Optimization of growth and ordering of Ag nanoparticle arrays on ripple patterned alumina surfaces for strong plasmonic coupling.

Low-energy ion beam sputtering of alumina thin films followed by growth of metallic nanoparticles by glancing angle deposition is optimized in order to produce arrays of silver nanoparticle chains with a strong plasmonic dichroism. A systematic study is undertaken in order to establish the influence of the angle of silver deposition and the ordering of the pre-patterned rippled surface on the morphology and organization of the nanoparticles, and on their associated optical properties. High ion fluence for ripple formation and low glancing angle for metal deposition favor the formation of aligned and elongated particles with sub-nanometer gaps. Numerical simulations show that these nanoparticle arrays generate high electric field enhancements for an excitation parallel to the particle chains, and therefore can be used for surface enhanced spectroscopies.

Tuning the surface plasmon resonance of silver nanoclusters by oxygen exposure and low-energy plasma annealing.

Real-time surface differential reflectance spectroscopy in the visible range is used to study the optical response of silver nanoclusters, prepared by magnetron sputtering deposition, during cyclic treatments in different oxygen atmospheres and low-energy bias argon plasma. Changes in the reflectance show that the exposure to non-ionized (or partially ionized) oxygen causes a red-shift and damping (or complete vanishing) of the resonance, while bias plasma annealing induces the opposite effects, due to oxygen desorption and structural reshaping of the nanoclusters. These results open up new opportunities for developing plasmon-based devices with high tunability of the surface plasmon resonance (energy, width and amplitude) due to an interplay between morphological and chemical modifications of the nanoclusters.

Comments on "Surface plasmon resonance of metal nanoparticles sandwiched between dielectric layers: theoretical modeling".

The Maxwell-Garnett's and Toudert's methods detailed in Appl. Opt.48, 778 (2009)APOPAI0003-693510.1364/AO.48.000778, based on the Maxwell-Garnett and Yamaguchi effective medium models, respectively, have been used for calculating the absorbance alpha of a (BaF(2)/Ag)(5)/BaF(2) nanocomposite thin film identical to the one presented in Fig. 1 of Appl. Opt.48, 778 (2009)APOPAI0003-693510.1364/AO.48.000778]. We propose that the discrepancies observed in this reference between the alpha spectra calculated by the two methods are due to a non rigorous use of both effective medium models by the author and show that adequate calculations lead to superposed spectra.

Linear and third-order nonlinear optical responses of multilayered Ag:Si3N4 nanocomposites.

The linear and third-order nonlinear responses of tailored Si3N4/Ag/Si3N4 trilayers and (Si3N4/Ag)n/Si3N4 multilayers grown by alternating ion-beam sputtering have been studied by combining complementary characterization techniques such as transmission electron microscopy, spectroscopic ellipsometry and degenerate four-wave mixing. The linear optical response dominated by the surface plasmon resonance of Ag nanoparticles has been measured over the whole visible range while the third-order nonlinear susceptibility has been probed at the surface plasmon resonance wavelength. Due to the weak in-plane interaction between Ag nanoparticles, the linear and nonlinear optical responses of the Si3N4/Ag/Si3N4 trilayers are mainly influenced by the size and shape of the nanoparticles. A maximum value of 1.1 x 10(-7) esu has been found at 635 nm for the effective third-order nonlinear susceptibility of the trilayer with the highest amount of silver. The linear optical response of the (Si3N4/Ag)n/Si3N4 multilayers is shown to be dominated by the surface plasmon resonance of isolated layers of weakly interacting nanoparticles at wavelengths shorter than 600 nm whereas a contribution due to vertical interactions has been shown for higher wavelengths. Below the vertical percolation threshold, their nonlinear optical response at the surface plasmon resonance wavelength is similar to the one of an isolated assembly of nanoparticles, and the effective third-order nonlinear susceptibility is slightly increased by decreasing the thickness of the Si3N4 spacer.

Quantitative modelling of the surface plasmon resonances of metal nanoclusters sandwiched between dielectric layers: the influence of nanocluster size, shape and organization.

The effects of size, shape and organization on the surface plasmon resonances of Ag nanoclusters sandwiched between Si(3)N(4) layers are studied by transmission electron microscopy and anisotropic spectroscopic ellipsometry. We present an easy-to-handle model that quantitatively links the nanostructure and optical response of the films, which are considered as dielectric/metal:dielectric/dielectric trilayers, with the central nanocomposite layer being an effective medium whose optical properties are described by an anisotropic dielectric tensor. The components of this tensor are calculated using a generalization of the Yamaguchi theory taking into account the real organization, size and shape distributions of ellipsoidal nanoclusters, whose electronic properties are assumed to reflect shape-dependent finite size effects. Using this model, it is shown that the optical response of the films in the visible range is dominated by the excitation of the surface plasmon resonance of the clusters along their in-plane long axis, while no surface plasmon resonance resulting from an excitation along their in-plane short axis can be observed due to damping effects. Moreover, the spectral position of this resonance appears to be mainly affected by the average shape of the clusters, and weakly by their size, their shape distribution and the electromagnetic interaction between them.

Optical evidence for reactive processes when embedding Cu nanoparticles in Al(2)O(3) by pulsed laser deposition.

The optical response of nanocomposite thin films formed by Cu nanoparticles (NPs) embedded in amorphous aluminium oxide (Al(2)O(3)) prepared by pulsed laser deposition (PLD) in vacuum is studied in order to investigate the possible existence of reactive processes on the Cu NPs during their covering with Al(2)O(3). The study is performed as a function of the laser fluence on the Al(2)O(3) target (0.6-4.6 J cm(-2)), while the laser fluence for Cu ablation is kept constant (1.8 J cm(-2)). The structural analysis of the films shows that they are formed by a high density of NPs with average dimensions in the 4.9-5.9 nm range. The optical response of the films has been followed in situ by real-time reflectivity measurements at 633 nm and after deposition by transmission measurements as a function of wavelength around the surface plasmon resonance (SPR). For low laser fluences on the Al(2)O(3) target, the absorption spectrum is dominated by a well-defined SPR absorption band at 1.9 eV. As the laser fluence is increased, the intensity of the absorption band associated with the SPR decreases and shifts to 2.1 eV. The films deposited at low fluences contain metallic Cu NPs and, as the laser fluence increases sputtering of Cu from the NPs and mixing of the species from the Al(2)O(3) deposition with the Cu from the NPs surface takes place. The latter process leads to the formation of an Al-Cu oxide cover on the Cu NPs. The present results provide evidence for mixing of species from the host and Cu at the surface of the NPs, and it is shown how the degree of mixing depends on the laser fluence used to ablate the Al(2)O(3) host target.