Due to their peculiar qualities, metal-based nanostructures have been extensively used in applications such as catalysis, electronics, photography, and information storage, among others. New applications for metals in areas such as photonics, sensing, imaging, and medicine are also being developed. Significantly, most of these applications require the use of metals in the form of nanostructures with specific controlled properties. The properties of nanoscale metals are determined by a set of physical parameters that include size, shape, composition, and structure. In recent years, many research fields have focused on the synthesis of nanoscale-sized metallic materials with complex shape and composition in order to optimize the optical and electrical response of devices containing metallic nanostructures. The present paper aims to overview the most recent results—in terms of fabrication methodologies, characterization of the physico-chemical properties and applications—of complex-morphology metal-based nanostructures. The paper strongly focuses on the correlation between the complex morphology and the structures’ properties, showing how the morphological complexity (and its nanoscale control) can often give access to a wide range of innovative properties exploitable for innovative functional device production. We begin with an overview of the basic concepts on the correlation between structural and optical parameters of nanoscale metallic materials with complex shape and composition, and the possible solutions offered by nanotechnology in a large range of applications (catalysis, electronics, photonics, sensing). The aim is to assess the state of the art, and then show the innovative contributions that can be proposed in this research field. We subsequently report on innovative, versatile and low-cost synthesis techniques, suitable for providing a good control on the size, surface density, composition and geometry of the metallic nanostructures. The main purpose of this study is the fabrication of functional nanoscale-sized materials, whose properties can be tailored (in a wide range) simply by controlling the structural characteristics. The modulation of the structural parameters is required to tune the plasmonic properties of the nanostructures for applications such as biosensors, opto-electronic or photovoltaic devices and surface-enhanced Raman scattering (SERS) substrates. The structural characterization of the obtained nanoscale materials is employed in order to define how the synthesis parameters affect the structural characteristics of the resulting metallic nanostructures. Then, macroscopic measurements are used to probe their electrical and optical properties. Phenomenological growth models are drafted to explain the processes involved in the growth and evolution of such composite systems. After the synthesis and characterization of the metallic nanostructures, we study the effects of the incorporation of the complex morphologies on the optical and electrical responses of each specific device.

Ge nanoclusters (NCs), synthesized by ion implantation and annealing up to 900 °C, result small (∼2 nm) and amorphous in Si3N4, crystalline and much larger in SiO2. The NCs ripening and crystallization kinetics in Si3N4 is retarded by larger interfacial energy and lower diffusivity of Ge in comparison to SiO2. Ge NCs absorb light more efficiently when embedded in Si3N4 than in SiO2. A significant effect of the barrier height on absorption was evidenced, in agreement with effective mass theory predictions. The smaller bandgap of Ge NCs embedded in Si3N4 and their closeness is promising features for light harvesting applications.

In this work, we propose a methodology to synthesize metallic nanoparticles on textured Fluorine Tin Oxide (FTO) surface by laser irradiations of deposited Au films. In particular, the breakup of the Au films into nanoparticles (NPs) is observed as a consequence of the melting and solidification processes induced by laser irradiations. The mean Au NPs size and surface density evolution are analyzed as a function of the laser fluence. Optical characterizations of the glass/FTO/Au NPs multilayer show, in the absorption spectra, plasmonic peaks due to the Au NPs and an improvement of the light absorption efficiency from the sample with larger Au NPs. The simulated trends of the ratio between the scattering and absorption cross section suggest that the absorption efficiency dominates over the scattering efficiency in the spectral range between 200 and 600 nm. The simulation shows that, by varying the NPs radius from about 18 to 24 nm, the radiation-scattered intensity remains symmetric in forward and reverse directions. These results indicate that the surface coverage size distribution of Au NPs is the key parameter to correlate the structural and optical properties of the glass/FTO/Au NPs multilayer. Furthermore, electrical characterizations highlight a reduction in the sheet resistance of the textured FTO due to the presence of the NPs. We compare these results with those obtained for the same systems when standard furnace annealing processes are used to obtain the Au NPs on the textured FTO surface.