In this article the luminescence properties of Si nanocrystals (nc) formed by plasma enhanced chemical vapor deposition and their interaction with Er ions introduced by ion implantation are investigated in detail. Si nc with different size distributions and densities were produced and all show quite intense room temperature luminescence (PL) in the range 700–1100 nm. It is shown that the time-decay of the luminescence follows a stretched exponential function whose shape tends towards a single exponential for almost isolated nc. This suggests that stretched exponential decays are related to the energy transfer from smaller towards larger nc. Indeed, by comparing samples with similar nc size distributions, but with very different nc densities, it is demonstrated that the PL has a quite strong redshift in the high density case, demonstrating a clear energy redistribution within the sample. Excitation cross sections have been measured in all samples yielding a value of ∼1.8×10−16 cm2 for isolated nc excited with 2.54 eV photons. This effective excitation cross section is shown to increase by a factor of 4 in interacting nc as a result of the energy transfer within the sample. When Er ions are introduced in these samples a strong nc–Er interaction sets in and the energy is preferentially transferred from the nc to the Er ions. The nc-related luminescence is quenched and the Er-related luminescence at 1.54 μm appears. The effective excitation cross section of Er ions through Si nc has been determined to be ∼1.1×10−16 cm2. This number resembles the excitation cross section of nc themselves demonstrating that the coupling is extremely strong. Moreover, by increasing the Er content the effective excitation cross section is seen to increase. In the same concentration range the Er lifetime decreases demonstrating that “concentration quenching” effects, with the energy transferred among Er ions, are setting in. These Er–Er interactions are responsible for the effective increase of the cross section. However, since the increase in the cross section is related to a simultaneous decrease in lifetime the net effect for the luminescence efficiency is negative. The best Er content to take advantage of the sensitizer action of Si nc avoiding the detrimental Er–Er interactions has been determined to be ∼2×1020/cm3. These data are presented and their implications discussed.
Strategies for in-liquid molecular detection via Surface Enhanced Raman Scattering (SERS) are currently based on chemically-driven aggregation or optical trapping of metal nanoparticles in presence of the target molecules. Such strategies allow the formation of SERS-active clusters that efficiently embed the molecule at the “hot spots” of the nanoparticles and enhance its Raman scattering by orders of magnitude. Here we report on a novel scheme that exploits the radiation pressure to locally push gold nanorods and induce their aggregation in buffered solutions of biomolecules, achieving biomolecular SERS detection at almost neutral pH. The sensor is applied to detect non-resonant amino acids and proteins, namely Phenylalanine (Phe), Bovine Serum Albumin (BSA) and Lysozyme (Lys), reaching detection limits in the μg/mL range. Being a chemical free and contactless technique, our methodology is easy to implement, fast to operate, needs small sample volumes and has potential for integration in microfluidic circuits for biomarkers detection.
We explore the effect of re-radiation in surface-enhanced Raman scattering (SERS) through polarization-sensitive experiments on self-organized gold nanowires on which randomly oriented Methylene Blue molecules are adsorbed. We provide the exact laws ruling the polarized, unpolarized, and parallel- and cross-polarized SERS intensity as a function of the field polarizations. We show that SERS is polarized along the wire-to-wire nanocavity axis, independently from the excitation polarization. This proves the selective enhancement of the Raman dipole component parallel to the nanocavity at the single molecule level. Introducing a field enhancement tensor to account for the anisotropic polarization response of the nanowires, we work out a model that correctly predicts the experimental results for any excitation/detection polarization and goes beyond the E(4) approximation. We also show how polarization-sensitive SERS experiments permit one to evaluate independently the excitation and the re-radiation enhancement factors accessing the orientation-averaged non-diagonal components of the molecular Raman polarizability tensor.
Here we report on the fabrication of a new low-cost transparent cathode based on platinum nanoparticles prepared by a bottom-up synthetic approach. Scanning Electron Microscope (SEM) images showed the platinum nanoparticles homogeneously distributed on a fluorine doped tin oxide conductive glass surface. We demonstrated that, with such a type of cathode, the solar energy conversion efficiency is the same as that obtained with a platinum sputtered counter-electrode, and is more than 50% greater than that obtained with a standard electrode, i.e. one prepared by chlorine platinum acid thermal decomposition, in similar working conditions. Using a special back-reflecting layer of silver, we improved upon the performance of a counter-electrode based on platinum sputtering, achieving an overall solar conversion efficiency of 4.75% at 100 mW cm À2 (AM 1.5) of simulated sunlight.
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