V. Dupuis

Magnetic anisotropy of a single cobalt nanocluster.

Using a new micro-SQUID setup, we investigate magnetic anisotropy in a single 1000-atom cobalt cluster. This system opens new fields in the characterization and understanding of the origin of magnetic anisotropy in such nanoparticles. For this purpose, we report three-dimensional switching field measurements performed on a 3 nm cobalt cluster embedded in a niobium matrix. We are able to separate the different magnetic anisotropy contributions and evidence the dominating role of the cluster surface.

FROM FREE CLUSTERS TO CLUSTER-ASSEMBLED MATERIALS

In this paper the specific properties of free clusters and the formation of new cluster-assembled materials using the low energy cluster beam deposition (LECBD) technique are discussed. Recent results obtained for free clusters are summarized with special attention to new observed structures. As for the specific structures and properties of cluster-assembled materials, two main aspects are specially emphasized: the memory effect of the free cluster properties leading to the formation of new phases and the effect of the specific nanostructure of the cluster-assembled materials related to the random cluster stacking mechanism characteristic of the LECBD. These effects and the corresponding potential applications are illustrated using some selected examples: new diamond-like carbon films produced by fullerene depositions (memory effect) and grain effect on the magnetic properties of cluster-assembled transition metal films.

Nontrivial Redox Behavior of Nanosized Cobalt: New Insights from Ambient Pressure X-ray Photoelectron and Absorption Spectroscopies

The reduction and oxidation of carbon-supported cobalt nanoparticles (3.50±0.22 nm) and a Co (0001) single crystal was investigated by ambient pressure X-ray photoelectron (APPES) and X-ray absorption (XAS) spectroscopies, applied in situ under 0.2 mbar hydrogen or oxygen atmospheres and at temperatures up to 620 K. It was found that cobalt nanoparticles are readily oxidized to a distinct CoO phase, which is significantly more stable to further oxidation or reduction compared to the thick oxide films formed on the Co(0001) crystal. The nontrivial size-dependence of redox behavior is followed by a difference in the electronic structure as suggested by theoretical simulations of the Co L-edge absorption spectra. In particular, contrary to the stable rocksalt and spinel phases that exist in the bulk oxides, cobalt nanoparticles contain a significant portion of metastable wurtzite-type CoO.

High sensitivity magnetization measurements of nanoscale cobalt clusters

Presented is a novel high sensitivity magnetometer allowing us to measure the magnetization reversal of about IO4 pB corresponding to a sensitivity of about IO-r6 emu. The detector is a niobium micro-bridge DC superconducting quantum interference device (SQUID), fabricated using electron-beam lithography. It is operational in the temperature range of O-7 K. Furthermore, we present a method to deposit on the SQUID loop a small number of Co clusters of about 2-5 nm in diameter. The first results obtained on these samples show that there is still a ferromagnetic coupling between the clusters and the magnetization reversal takes place by small avalanches

Structure and magnetism of well defined cobalt nanoparticles embedded in a niobium matrix

Our recent studies on Co-clusters embedded in various matrices reveal that the co-deposition technique (simultaneous deposition of two beams : one for the pre-formed clusters and one for the matrix atoms) is a powerful tool to prepare magnetic nanostructures with any couple of materials even though they are miscible. We study, both sharply related, structure and magnetism of the Co/Nb system. Because such a heterogeneous system needs to be described at different scales, we used microscopic and macroscopic techniques but also local selective absorption ones. We conclude that our clusters are 3 nm diameter f.c.c truncated octahedrons with a pure cobalt core and a solid solution between Co and Nb located at the interface which could be responsible for the magnetically inactive monolayers we found. The use of a very diluted Co/Nb film, further lithographed, would allow us to achieve a pattern of microsquid devices in view to study the magnetic dynamics of a single-Co cluster.

Accurate determination of the magnetic anisotropy in cluster-assembled nanostructures

The simultaneous triple adjustment of experimental magnetization curves under different conditions is shown to allow the unambiguous and consistent determination of both the magnetic particle size distribution and anisotropy for granular nanostructures of Co clusters embedded in protective matrices. The importance of interface effects resulting in magnetically dead layers is demonstrated.

Functional nanostructures from clusters

Functional cluster-assembled nanostructures with original structures and properties are prepared using the Low Energy Cluster Beam Deposition method (LECBD). This technique consists in depositing supersonic clusters produced in the gas phase using a combined laser vapourisation-inert gas condensation source. Low energy clusters with typical sizes ranging from ∼1 to a few nm are not fragmented upon impact on the substrate (soft landing regime) leading to the formation of cluster-assembled nanostructures which retain the original structures and properties of the incident free clusters. Model nanostructured systems of any kind of materials (metallic, covalent, oxides) well suited for fundamental studies in various fields (nanoelectronics, nanomagnetism, nanophotonics, catalysis or nanobiology) and for applications to very high integration-density devices (∼Tbits/in/²) are prepared using this method. After a brief review of techniques to produce, analyse, mass select, and deposit clusters in the LECBD-regime, the specific aspects of the nucleation and growth process which govern the formation of cluster-assembled nanostructures on the substrate are presented, especially the preparation of 2D-organised arrays of cluster-assembled dots by depositing low energy clusters on FIB-functionalised substrates. Characteristic examples of cluster systems prepared by LECBD are also described: i) metallic (Au, Ag, Au-Ag, Ag-Ni, Ag-Pt)) and oxide (Gd2O3, ZnO) cluster-assembled nanostructures for applications to linear and non linear nano-optics; ii) magnetic nanostructures from Co-based nanoclusters (i.e., Co-Pt) exhibiting a high magnetic anisotropy which is well suited for applications to high density data storage devices; iii) gold or Pd-Pt or Au-Ti clusters for chemical reactivity and catalysis applications. In some specific cases, we were able to perform studies from an isolated individual nanocluster up to 2D or 3D-collections of non-interacting or interacting particles leading to a rather good understanding of the intrinsic as well as the collective properties at nanoscale.

When a Metastable Oxide Stabilizes at the Nanoscale: Wurtzite CoO Formation upon Dealloying of PtCo Nanoparticles

Ambient pressure photoelectron and absorption spectroscopies were applied under 0.2 mbar of O2 and H2 to establish an unequivocal correlation between the surface oxidation state of extended and nanosized PtCo alloys and the gas-phase environment. Fundamental differences in the electronic structure and reactivity of segregated cobalt oxides were associated with surface stabilization of metastable wurtzite-CoO. In addition, the promotion effect of Pt in the reduction of cobalt oxides was pronounced at the nanosized particles but not at the extended foil.

Magnetic properties of nanostructured iron films obtained by low energy neutral cluster beam deposition

Abstract Nanocrystallized films of iron have been elaborated using for the first time the Low Energy Cluster Beam Deposition techniques. Structural characterizations have shown that the grain size distribution is very narrow and centered around 5 nm. The grain shape is almost spherical. Moreover, the density of the films is around 62% of bulk iron. Magnetic properties of the samples were studied using Mossbauer spectroscopy, ferromagnetic resonance and SQUID magnetometry. Experimental results have been quantitatively interpreted in the framework of the Random Anisotropy Model, with an exponential correlation of anisotropy directions extending up to 5 nm. In particular, the anisotropy and inter-grains exchange coupling energies have been determined.

STRUCTURAL, VIBRATIONAL, AND OPTICAL PROPERTIES OF SILICON CLUSTER ASSEMBLED FILMS

Distributions of neutral Si-clusters centered around mean sizes of 50 and 200 atoms have been produced using a laser vaporization source and deposited on various substrates at room temperature in ultrahigh vacuum. The Si-cluster assembled films obtained, resulting from the random stacking of incident free nanosize clusters, were subsequently coated by appropriate protective layers before removing in air to perform ex situ infrared, visible, Raman, and photoluminescence spectrometry measurements, as well as transmission electron microscopy observations. The main characteristics of the cluster films are comparable to those observed for amorphous hydrogenated silicon and quite different to those of conventional nanoporous structures or clusters larger than 2–3 nm. The observed intense photoluminescence signal and band gap suggest the presence of a low number of dangling bonds probably due to surface reconstruction effects, connections between adjacent clusters, and oxygen contamination. As for the oxygen con...