Cristiano D'Andrea

The controlled pulsed laser deposition of Ag nanoparticle arrays for surface enhanced Raman scattering

An effective method for the production of surface enhanced Raman scattering (SERS) active substrates is presented. Nanostructured silver thin films are pulsed laser deposited in an argon atmosphere. The films consist of arrays of nanoparticles whose size is controlled by the Ar pressure. The surface morphology of the films can be tuned by the laser pulse number. Nanoparticle size is calculated by a phenomenological model taking into account the dynamics of the laser generated silver plasma. The SERS activity of the films is investigated by Raman scattering of adsorbed rhodamine 6G at different concentrations.

Strongly enhanced light trapping in a two-dimensional silicon nanowire random fractal array

We report on the unconventional optical properties exhibited by a two-dimensional array of thin Si nanowires arranged in a random fractal geometry and fabricated using an inexpensive, fast and maskless process compatible with Si technology. The structure allows for a high light-trapping efficiency across the entire visible range, attaining total reflectance values as low as 0.1% when the wavelength in the medium matches the length scale of maximum heterogeneity in the system. We show that the random fractal structure of our nanowire array is responsible for a strong in-plane multiple scattering, which is related to the material refractive index fluctuations and leads to a greatly enhanced Raman scattering and a bright photoluminescence. These strong emissions are correlated on all length scales according to the refractive index fluctuations. The relevance and the perspectives of the reported results are discussed as promising for Si-based photovoltaic and photonic applications.

Decoration of silicon nanowires with silver nanoparticles for ultrasensitive surface enhanced Raman scattering.

Silicon nanowires (Si NWs), produced by the chemical etching technique, were decorated with silver nanoparticles (NPs) produced at room temperature by the pulsed laser deposition (PLD) technique. Silver NPs were obtained by means of nanosecond pulsed laser ablation of a target in the presence of a controlled Ar atmosphere. Two different laser pulse numbers and Si NWs having different lengths were used to change the NP number density on the Si NW surface. The resulting Ag NP morphologies were studied by scanning electron microscopy imaging. The results show that this industrially compatible technological approach allows the coverage of the Si NW walls with Ag NPs with a strong control of the NP size distribution and spatial arrangement. The obtained Ag NP decorated Si NWs are free from chemicals contamination and there is no need of post deposition high temperature processes. The optical properties of Si NW arrays were investigated by reflectance spectroscopy that showed the presence of a plasmon related absorption peak, whose position and width is dependent on the Ag NP surface morphology. Coupling the huge surface-to-volume ratio of Si NW arrays with the plasmonic properties of silver nanoparticles resulted in a 3D structure suitable for very sensitive surface enhanced Raman scattering (SERS) applications, as demonstrated by the detection of Rhodamine 6G in aqueous solution at a concentration level of 10(-8) M.

Functionalization of silicon nanowire arrays by silver nanoparticles for the laser desorption ionization mass spectrometry analysis of vegetable oils

In this work, novel hybrid nanostructured surfaces, consisting of dense arrays of silicon nanowires (SiNWs) functionalized by Ag nanoparticles (AgNP/SiNWs), were used for the laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) analysis of some typical unsaturated food components (e.g. squalene, oleic acid) to assess their MS performance. The synthesis of the novel platforms is an easy, cost-effective process based on the maskless wet-etching preparation at room temperature of SiNWs followed by their decoration with AgNPs, produced by pulsed laser deposition. No particular surface pretreatment or addition of organic matrixes/ionizers was necessary. Moreover, oil extracts (e.g. extra virgin olive oil, peanut oil) could be investigated on AgNP/SiNWs surfaces, revealing their different MS profiles. It was shown that such substrates operate at reduced laser energy, typically generating intense silver cluster ions and analyte adducts. A comparison with bare SiNWs was also performed, indicating the importance of AgNP density on NW surface. In this case, desorption/ionization on silicon was invoked as probable LDI mechanism. Finally, the influence of SiNW length and surface composition on MS results was assessed. The combination of typical properties of SiNWs (hydrophobicity, antireflectivity) with ionization ability of metal NPs can be a valid methodology for the further development of nanostructured surfaces in LDI-TOF MS applications. Copyright

Preparation and characterization of SERS substrates: From colloids to solid substrates

Surface enhanced Raman spectroscopy is an important technique for detection of wide number of analytes. Today, there is a growing need for the development of stable, sensitive, reproducible and portable SERS-active substrates for use in different fields. Some of the most extensively used SERS substrates are metal colloids. However, the use of the colloid solutions for SERS deals with important issues, like stability and reproducibility. Other popular types of substrates are rough or nanoporous surfaces, such as porous silicon, coated with noble metals. Porous silicon (pSi) is a semiconducting material typically obtained by electrochemical etching in hydrofluoric acid (HF). Due to its high surface-to-volume ratio pSi is an interesting material for photonic and sensing devices, drug delivery systems as well as for use in SERS. In this paper, attempts are made to prepare a stable and uniform noble metal colloidal solution as well as solid substrate using porous silicon (pSi) with deposited silver and gold nanostructures. SERS substrates obtained by different methods are evaluated for SERS efficiency using methylene blue and rhodamine 6G (R6G) at 514.5 and 633 nm. The prepared substrates showed good stability and reproducibility. For some substrates the concentrations detected were below nanomolar range.

Nanoscale Discrimination between Toxic and Nontoxic Protein Misfolded Oligomers with Tip-Enhanced Raman Spectroscopy

Highly toxic protein misfolded oligomers associated with neurological disorders such as Alzheimers and Parkinsons diseases are nowadays considered primarily responsible for promoting synaptic failure and neuronal death. Unraveling the relationship between structure and neurotoxicity of protein oligomers appears pivotal in understanding the causes of the pathological process, as well as in designing novel diagnostic and therapeutic strategies tuned toward the earliest and presymptomatic stages of the disease. Here, it is benefited from tip-enhanced Raman spectroscopy (TERS) as a surface-sensitive tool with spatial resolution on the nanoscale, to inspect the spatial organization and surface character of individual protein oligomers from two samples formed by the same polypeptide sequence and different toxicity levels. TERS provides direct assignment of specific amino acid residues that are exposed to a large extent on the surface of toxic species and buried in nontoxic oligomers. These residues, thanks to their outward disposition, might represent structural factors driving the pathogenic behavior exhibited by protein misfolded oligomers, including affecting cell membrane integrity and specific signaling pathways in neurodegenerative conditions.

Plasmon-enhanced Raman detection of body-fluid components

Plasmon-enhanced spectroscopies such as surface-enhanced Raman spectroscopy (SERS) concern the detection of enhanced optical responses of molecules in close proximity to plasmonic structures, which results in a strong increase in sensitivity. Recent advancements in nanofabrication methods have paved the way for a controlled design of tailor-made nanostructures with fine-tuning of their optical and surface properties. Among these, silver nanocubes (AgNCs) represent a convenient choice in SERS owing to intense electromagnetic fields localized at their extremities, which are further intensified in the gap regions between closely spaced nanoparticles. The integration of AgNCs assemblies within an optofluidic platform may confer potential for superior optical investigation due to a molecular enrichment on the plasmonic structures to collect an enhanced photonic response. We developed a novel sensing platform based on an optofluidic system involving assembled silver nanocubes of 50 nm in size for ultrasensitive SERS detection of biomolecules in wet conditions. The proposed system offers the perspective of advanced biochemical and biological characterizations of molecules as well as of effective detection of body fluid components and other molecules of biomedical interest in their own environment.

STRONGLY POLARIZED SCATTERING IN SURFACE ENHANCED RAMAN SPECTROSCOPY OF RANDOMLY DISTRIBUTED MOLECULES ON GOLD NANOWIRES

We study the polarized Surface Enhanced Raman Scattering from randomly oriented molecules adsorbed on near-field coupled gold nanowires. We show that the scat- tering is polarized always along the wire-to-wire nanocavities. We find the exact angular dependence for the polarized, unpolarized, parallel- and cross-polarized SERS intensity. Finally we develop a model that fits the experimental data and allows to measure the field enhancement and the re-radiation enhancement factors, independently, and retrieve the de- polarization ratio of the probe molecules.

Tuning the structural and optical properties of gold/silver nanoalloys prepared by laser ablation in liquids for ultra-sensitive spectroscopy and optical trapping

The plasmon resonance of metallic Au/Ag alloys in the colloidal state was tuned from 400 nm to 500 nm using a laser irradiated technique, performed directly in the liquid state. Interesting optical nonlinearities, trapping effects and spectroscopic enhancements were detected as function of gold concentration in the nanoalloys. In particular a reduction of the limiting threshold was observed by increasing the gold amount. The SERS activity of the Au/Ag alloys was tested in liquid and in solid state in presence of linear carbon chains as probe molecules. The dependence of the increased Raman signals on the nanoparticle Au/Ag atomic ratio is presented and discussed. Finally preliminary studies and prospects for optical and Raman tweezers experiments are discussed.

Surface Enhanced Raman Spectroscopy of biomolecules in buffer solution

Controlled creation of SERS-active hot spots in liquid is a challenge in which optical forces can play an important role by promoting the aggregation of metal nanoparticles by optical trapping or by exploiting the radiation pressure. Here we show that laser induced aggregation of gold nanorods in a buffered solution of Bovine Serum Albumin (BSA) leads to the formation of SERS-active agglomerates capable to enhance the Raman scattering of BSA by 5 orders of magnitude, thus allowing the detection of BSA at concentrations as low as 10 -6 M. This occurrence involves optical, mechanical and thermal effects.