Self-Assembled Metal Nanohole Arrays with Tunable Plasmonic Properties for SERS Single-Molecule Detection.

Arrays of metal nano-holes have proved to be among of the most promising structures for applications in the field of nano-photonics and optoelectronics. Supporting both localized and propagating surface plasmons resonances, they are characterized by very high versatility thanks to the tunability of these modes, by means of the change of their periodicity, the size of the holes and metal composition. The interaction between different optical features can be exploited to modulate electromagnetic field distribution leading various hot-spots excitations on the metal surfaces. In this work, long range ordered arrays of nano-holes in thin gold films, with different geometrical characteristics, were fabricated by a modified nano-sphere lithography protocol, which allows precise control on holes' dimensions together with the preservation of the order and of the pristine periodicity of the array. An in-depth analysis of the correlation between surface plasmon modes interference and its effect on electromagnetic field distribution is proposed, both by numerical simulations and experimentally. Finally, metal nano-holes arrays are exploited for surface enhanced Raman experiments, evaluating and comparing their performances by the estimation of the enhancement factor. Values close to the single molecule detection are obtained for most of the samples, proving their potentialities in surface enhanced spectroscopy applications.

Light Emission Properties of Thermally Evaporated CH3NH3PbBr3 Perovskite from Nano- to Macro-Scale: Role of Free and Localized Excitons.

Over the past decade, interest about metal halide perovskites has rapidly increased, as they can find wide application in optoelectronic devices. Nevertheless, although thermal evaporation is crucial for the development and engineering of such devices based on multilayer structures, the optical properties of thermally deposited perovskite layers (spontaneous and amplified spontaneous emission) have been poorly investigated. This paper is a study from a nano- to micro- and macro-scale about the role of light-emitting species (namely free carriers and excitons) and trap states in the spontaneous emission of thermally evaporated thin layers of CH3NH3PbBr3 perovskite after wet air UV light trap passivation. The map of light emission from grains, carried out by SNOM at the nanoscale and by micro-PL techniques, clearly indicates that free and localized excitons (EXs) are the dominant light-emitting species, the localized excitons being the dominant ones in the presence of crystallites. These species also have a key role in the amplified spontaneous emission (ASE) process: for higher excitation densities, the relative contribution of localized EXs basically remains constant, while a clear competition between ASE and free EXs spontaneous emission is present, which suggests that ASE is due to stimulated emission from the free EXs.

Investigation of the exciton relaxation processes in poly(9,9-dioctylfluorene-co-benzothiadiazole):CsPbI1.5Br1.5 nanocrystal hybrid polymer-perovskite nanocrystal blend.

The combination of lead halide perovskite nanocrystals and conjugated polymer in a blend film opens the way to the realization of hybrid active layers with widely tunable optical and electrical properties. However, the interaction between the polymeric and the perovskite component of the blends is mainly unexplored to date. In this work we perform temperature-dependent photoluminescence and time resolved photoluminescence measurements in order to deeply investigate the photophysics of a poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT):CsPbI1.5Br1.5 nanocrystal hybrid film. Our results suggest that the primary interaction channel is charge transfer, both from F8BT to the NCs and from the NCs to F8BT, while Förster resonant energy transfer has no visible effects. Moreover, we show that the charge transfer is assisted by energy migration within the F8BT excited state distribution and that it is dependent on the local micromorphology of the film. Our work improves the current understanding of the polymer:perovskite NC interactions in hybrid films, and it is expected to be relevant for the development of hybrid organic-perovskite optoelectronic devices.

Local Morphology Effects on the Photoluminescence Properties of Thin CsPbBr3 Nanocrystal Films.

Lead halide perovskites are emerging as extremely interesting active materials for a wide variety of optoelectronic and photonic devices. A deep understanding of their photophysics is thus fundamental in order to properly understand the origins of the materials active properties and to provide strategies for improving them. In this work, we exploit the local morphological variations in a drop-cast thin CsPbBr3 nanocrystal film to show that the aggregation of NCs has strong effects on the peak wavelengths of PL spectra, the linewidth, and the intensity of dependence on temperature. An analysis based on models that are frequently used in the literature led to completely different conclusions about the intrinsic NC emission properties extracted from spectra measured in points with different contribution of the PL from the aggregates. Our results demonstrate that extreme care has to be used in order to correctly correlate the spectral PL features with the intrinsic emission properties of lead halide perovskite NC films.

Amplified spontaneous emission in thin films of quasi-2D BA3MA3Pb5Br16 lead halide perovskites.

Quasi-2D (two-dimensional) hybrid perovskites are emerging as a new class of materials with high photoluminescence yield and improved stability compared to their three-dimensional (3D) counterparts. Nevertheless, despite their outstanding emission properties, few studies have been reported on amplified spontaneous emission (ASE) and a thorough understanding of the photophysics of these layered materials is still lacking. In this work, we investigate the ASE properties of multilayered quasi-2D BA3MA3Pb5Br16 films through the dependence of the photoluminescence on temperature and provide a novel insight into the emission processes of quasi-2D lead bromide perovskites. We demonstrate that the PL and ASE properties are strongly affected by the presence, above 190 K, of a minor fraction of the high temperature (HT) phase. This phase dominates the PL spectra at low excitation density and strongly affects the ASE properties. In particular, ASE is only present between 13 K and 230 K, and, at higher temperatures, it is suppressed by absorption of charge transfer states of the HT phase. Our results improve the understanding of the difficulties to obtain ASE at room temperature from these quasi-2D materials and are expected to guide possible materials improvement in order to exploit their excellent emission properties also for the realization of low threshold optically pumped lasers.

Photo-ignition process of multiwall carbon nanotubes and ferrocene by continuous wave Xe lamp illumination.

This work aims to investigate and characterize the photo-ignition phenomenon of MWCNT/ferrocene mixtures by using a continuous wave (CW) xenon (Xe) light source, in order to find the power ignition threshold by employing a different type of light source as was used in previous research (i.e., pulsed Xe lamp). The experimental photo-ignition tests were carried out by varying the weight ratio of the used mixtures, luminous power, and wavelength range of the incident Xe light by using selective optical filters. For a better explanation of the photo-induced ignition process, the absorption spectra of MWCNT/ferrocene mixtures and ferrocene only were obtained. The experimental results show that the luminous power (related to the entire spectrum of the Xe lamp) needed to trigger the ignition of MWCNT/ferrocene mixtures decreases with increasing metal nanoparticles content according to previously published results when using a different type of light source (i.e., pulsed vs CW Xe light source). Furthermore, less light power is required to trigger photo-ignition when moving towards the ultraviolet (UV) region. This is in agreement with the measured absorption spectra, which present higher absorption values in the UV-vis region for both MWCNT/ferrocene mixtures and ferrocene only diluted in toluene. Finally, a chemo-physical interpretation of the ignition phenomenon is proposed whereby ferrocene photo-excitation, due to photon absorption, produces ferrocene itself in its excited form and is thus capable of promoting electron transfer to MWCNTs. In this way, the resulting radical species, FeCp2 +∙ and MWCNT-, easily react with oxygen giving rise to the ignition of MWCNT/ferrocene samples.