F. Bisio

Deep ultraviolet plasmon resonance in aluminum nanoparticle arrays.

Small aluminum nanoparticles have the potential to exhibit localized surface plasmon resonances in the deep ultraviolet region of the electromagnetic spectrum, however technical and scientific challenges make it difficult to attain this limit. We report the fabrication of arrays of Al/Al2O3 core/shell nanoparticles with a metallic-core diameter between 12 and 25 nm that display sharp plasmonic resonances at very high energies, up to 5.8 eV (down to λ = 215 nm). The arrays were fabricated by means of a straightforward self-organization approach. The experimental spectra were compared with theoretical calculations that allow the correlation of each feature to the corresponding plasmon modes.

Rapid CVD growth of millimetre-sized single crystal graphene using a cold-wall reactor

In this work we present a simple pathway to obtain large single-crystal graphene on copper (Cu) foils with high growth rates using a commercially available cold-wall chemical vapour deposition (CVD) reactor. We show that graphene nucleation density is drastically reduced and crystal growth is accelerated when: (i) using ex situ oxidized foils; (ii) performing annealing in an inert atmosphere prior to growth; (iii) enclosing the foils to lower the precursor impingement flux during growth. Growth rates as high as 14.7 and 17.5 μm min−1 are obtained on flat and folded foils, respectively. Thus, single-crystal grains with lateral size of about 1 mm can be obtained in just 1 h. The samples are characterized by optical microscopy, scanning electron microscopy, x-ray photoelectron spectroscopy, Raman spectroscopy as well as selected area electron diffraction and low-energy electron diffraction, which confirm the high quality and homogeneity of the films. The development of a process for the quick production of large grain graphene in a commonly used commercial CVD reactor is a significant step towards an increased accessibility to millimetre-sized graphene crystals.

Modulation of resistance switching in Au/Nb:SrTiO3 Schottky junctions by ambient oxygen

We investigated the room-temperature current-voltage characteristics of Au/Nb:SrTiO3 Schottky junctions under various atmospheres and working pressures. We observed that oxygen partial pressure reversibly modulates junction response, briefly individual specimens behave as high-quality rectifiers in oxygen-rich atmospheres and as bipolar resistive switches in vacuum and inert gases. A two orders of magnitude modulation of resistance switching characterizes samples with the highest content of interfacial oxygen vacancies. We attribute this behavior to oxygen ionosorption and chemical oxidation at the metal-oxide interface. Our results are relevant to oxide devices displaying resistive switching at ambient-exposed interfaces, and might be exploited for gas detection purposes.

Optical properties of Yeast Cytochrome c monolayer on gold: an in situ spectroscopic ellipsometry investigation.

The adsorption of Yeast Cytochrome c (YCC) on well defined, flat gold substrates has been studied by Spectroscopic Ellipsometry (SE) in the 245-1000 nm wavelength range. The investigation has been performed in aqueous ambient at room temperature, focusing on monolayer-thick films. In situ δΨ and δΔ difference spectra have shown reproducibly well-defined features related to molecular optical absorptions typical of the so-called heme group. The data have been reproduced quantitatively by a simple isotropic optical model, accounting for the molecular absorption spectrum and film-substrate interface effects. The simulations allowed a reliable estimate of the film thickness and the determination of the position and the shape of the so-called Soret absorption peak that, within the experimental uncertainty, is the same found for molecules in liquid. These findings suggest that YCC preserves its native structure upon adsorption. The same optical model was able to reproduce also ex situ results on rinsed and dried samples, dominated by the spectral features associated to the polypeptide chain that tend to overwhelm the heme absorption features.

Growth dynamics of L-cysteine SAMs on single-crystal gold surfaces: a metastable deexcitation spectroscopy study.

We report on a metastable deexcitation spectroscopy investigation of the growth of L-cysteine layers deposited under UHV conditions on well-defined Au(110)- (1 × 2) and Au(111) surfaces. The interaction of He(*) with molecular orbitals gave rise to well-defined UPS-like Penning spectra which provided information on the SAM assembly dynamics and adsorption configurations. Penning spectra have been interpreted through comparison with molecular orbital DFT calculations of the free molecule and have been compared with XPS results of previous works. Regarding adsorption of first-layer molecules at room temperature (RT), two different growth regimes were observed. On Au(110), the absence of spectral features related to orbitals associated with SH groups indicated the formation of a compact SAM of thiolate molecules. On Au(111), the data demonstrated the simultaneous presence, since the early stages of growth, of strongly and weakly bound molecules, the latter showing intact SH groups. The different growth mode was tentatively assigned to the added rows of the reconstructed Au(110) surface which behave as extended defects effectively promoting the formation of the S-Au bond. The growth of the second molecular layer was instead observed to proceed similarly for both substrates. Second-layer molecules preferably adopt an adsorption configuration in which the SH group protrudes into the vacuum side.

Interaction of alkanethiols with nanoporous cluster-assembled Au films.

This article presents a study of the interaction of octadecanethiol molecules (C(18)) with nanoporous cluster-assembled gold films under a liquid environment based on a combined spectroscopic ellipsometry and X-ray photoelectron spectroscopy investigation. By comparing the optical response, following the deposition of C(18), of cluster-assembled films with varying degrees of porosity with that of flat surfaces and by resolving the corresponding features of the molecule-Au bond, we have been able to define the conditions that either favor molecular in-depth diffusion into the pores or promote the formation of a molecular self-assembled monolayer (SAM) restricted to the film surface. In the presence of abundant open pores, C(18) molecules strongly diffuse within the film interior and bind to the pore walls, whereas in the presence of porous films with less abundant open pores we have observed that the molecules tend to remain confined to the surface region, adopting a SAM-like configuration.

Plasmonic Color-Graded Nanosystems with Achromatic Subwavelength Architectures for Light Filtering and Advanced SERS Detection.

Plasmonic color-graded systems are devices featuring a spatially variable plasmonic response over their surface. They are widely used as nanoscale color filters; their typical size is small enough to allow integration with miniaturized electronic circuits, paving the way to realize novel nanophotonic devices. Currently, most plasmonic color-graded systems are intrinsically discrete because their chromatic response exploits the tailored plasmon resonance of microarchitectures characterized by different size or geometry for each target color. Here, we report the realization of multifunctional plasmon-graded devices where continuously graded chromatic response is achieved by smoothly tuning the composition of the resonator material while simultaneously maintaining an achromatic nanoscale geometry. The result is a new class of versatile materials: we show their application as plasmonic filters with a potential pixel size smaller than half of the exciting wavelength but also as multiplexed surface-enhanced Raman spectroscopy (SERS) substrates. Many more implementations, such as photovoltaic efficiency boosters or color routers, await and will benefit from the low fabrication cost and intrinsic plasmonic flexibility of the presented systems.

Tuning the magnetic anisotropy of ultrathin Fe∕Ag(001) films from biaxial to uniaxial by ion sculpting

Ion sculpting of ultrathin Fe∕Ag(001) films induces the self-assembled formation of nanometric surface ripples oriented along the ion beam direction and the corresponding onset of an in-plane uniaxial contribution to magnetic anisotropy. The authors show that fine tuning of the ion dose impinging on the film allows to tailor the in-plane magnetic anisotropy of such films from purely biaxial in the as-grown state to purely uniaxial. The magnitude of magnetic anisotropy in the pure uniaxial state can be tailored by varying the Fe film thickness prior to irradiation.

Optical properties of nanogranular and highly porous TiO2 thin films

We present a systematic investigation of the optical properties of cluster-assembled TiO2 films (20–150 nm nominal thickness) deposited onto Si wafers and processed with two types of ex-situ oxidation treatments. Spectroscopic ellipsometry (0.7–5 eV energy range), supported by x-ray photoelectron spectroscopy and atomic force microscopy measurements, allowed us to obtain information on the depth-dependent morphology of the films in a non-destructive mode. The characteristic grainy and porous structure of the films was modelled by means of a flexible effective-medium approach, allowing us to obtain a reliable estimate of the amount and distribution of voids into the films and their accessibility to foreign liquids. The absorption-edge broadening and significant optical absorptions within the gap were attributed to the intrinsically nanogranular morphology and to the interrelated defective structure/stoichiometry of the particles, also in relation to the occurrence of poorly accessible interstices or pores in the inner parts of the film.

Tuning the magneto-optical response of iron oxide nanocrystals in Au- and Ag-based plasmonic media.

We investigated the magneto-optical response of chemically synthesized iron oxide magnetic nanocrystals, optically coupled with ordered planar arrays of plasmonic nanoparticles. We compare the signals from two classes of systems, featuring either Au or Ag as the plasmonic counterpart. The localized surface plasmon resonance of the Ag and Au nanoparticles arrays were superimposed or detuned, respectively, with respect to the dominant magneto-optical transitions of the magnetic material. Under resonance, a significant enhancement of the magneto-optical signal was observed. In both cases, we could separate the purely plasmonic and the magnetic contributions in the magneto-optical spectrum of the optically coupled composite based on their different magnetic-field dependence.