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Effective methods for the synthesis of high-purity nanoparticles (NPs) have been extensively studied for a few decades. Among others, cold plasma-based sputtering metals onto a liquid substrate appears to be a very promising technique for the synthesis of high-purity NPs. The process enables the production of very small NPs without using any toxic reagents and complex chemical synthesis routes, and enables the synthesis of alloy NPs which can be the first step towards the formation of porous NPs. In this paper, the synthesis of gold-copper alloy NPs has been performed by co-sputtering gold and copper targets over pentaerythritol ethoxylate. The resulting solutions contain a mixture of gold, copper oxide, and alloy NPs having a radius of few angstroms. The annealing of these NPs, inside the solution, has been performed in order to increase their size and further induce the dealloying of the Au-Cu NPs. The resulting NPs exhibit either a nanoporous structure or are self-organized in an agglomerate of small NPs.

Lamellar nanoporous gold thin films, constituted of a stack of very thin layers of porous gold, are synthesized by chemical etching from a stack of successively deposited nanolayers of copper and gold. The gold ligament size, the pore size and the distance between lamellas are tunable in the few tens nanometer range by controlling the initial thickness of the layers and the etching time. The SERS activity of these lamellar porous gold films is characterized by their SERS responses after adsorption of probe bipyridine and naphtalenethiol molecules. The SERS signal is investigated as a function of the bipyridine concentration from 10 -14 mol L -1 to 10 -3 mol L -1 . The higher SERS response corresponds to an experimental detection limit down to 10 -12 mol L -1 . These performance is mainly attributed to the specific nanoporous gold architecture and the larger accessible surface to volume ratio. The lamellar nanoporous gold substrate is explored for sensitive SERS detection of dimethyl methylphosphonate (DMMP), a surrogate molecule of the highly toxic G-series nerve agents. The resultant nanostructure facilitates the diffusion of target molecules through the nanopores and their localization at the enhancing metallic surface leading to the unequivocal Raman signature of DMMP at a concentration of 5 parts per million.

We report on a novel fabrication approach of metal nanowires with complex surface. Taking advantage of nodular growth triggered by the presence of surface defects created intentionally on the substrate as well as the high tilt angle between the magnetron source axis and the normal to the substrate, metal nanowires containing hillocks emerging out of the surface can be created. The approach is demonstrated for several metals and alloys including gold, copper, silver, gold-copper and gold-silver. We demonstrate that applying an electrochemical dealloying process to the gold-copper alloy nanowire arrays allows for transforming the hillocks into ring-like shaped nanopores. The resulting porous gold nanowires exhibit a very high roughness and high specific surface making of them a promising candidate for the development of SERS-based sensors.

Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure. On the other hand, by applying a sequential oxidation and reduction reactions to copper nanowires, one can synthesize hollow nanoobjects with complex shapes and morphologies that cannot be obtained using the Kirkendall effect alone, such as necklace-like cuprous oxide nanotubes, periodic solid copper nanoparticles or hollow cuprous oxide nanospheres interconnected with single crystal cuprous oxide nanorods, and aligned and periodic hollow nanospheres embedded in a cuprous oxide nanotube. The strategy demonstrated in this study opens new avenues for the engineering of hollow nanostructures with potential applications in gas sensing, catalysis, and energy storage., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanoporous materials are of great interest for various technological applications including sensors based on surface-enhanced Raman scattering, catalysis, and biotechnology. Currently, tremendous efforts are dedicated to the development of porous one-dimensional materials to improve the properties of such class of materials. The main drawback of the synthesis approaches reported so far includes (i) the short length of the porous nanowires, which cannot reach the macroscopic scale, and (ii) the poor organization of the nanostructures obtained by the end of the synthesis process. In this work, we report for the first time on a two-step approach allowing creating highly ordered porous gold nanowire arrays with a length up to a few centimeters. This two-step approach consists of the growth of gold/copper alloy nanowires by magnetron cosputtering on a nanograted silicon substrate, serving as a physical template, followed by a selective dissolution of copper by an electrochemical anodic process in diluted sulfuric acid. We demonstrate that the pore size of the nanowires can be tailored between 6 and 21 nm by tuning the dealloying voltage between 0.2 and 0.4 V and the dealloying time within the range of 150-600 s. We further show that the initial gold content (11 to 26 atom %) and the diameter of the gold/copper alloy nanowires (135 to 250 nm) are two important parameters that must carefully be selected to precisely control the porosity of the material.

Nanoporous materials are of great importance for a broad range of applications including catalysis, optical sensors and water filtration. Although several approaches already exist for the creation of nanoporous materials, the race for the development of versatile methods, more suitable for the nanoelectronics industry, is still ongoing. In this communication we report for the first time on the possibility of generating nanoporosity in silver nanocolumns using a dry approach based on the oxidation of silver by direct exposure to a commercially available radio-frequency air plasma. The silver nanocolumns are created by glancing angle deposition using magnetron sputtering of a silver target in pure argon plasma. We show that upon exposure to the rf air plasma, the nanocolumns transform from solid silver into nanoporous silver oxide. We further show that by tuning the plasma pressure and the exposure duration, the oxidation process can be finely adjusted allowing for precisely controlling the morphology and the nanoporosity of the silver oxide nanocolumns. The generation of porosity within the silver nanocolumns is explained according to a cracking-induced oxidation mechanism based on two repeated events occurring alternately during the oxidation process: (i) oxidation of silver upon exposure to the air plasma and (ii) generation of nanocracks and blisters within the oxide layer due to the high internal stress generated within the material during oxidation.

Understanding the dealloying mechanisms of gold-based alloy thin films resulting in the formation of nanoporous gold with a sponge-like structure is essential for the future design and integration of this novel class of material in practical devices. Here we report on the synthesis of nanoporous gold thin films using a free-corrosion approach in nitric acid applied to cosputtered Au-Cu thin films. A relationship is established between the as-grown Au-Cu film characteristics (i.e., composition, morphology, and structure) and the porosity of the sponge-like gold thin films. We further demonstrate that the dealloying approach can be applied to nonhomogenous Au-Cu alloy thin films consisting of periodic and alternate Au-rich/Au-poor nanolayers. In such a case, however, the dealloying process is found to be altered and unusual etching stages arise. Thanks to defects and column boundaries playing the role of channels, the nitric acid is found to quickly penetrate within the films and then laterally (i.e., parallel to the film surface) attacks the nanolayers rather than perpendicularly. As a consequence to this anisotropic etching, the Au-poor layers are etched preferentially and transform into Au pillars holding the Au-rich layers and preventing them against collapsing. A further exposure to nitric acid results in the collapsing of the Au-rich layers accompanied by a transition from a multilayered to a sponge-like structure. A scenario, supported by experimental observations, is further proposed to provide a detailed explanation of the fundamental mechanisms occurring during the dealloying process of films with a multilayered structure.

The nanomanipulation of metal nanoparticles inside oxide nanotubes, synthesized by means of the Kirkendall effect, is demonstrated. In this strategy, a focused electron beam, extracted from a transmission electron microscope source, is used to site-selectively heat the oxide material in order to generate and steer a metal ion diffusion flux inside the nanochannels. The metal ion flux generated inside the tube is a consequence of the reduction of the oxide phase occurring upon exposure to the e-beam. We further show that the directional migration of the metal ions inside the nanotubes can be achieved by locally tuning the chemistry and the morphology of the channel at the nanoscale. This allows sculpting organized metal nanoparticles inside the nanotubes with various sizes, shapes, and periodicities. This nanomanipulation technique is very promising since it enables creating unique nanostructures that, at present, cannot be produced by an alternative classical synthesis route.

Highly ordered ultra-long oxide nanotubes are fabricated by a simple two-step strategy involving the growth of copper nanowires on nanopatterned template substrates by magnetron sputtering, followed by thermal annealing in air. The formation of such tubular nanostructures is explained according to the nanoscale Kirkendall effect. The concept of this new fabrication route is also extendable to create periodic zero-dimensional hollow nanostructures., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The growth of single-crystal CuO nanowires by thermal annealing of copper thin films in air is studied. We show that the density, length, and diameter of the nanowires can be controlled by tuning the morphology and structure of the copper thin films deposited by DC magnetron sputtering. After identifying the optimal conditions for the growth of CuO nanowires, chemical bath deposition is employed to coat the CuO nanowires with CdS in order to form p-n nanojunction arrays. As revealed by high-resolution TEM analysis, the thickness of the polycrystalline CdS shell increases when decreasing the diameter of the CuO core for a given time of CdS deposition. Near-edge x-ray absorption fine-structure spectroscopy combined with transmission x-ray microscopy allows the chemical analysis of isolated nanowires. The absence of modification in the spectra at the Cu L and O K edges after the deposition of CdS on the CuO nanowires indicates that neither Cd nor S diffuse into the CuO phase. We further demonstrate that the core-shell nanowires exhibit the I-V characteristic of a resistor instead of a diode. The electrical behavior of the device was found to be photosensitive, since increasing the incident light intensity induces an increase in the collected electrical current.

We report on an efficient strategy for the fabrication of an ultra-long suspended nanowire mesh suitable for nanodevice architectures on a polymer surface. First, nickel nanowires are synthesized directly on a template substrate by magnetron sputtering. Laser interference lithography followed by deep reactive ion etching is used to create the nanograted template substrate constituted of one-dimensional line pattern arrays of 240 nm in periodicity. Ordered alignment of ultra-long nanowires (∼180 nm in diameter) with high fidelity to the template pattern is observed by scanning electron microscopy. The transfer of the pre-defined parallel nanowire array from the template surface to a target polymer substrate for electrical characterization of the system is demonstrated. The electrical behaviour of the nanowire mesh, suspended between two electrodes, was found to be linear, stable, and reproducible. This result suggests that this nanofabrication process will open an efficient way to the design and construction of novel nanodevices.

We report on the synthesis and magnetic characterization of ultralong (1 cm) arrays of highly ordered coaxial nanowires with nickel cores and graphene stacking shells (also known as metal-filled carbon nanotubes). Carbon-containing nickel nanowires are first grown on a nanograted surface by magnetron sputtering. Then, a post-annealing treatment favors the metal-catalyzed crystallization of carbon into stacked graphene layers rolled around the nickel cores. The observed uniaxial magnetic anisotropy field oriented along the nanowire axis is an indication that the shape anisotropy dominates the dipolar coupling between the wires. We further show that the thermal treatment induces a decrease in the coercivity of the nanowire arrays. This reflects an enhancement of the quality of the nickel nanowires after annealing attributed to a decrease of the roughness of the nickel surface and to a reduction of the defect density. This new type of graphene-ferromagnetic-metal nanowire appears to be an interesting building block for spintronic applications.

Hierarchical carbon nanostructures based on ultra-long carbon nanofibers (CNF) decorated with carbon nanotubes (CNT) have been prepared using plasma processes. The nickel/carbon composite nanofibers, used as a support for the growth of CNT, were deposited on nanopatterned silicon substrate by a hybrid plasma process, combining magnetron sputtering and plasma-enhanced chemical vapor deposition (PECVD). Transmission electron microscopy revealed the presence of spherical nanoparticles randomly dispersed within the carbon nanofibers. The nickel nanoparticles have been used as a catalyst to initiate the growth of CNT by PECVD at 600°C. After the growth of CNT onto the ultra-long CNF, SEM imaging revealed the formation of hierarchical carbon nanostructures which consist of CNF sheathed with CNTs. Furthermore, we demonstrate that reducing the growth temperature of CNT to less than 500°C leads to the formation of carbon nanowalls on the CNF instead of CNT. This simple fabrication method allows an easy preparation of hierarchical carbon nanostructures over a large surface area, as well as a simple manipulation of such material in order to integrate it into nanodevices.

The incorporation of metal or metal carbide nanoparticles into carbon nanofibers modifies their properties and enlarges their field of application. The purpose of this work is to report a new non-catalytic and easy method to prepare organized metal carbide-carbon composite nanofibers on nanopatterned silicon substrates prepared by laser interference lithography coupled with deep reactive ion etching. Titanium carbide-carbon composite nanofibers were grown on the top of the silicon lines parallel to the substrate by a hybrid plasma process combining physical vapor deposition and plasma enhanced chemical vapor deposition. The prepared nanofibers were analyzed by scanning electron microscopy, x-ray photoelectron spectroscopy, Raman spectroscopy and transmission electron microscopy. We demonstrate that the shape, microstructure and the chemical composition of the as-grown nanofibers can be tuned by changing the plasma conditions.

An original approach was developed and validated for the fabrication of a carbon nanotube (CNT) electrode synthesized directly onto a carbon buffer thin film deposited on a highly doped monocrystalline silicon surface. The buffer layer of amorphous carbon thin film was deposited by physical vapour deposition on the silicon substrate before CNT synthesis. For this purpose, nickel was deposited on the carbon buffer layer by an electrochemical procedure and used as a catalyst for the CNT growth. The CNT synthesis was achieved by plasma enhanced chemical vapour deposition (PECVD) in an electron cyclotron resonance (ECR) plasma chamber using a C(2)H(2)/NH(3) gas mixture. In order to evaluate the electrochemical behaviour of the CNT-based electrode, the carbon layer and the silicon/carbon interface were studied. The resulting buffer layer enhanced the electronic transport from the doped silicon to the CNTs. The electrode surface was studied by XPS and characterized by both SEM and TEM. The electrochemical response exhibited by the resulting electrodes modified with CNTs was also examined by cyclic voltammetry. The whole process was found to be compatible with silicon microtechnology and could be envisaged for the direct integration of microsensors on silicon chips.