optimum at a CNT density of 25 mg/cm3, for which a maximum change of the material resistivity (e.g., ρ0/ρ50 = 4 at 50% strain) is achieved under compression. Further static and dynamic characterization of the pPDMS/CNT foams with 25 mg/cm3 of CNTs highlights that detection limits for strain and pressure are 0.03% (3 μm displacement over 10 mm) and 6 Pa (0.6 mN over an area of 1 cm2), respectively; moreover, good stability and limited hysteresis are apparent by cycling the foams with 255 compression-release cycles over the strain range of 0-60%, at different strain rates up to 10 mm/min. Our results on piezoresistive, flexible pPDMS/CNT foams pave the way toward breakthrough applications for personalized health care, though not limited to these, which have not been fully addressed to date with flexible strain/stress sensors.

Ionic Strength Responsive Sulfonated Polystyrene Opals

Stimuli-responsive photonic crystals (PCs) represent an intriguing class of smart materials very promising for sensing applications. Here, selective ionic strength responsive polymeric PCs are reported. They are easily fabricated by partial sulfonation of polystyrene opals, without using toxic or expensive monomers and etching steps. The color of the resulting hydrogel-like ordered structures can be continuously shifted over the entire visible range (405-760 nm) by changing the content of ions over an extremely wide range of concentration (from about 70 μM to 4 M). The optical response is completely independent from pH and temperature, and the initial color can be fully recovered by washing the sulfonated opals with pure water. These new smart photonic materials could find important applications as ionic strength sensors for environmental monitoring as well as for healthcare screening.

Experimental and Computational Study on the Temperature Behavior of CNT Networks

We report on the electrical properties of carbon nanotubes (CNT) networks deposited using spray deposition onto interdigitated gold structures. The properties have been measured experimentally and analyzed using a computational method. In particular we studied the variation of resistance as function of the temperature in networks having different nanotubes density. We found a good agreement between the simulation and the experimentally obtained results for the networks with higher densities. Our results suggest that the change in the temperature behavior is due to the desorption of oxygen molecules at relatively high temperature. This effect is found to be function of the network density. To have a better insight on the conduction properties of the networks we also model the voltage drop and the current flows across the networks and these results have been found in good agreement with experimental one reported in literature.

Hybrid-organic photonic structures for light emission modification

We report the modification of the photoluminescence (PL) and decay rates of two different green-emitting conjugated polymers incorporated into photonic crystals with the stop-bands spectrally tuned on their emission. We observe both suppression (in the stop-band) and enhancement (at the high-energy band-edge) of the photoluminescence. Time-resolved measurements also reveal a concomitant modification of the emission lifetime that is enhanced at the band-edge and suppressed within the stop-band, thus confirming a variation of the radiative decay rate of the excitations in such photonic nanostructures. We propose two examples of fluorescent photonic composite systems. The first consists of a hybrid Si-organic system, obtained by infiltration of the polymer inside a rugate filter (a 1D photonic crystal). The second example is a fully organic system obtained by self-assembling of solvent-compatible microspheres-polymer system for obtaining a synthetic opal (a 3D photonic crystal) with a uniform distribution of the emitting material across the photonic structure.

Room-Temperature Low-Threshold Lasing From Monolithically Integrated Nanostructured Porous Silicon Hybrid Microcavities

Silicon photonics would strongly benefit from monolithically integrated low-threshold silicon-based laser operating at room temperature, representing today the main challenge toward low-cost and power-efficient electronic–photonic integrated circuits. Here we demonstrate low-threshold lasing from fully transparent nanostructured porous silicon (PSi) monolithic microcavities (MCs) infiltrated with a polyfluorene derivative, namely, poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO). The PFO-infiltrated PSiMCs support single-mode blue lasing at the resonance wavelength of 466 nm, with a line width of ∼1.3 nm and lasing threshold of 5 nJ (15 μJ/cm2), a value that is at the state of the art of PFO lasers. Furthermore, time-resolved photoluminescence shows a significant shortening (∼57%) of PFO emission lifetime in the PSiMCs, with respect to nonresonant PSi reference structures, confirming a dramatic variation of the radiative decay rate due to a Purcell effect. Our results, given also that blue lasing is a worst case for silicon photonics, are highly appealing for the development of low-cost, low-threshold silicon-based lasers with wavelengths tunable from visible to the near-infrared region by simple infiltration of suitable emitting polymers in monolithically integrated nanostructured PSiMCs.

C-Si hybrid photonic structures by full infiltration of conjugated polymers into porous silicon rugate filters

Loading of one-dimensional (1-D) porous silicon photonic crystals (PS-PhCs), known as rugate filters, with luminescent materials is generally limited by the potential for (undesired) “pore clogging,” in relation to the size of the nanoparticles (e.g. quantum dots) or molecular species, and so far mainly restricted to small molecular weight materials or small nanocrystals, or in situ polymerized dyes. Here we report the infiltration 1-D PS-PhCs with a green-emitting commercial luminescent polymer (F8BT, poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)]), with a molecular weight of approximately 46 kDa across their whole depth (approximately 7.5 μm), thereby showing that pore clogging is not a concern for these structures. We also characterize the modification of the photoluminescence (PL) and decay rates, and investigate the detailed inner morphology of the filters with the help of (scanning) transmission electron microscopy. We observe both suppression (in the stop-band) and enhancement (at the high-energy band-edge) of the PL. We also find that the photonic stop-band is red-shifted after polymer infiltration, due to the increased effective refractive index of the polymer-infiltrated nanostructured system. The presence of just one unbroadened peak in the reflectance spectra after infiltration confirms that infiltration extends for the whole depth of the rugate filters.

Polystyrene nanoparticle-templated hollow titania nanosphere monolayers as ordered scaffolds

We report a novel multi-step method for the preparation of ordered mesoporous titania scaffolds and show an illustrative example of their application to solar cells. The method is based on (monolayer) colloidal nanosphere lithography that makes use of polystyrene nanoparticles organised at a water–air interface and subsequently transferred onto a solid substrate. A titania precursor solution (titanium(IV) isopropoxide in ethanol) is then drop-cast onto the monolayer and left to “incubate” overnight. Surprisingly, instead of the expected inverse monolayer-structure, a subsequent calcination step of the precursor yields an ordered monolayer of hollow titania nanospheres with a wall thickness of ∼30–50 nm, and a slightly larger diameter than that of the starting spheres. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterization of such scaffolds confirm that they consist of nanocrystalline anatase titania, and that any polystyrene/carbon residues in the scaffolds are below the XPS detection level. As an illustrative application we prepared perovskite solar cells incorporating the templated-nanoparticle scaffolds displaying a respectable power conversion efficiency of ∼9%, twice as large as that of our unoptimized “reference” cells (i.e. incorporating conventional mesoporous or compact titania scaffolds), thereby also demonstrating that the process is relatively robust with respect to optimization of the process parameters.

Black GaAs by Metal-Assisted Chemical Etching

Large area surface microstructuring is commonly employed to suppress light reflection and enhance light absorption in silicon photovoltaic devices, photodetectors, and image sensors. To date, however, there are no simple means to control the surface roughness of III-V semiconductors by chemical processes similar to the metal-assisted chemical etching of black Si. Here, we demonstrate the anisotropic metal-assisted chemical etching of GaAs wafers exploiting the lower etching rate of the monoatomic Ga<111> and <311> planes. By studying the dependence of this process on different crystal orientations, we propose a qualitative reaction mechanism responsible for the self-limiting anisotropic etching and show that the reflectance of the roughened surface of black GaAs reduces up to ∼50 times compared to polished wafers, nearly doubling its absorption. This method provides a new, simple, and scalable way to enhance light absorption and power conversion efficiency of GaAs solar cells and photodetectors.