Tuning the size, composition and structure of Au and Co50Au50 nanoparticles by high-power impulse magnetron sputtering in gas-phase synthesis.

Gas-phase synthesis of nanoparticles with different structural and chemical distribution is reported using a circular magnetron sputtering in an ion cluster source by applying high-power impulses. The influence of the pulse characteristics on the final deposit was evaluated on Au nanoparticles. The results have been compared with the more common direct current approach. In addition, it is shown for the first time that high-power impulses in magnetron based gas aggregation sources allows the growth of binary nanoparticles, CoAu in this case, with a variety of crystalline and chemical arrangements which are analyzed at the atomic level.

Gas-Phase Synthesis of Nanoparticles: present status and perspectives.

There is an increasing interest in the generation of well-defined nanoparticles (NPs) not only because of their size-related particular properties, but also because they are promising building blocks for more complex materials in nanotechnology. Here, we will shortly introduce the gas phase synthesis technology that has evolved rapidly in the last years and allows the fabrication of complex NPs with controllable and tuneable chemical composition and structure while keeping very good control over the size distribution. We will also address some limitations of the technology (stability over time, production yield…) and discuss possible solutions.

Precisely controlled fabrication, manipulation and in-situ analysis of Cu based nanoparticles.

The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu0 to CuO through Cu2O, and their mixtures) at different stages in the machine.

Core@shell, Au@TiOx nanoparticles by gas phase synthesis.

Herein, gas phase synthesis and characterization of multifunctional core@shell, Au@TiOx nanoparticles have been reported. The nanoparticles were produced via a one-step process using a multiple-ion cluster source under a controlled environment that guaranteed the purity of the nanoparticles. The growth of the Au cores (6 nm diameter) is stopped when they pass through the Ti plasma where they are covered by an ultra-thin (1 nm thick) and homogeneous titanium shell that is oxidized in-flight before the soft-landing of the nanoparticles. The Au cores were found to be highly crystalline with icosahedral (44%) and decahedral (66%) structures, whereas the shell, mainly composed of TiO2 (79%), was not ordered. The highly electrical insulating behaviour of the titanium oxide shell was confirmed by the charging effect produced during X-ray photoemission spectroscopy.

Dispersion and Functionalization of Nanoparticles Synthesized by Gas Aggregation Source: Opening New Routes Toward the Fabrication of Nanoparticles for Biomedicine.

The need to find new nanoparticles for biomedical applications is pushing the limits of the fabrication methods. New techniques with versatilities beyond the extended chemical routes can provide new insight in the field. In particular, gas aggregation sources offer the possibility to fabricate nanoparticles with controlled size, composition, and structure out of thermodynamics. In this context, the milestone is the optimization of the dispersion and functionalization processes of nanoparticles once fabricated by these routes as they are generated in the gas phase and deposited on substrates in vacuum or ultra-high vacuum conditions. In the present work we propose a fabrication route in ultra-high vacuum that is compatible with the subsequent dispersion and functionalization of nanoparticles in aqueous media and, which is more remarkable, in one single step. In particular, we will present the fabrication of nanoparticles with a sputter gas aggregation source using a Fe50B50 target and their further dispersion and functionalization with polyethyleneglycol (PEG). Characterization of these nanoparticles is carried out before and after PEG functionalization. During functionalization, significant boron dissolution occurs, which facilitates nanoparticle dispersion in the aqueous solution. The use of different complementary techniques allows us to prove the PEG attachment onto the surface of the nanoparticles, creating a shell to make them biocompatible. The result is the formation of nanoparticles with a structure mainly composed by a metallic Fe core and an iron oxide shell, surrounded by a second PEG shell dispersed in aqueous solution. Relaxivity measurements of these PEG-functionalized nanoparticles assessed their effectiveness as contrast agents for magnetic resonance imaging (MRI) analysis. Therefore, this new fabrication route is a reliable alternative for the synthesis of nanoparticles for biomedicine.

The ultimate step towards a tailored engineering of core@shell and core@shell@shell nanoparticles.

Complex core@shell and core@shell@shell nanoparticles are systems that combine the functionalities of the inner core and outer shell materials together with new physico-chemical properties originated by their low (nano) dimensionality. Such nanoparticles are of prime importance in the fast growing field of nanotechnology as building blocks for more sophisticated systems and a plethora of applications. Here, it is shown that although conceptually simple a modified gas aggregation approach allows the one-step generation of well-controlled complex nanoparticles. In particular, it is demonstrated that the atoms of the core and the shell of the nanoparticles can be easily inverted, avoiding intrinsic constraints of chemical methods.

Matrix and interaction effects on the magnetic properties of Co nanoparticles embedded in gold and vanadium.

The study of the magnetic properties of Co nanoparticles (with an average diameter of 10.3 nm) grown using a gas-phase aggregation source and embedded in Au and V matrices is presented. We investigate how the matrix, the number of embedded nanoparticles (counted by coverage percentage), the interparticle interactions and the complex nanoparticles/matrix interface structure define the magnetic properties of the studied systems. A threshold coverage of 3.5% of a monolayer was found in both studied systems: below this coverage, nanoparticles behave as an assembly of independent single-domain magnetic entities with uniaxial anisotropy. Above the threshold it is found that the magnetic behavior of the systems is more matrix dependent. While magnetic relaxation and Henkel plots measurements stress the importance of the dipolar interactions and the formation of coherent clusters in the case of the Au matrix, the magnetic behavior of cobalt clusters embedded in the vanadium matrix is explained through the formation of a spin glass-like state at the V-Co interface that screens the magnetic interactions between NPs.

Generation of nanoparticles with adjustable size and controlled stoichiometry: recent advances.

We present a bottom-up fabrication route based on the sputtering gas aggregation source that allows the generation of nanoparticles with controllable and tunable chemical composition while keeping the control of the cluster size. We demonstrate that the chemical composition of the particles can be monitored by the individual adjustment of the working parameters of the magnetrons inserted in a gas aggregation zone. Such control of the parameters leads to a fine control of the ion density of each target material and hence to the control of the chemical composition of the nanoparticles. In particular, we show through X-ray photoemission, atomic force microscopy, and high-resolution transmission electron microscopy that it is possible to generate bimetallic (AgAu) and trimetallic (AgAuPd) alloy nanoparticles with well-defined and tunable stoichiometries from three targets of pure Ag, Au, and Pd. The proposed route for the generation of nanoparticles opens new possibilities for the fabrication of nanoparticles using a physical method that, for some applications, could be complementary to the chemical methods.

Aspect-ratio and lateral-resolution enhancement in force microscopy by attaching nanoclusters generated by an ion cluster source at the end of a silicon tip.

One of the factors that limit the spatial resolution in atomic force microscopy (AFM) is the physical size of the probe. This limitation is particularly severe when the imaged structures are comparable in size to the tip's apex. The resolution in the AFM is usually enhanced by using sharp tips with high aspect ratios. In the present paper we propose an approach to modify AFM tips that consists of depositing nanoclusters on standard silicon tips. We show that the use of those tips leads to atomic force microscopy images of higher aspect ratios and spatial resolution. The present approach has two major properties. It provides higher aspect-ratio images of nanoscale objects and, at the same time, enables to functionalize the AFM tips by depositing nanoparticles with well-controlled chemical composition.

Study of the valence state and electronic structure in Sr(2)FeMO(6) (M = W, Mo, Re and Sb) double perovskites.

The knowledge of the oxidation state of the transition metal cations in Sr(2)FeMO(6) (M = W, Mo, Re and Sb) double perovskites is of paramount importance to understand their appealing magnetoresistive or magnetic properties. We present a systematic investigation of the valences of Fe, W, Mo, Re and Sb cations in these perovskites using three different and complementary techniques of analysis. We have used a diffraction method, neutron powder diffraction (NPD), coupled with the bond-valence model; and two spectroscopy methods, X-ray photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). These two techniques are also complementary since XPS analyses the surface of the samples whereas XAS probes the bulk material. The analysis of the Fe K-edge spectra of the four samples shows a clear shift of the Fe K-edge as the valence of iron increases in the sequence M = W, Mo, Re and Sb. In addition, XANES pre-edge structures unveil a progressive reduction in the occupancy level of the Fe-3d band as the oxidation state of iron increases along the sequence M = W, Mo, Re and Sb. Finally, XANES computations have determined the electronic structures of Sr(2)FeWO(6), Sr(2)FeMoO(6), Sr(2)FeReO(6) and Sr(2)FeSbO(6).

Patterning polymeric structures with 2 nm resolution at 3 nm half pitch in ambient conditions.

The miniaturization limits of electronic and mechanical devices depend on the minimum pattern periodicity that is stable in ambient conditions. Here we demonstrate an atomic force microscopy lithography that enables the patterning of 2 nm organic structures with 6 nm periodicities in air. We also demonstrate that the lithography can be up-scaled for parallel patterning. The method is based on the formation of a nanoscale octane meniscus between a sharp conductive protrusion and a silicon (100) surface. The application of a high electrical field ( approximately 10 V/nm) produces the polymerization and cross-linking of the octane molecules within the meniscus followed by their deposition. The resulting pattern periodicities are very close to the ultimate theoretical limits achievable in air ( approximately 3 nm). The chemical composition of the patterns has been characterized by photoemission spectroscopy.

A study of the response of Y3Al5O12:Ce phosphor powder screens in the vacuum ultraviolet and soft X-ray regions using synchrotron radiation.

Phosphor screens find application in many fields because of their ability to convert incident radiation to wavelengths that are readily measured by modern detectors. While the response of such screens in the X-ray region has been widely studied, much work still remains to be done regarding their response in the vacuum ultraviolet and soft X-ray regions, where the response is predicted to be non-linear owing to the presence of elemental absorption edges. Here, an experiment using synchrotron radiation to determine the response of thin Y(3)Al(5)O(12):Ce (1-21 mg cm(-2)) and Y(2)O(3):Eu (2.64 mg cm(-2)) powder phosphor screens in the spectral range 20-900 A (13.8-620 eV) is reported. Also, a custom-built camera is described which permits simultaneous collection of the forward- and backward-emitted light and that enables measurements to be made at various positions across the screens and at several screen/incident beam angles. Finally, features in the response spectra are identified, and efficiencies across the spectral range indicated for different screen thicknesses and operating modes are plotted, before a curve of the intrinsic radiant efficiency of Y(3)Al(5)O(12):Ce is produced. The results are discussed in the context of other measurements.