Lisandro J. Giovanetti

Experimental and theoretical investigation of the electronic structure of Cu2O and CuO thin films on Cu(110) using x-ray photoelectron and absorption spectroscopy

The electronic structure of Cu(2)O and CuO thin films grown on Cu(110) was characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The various oxidation states, Cu(0), Cu(+), and Cu(2+), were unambiguously identified and characterized from their XPS and XAS spectra. We show that a clean and stoichiometric surface of CuO requires special environmental conditions to prevent loss of oxygen and contamination by background water. First-principles density functional theory XAS simulations of the oxygen K edge provide understanding of the core to valence transitions in Cu(+) and Cu(2+). A novel method to reference x-ray absorption energies based on the energies of isolated atoms is presented.

Study of Nucleation and Growth Mechanism of the Metallic Nanodumbbells

We propose a general nucleation and growth model that can explain the mechanism of the formation of CoPt(3)/Au, FePt/Au, and Pt/Au nanodumbbells. Thus, we found that the nucleation event occurs as a result of reduction of Au(+) ions by partially oxidized surface Pt atoms. In cases when Au(3+) is used as a gold precursor, the surface of seeds should be terminated by ions (e.g., Co(2+), Pb(2+)) that can reduce Au(3+) to Au(+) ions, which can further participate in the nucleation of gold domain. Further growth of gold domain is a result of reduction of both Au(3+) and Au(+) by HDA at the surface of gold nuclei. We explain the different ability of CoPt(3), Pt, and FePt seeds to serve as a nucleation center for the reduction of gold and further growth of dumbbells. We report that the efficiency and reproducibility of the formation of CoPt(3)/Au, FePt/Au, and Pt/Au dumbbells can be optimized by the concentration and oxidation states of the surface ions on metallic nanocrystals used as seeds as well as by the type of the gold precursor.

Synthesis and characterization of gold at gold(i)-thiomalate core at shell nanoparticles.

In this paper, the synthesis of gold at gold(I)-thiolate core at shell nanoparticles is described for the first time. The chemical nature and structure of these nanoparticles were characterized by a multi-technique approach. The prepared particles consist of gold metallic cores, about 1 nm in size, surrounded by stable gold(I)-thiomalate shells (Au at Au(I)-TM). These nanoparticles could be useful in medicine due to the interesting properties that gold(I)-thiomalate has against rheumatoid arthritis. Furthermore, the described results give new insights in the synthesis and characterization of metallic and core at shell nanoparticles.

Ag2 and Ag3 clusters: synthesis, characterization, and interaction with DNA.

Subnanometric samples, containing exclusively Ag2 and Ag3 clusters, were synthesized for the first time by kinetic control using an electrochemical technique without the use of surfactants or capping agents. By combination of thermodynamic and kinetic measurements and theoretical calculations, we show herein that Ag3 clusters interact with DNA through intercalation, inducing significant structural distortion to the DNA. The lifetime of Ag3 clusters in the intercalated position is two to three orders of magnitude longer than for classical organic intercalators, such as ethidium bromide or proflavine.

Analysis of the main optical mechanisms responsible for fragmentation of gold nanoparticles by femtosecond laser radiation

Studies of fragmentation process of gold nanoparticles (Nps) in deionized water after generation by femtosecond laser ablation were performed. To analyze the fragmentation process, direct IR ultrafast pulses or super-continuum (SC) radiation focused in the colloidal solution were used in separate steps. IR pulses and SC generated externally in a sapphire crystal or directly inside the water were applied under low fluence regime. In the latter cases, to evaluate the effect on fragmentation of the different spectral bands present in the SC, we have determined different efficiency regions characterized by means of the product between the spectral response and the optical extinction spectrum corresponding to the initial Nps solution. From the analysis of this product function, we can conclude that the main fragmentation mechanism is due to linear absorption in the visible region. Likewise, the SC generated in water resulted more efficient than the SC obtained externally by a sapphire crystal. This fact may be...

Spontaneous oxidation of disordered fcc FePt nanoparticles

In this work we present new results on spontaneous oxidation of disordered fcc FePt nanoparticles. The “as-made” oleic acid and oleylamine coated FePt nanoparticles of average size 4 nm synthesized by a high-boiling coordinating solvent method were exposed to air over a period of days and characterized structurally and magnetically by means of different techniques such as XANES, XPS, EXAFS, and SQUID magnetometry. The “as-made” FePt nanoparticles stabilize in the disordered fcc structure and have a very low magnetic saturation (Ms=11 emu/g) and a huge coercive field (Hc=1800 Oe) compared to the low temperature bulk values of the disordered fcc FePt. We observed that the coercive field and the magnetic saturation change with the time the sample is exposed to air and these changes are associated with the oxidation or passivation of the nanoparticle surface that gives place to a core-shell structure. Indeed, the study on the electronic properties of the nanoparticles confirms the magnetic results and indicat...

Shape Changes of Pt Nanoparticles Induced by Deposition on Mesoporous Silica

Polyvinylpyrollidone (PVP)-capped platinum nanoparticles (NPs) are found to change shape from spherical to flat when deposited on mesoporous silica substrates (SBA-15). Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) analyses are used in these studies. The SAXS results indicate that, after deposition, the 2 nm NPs have an average gyration radius 22% larger than in solution, while the EXAFS measurements indicate a decrease in first neighbor co-ordination number from 9.3 to 7.4. The deformation of these small capped NPs is attributed to interactions with the surface of the SBA-15 support, as evidenced by X-ray absorption near-edge structure (XANES).

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

Formation of an extended CoSi2 thin nanohexagons array coherently buried in silicon single crystal

A Co‐doped silica film was deposited on the surface of a Si(100) wafer and isothermally annealed at 750 °C to form spherical Co nanoparticles embedded in the silica film and a few atomic layer thick CoSi2 nanoplatelets within the wafer. The structure, morphology, and spatial orientation of the nanoplatelets were characterized. The experimental results indicate that the nanoplatelets exhibit hexagonal shape and a uniform thickness. The CoSi2 nanostructures lattice is coherent with the Si lattice, and each of them is parallel to one of the four planes belonging to the {111} crystallographic form of the host lattice.

Synthesis of ultra-small cysteine-capped gold nanoparticles by pH switching of the Au(I)-cysteine polymer.

We report a synthetic approach for the production of ultra-small (0.6 nm) gold nanoparticles soluble in water with a precise control of the nanoparticle size. Our synthetic approach utilizes a pH-depending Au-cysteine polymer as a quencher for the AuNPs grown. The method extends the synthetic capabilities of nanoparticles with sizes down to 1 nm. In addition to the strict pH control, the existence of free -SH groups present in the mixture of reaction has been observed as a key requirement for the synthesis of small nanoparticles in mild conditions. UV-Vis, SAXS, XANES, EXAFS and HR-TEM, has been used to determinate the particle size, characterization of the gold precursor and gold-cysteine interaction.