Pressure stability and low compressibility of intercalated cagelike materials: the case of silicon clathrates

We study the behavior under pressure (up to 35 GPa) of intercalated silicon clathrates, combining x-ray diffraction experiments and ab initio calculations. We show that endohedral doping does not introduce a strong modification of the compressibility of the empty clathrate network and that in particular cases can raise it to values equivalent to the one of the silicon diamond phase. Intercalation can also prevent the collapse of the cage structure up to pressures at least 3 times higher than in the empty clathrate. Further we find that the stability of all studied silicon clathrate networks as well as stressed silicon diamond is limited to average Si-Si interatomic distances higher than 2.30 Angstrom

Guest displacement in silicon clathrates

We study both theoretically and experimentally the structure of the doped silicon clathrate II NaxSi34. We find that contrary to published works, the sodium atoms do not retain the T-d symmetry inside the Si-28 cages and move about 1 A away from the center of the cage. This displacement, in conjunction with that of a sodium atom in an adjacent Si-28 cage, leads to a "dimerization" of sodium atoms. As a consequence, Rietveld refinements of x-ray diffraction spectra and transport, vibrational, and electronic properties must be revisited

A new class of low compressibility materials: Clathrates of silicon and related materials

We discuss the high pressure properties of different silicon clathrate structures that we have investigated by means of X-ray diffraction and ab initio calculations. Compressibility transition pressures or phase transformations are interpreted as a function of the nature of the guest atom intercalation, The compressibility of the clathrate structure is in all cases close to that of silicon diamond whereas transition pressures or the high pressure phases are extremely depending on the nature of the guest atom. We address the implications for obtaining a metallic material as hard as diamond

Superconductivity in doped sp3 semiconductors: The case of the clathrates

We present a joint experimental and theoretical study of the superconductivity in doped silicon clathrates. The critical temperature in Ba-8@Si-46 is shown to strongly decrease with applied pressure. These results are corroborated by ab initio calculations using MacMillan's formulation of the BCS theory with the electron-phonon coupling constant lambda calculated from perturbative density functional theory. Further, the study of I-8@Si-46 and of gedanken pure silicon diamond and clathrate phases doped within a rigid-band approach show that the superconductivity is an intrinsic property of the sp(3) silicon network. As a consequence, carbon clathrates are predicted to yield large critical temperatures with an effective electron-phonon interaction much larger than in C-60

Structural and magnetic properties of CoPt mixed clusters

In this present work, we report a structural and magnetic study of mixed Co58Pt42 clusters. MgO, Nb and Si matrix can be used to embed clusters, avoiding any magnetic interactions between particles. Transmission Electron Microscopy (TEM) observations show that Co58Pt42 supported isolated clusters are about 2nm in diameter and crystallized in the A1 fcc chemically disordered phase. Grazing Incidence Small Angle X-ray Scattering (GISAXS) and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) reveal that buried clusters conserve these properties, interaction with matrix atoms being limited to their first atomic layers. Considering that 60% of particle atoms are located at surface, this interactions leads to a drastic change in magnetic properties which were investigated with conventional magnetometry and X-Ray Magnetic Circular Dichro\"{i}sm (XMCD). Magnetization and blocking temperature are weaker for clusters embedded in Nb than in MgO, and totally vanish in silicon as silicides are formed. Magnetic volume of clusters embedded in MgO is close to the crystallized volume determined by GIWAXS experiments. Cluster can be seen as a pure ferromagnetic CoPt crystallized core surrounded by a cluster-matrix mixed shell. The outer shell plays a predominant role in magnetic properties, especially for clusters embedded in niobium which have a blocking temperature 3 times smaller than clusters embedded in MgO

Interface magnetic anisotropy in cobalt clusters embedded in a platinum or niobium matrix

A low concentration of cobalt clusters with a fcc structure and containing almost one thousand atoms are embedded in two different metallic matrices: platinum and niobium. Samples have been prepared using a co-deposition technique. Cobalt clusters preformed in the gas phase and matrix atoms are simultaneously deposited on a silicon substrate under Ultra High Vacuum conditions. This original technique allows to prepare nanostructured systems from miscible elements such as Co/Pt and Co/Nb in which clusters keep a pure cobalt core surrounded with an alloyed interface. Magnetic measurements performed using a Vibrating Sample Magnetometer (VSM) reveal large differences in the magnetic properties of cobalt clusters in Pt and Nb pointing out the key role of cluster/matrix interfaces.Comment: 7 pages (LaTeX), 12 PostScript figures, 1 PostScript tabl

YAG nano-light sources with high Ce concentration

We investigate the luminescence properties of 10 nm YAG nanoparticles doped with Ce ions at 0.2%, 4% and 13% that are designed as active probes for Scanning Near field Optical Microscopy. They are produced by a physical method without any subsequent treatment, which is imposed by the desired application. The structural analysis reveals the amorphous nature of the particles, which we relate to some compositional defect as indicated by the elemental analysis. The optimum emission is obtained with a doping level of 4%. The emission of the YAG nanoparticles doped at 0.2% is strongly perturbed by the crystalline disorder whereas the 13% doped particles hardly exhibit any luminescence. In the latter case, the presence of Ce4+ ions is confirmed, indicating that the Ce concentration is too high to be incorporated efficiently in YAG nanoparticles in the trivalent state. By a unique procedure combining cathodoluminescence and Rutherford backscattering spectrometry, we demonstrate that the enhancement of the particles luminescence yield is not proportional to the doping concentration, the emission enhancement being larger than the Ce concentration increase. Time-resolved photoluminescence reveals the presence of quenching centres likely related to the crystalline disorder as well as the presence of two distinct Ce ions populations. Eventually, nano-cathodoluminescence indicates that the emission and therefore the distribution of the doping Ce ions and of the defects are homogeneous

Correlation between the Extraordinary Hall Effect and Resistivity

We study the contribution of different types of scattering sources to the extraordinary Hall effect. Scattering by magnetic nano-particles embedded in normal-metal matrix, insulating impurities in magnetic matrix, surface scattering and temperature dependent scattering are experimentally tested. Our new data, as well as previously published results on a variety of materials, are fairly interpreted by a simple modification of the skew scattering model

Fluorescent oxide nanoparticles adapted to active tips for near-field optics

We present a new kind of fluorescent oxide nanoparticles with properties well suited to active-tip based near-field optics. These particles with an average diameter in the range 5-10 nm are produced by Low Energy Cluster Beam Deposition (LECBD) from a YAG:Ce3+ target. They are studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), classical photoluminescence, cathodoluminescence and near-field scanning optical microscopy (NSOM). Particles of extreme photo-stability as small as 10 nm in size are observed. These emitters are validated as building blocks of active NSOM tips by coating a standard optical tip with a 10 nm thick layer of YAG:Ce3+ particles directly in the LECBD reactor and by subsequently performing NSOM imaging of test surfaces.Comment: Changes made following Referee's comments; added references; one added figure. See story on this article at: http://nanotechweb.org/cws/article/tech/3606

Engineered inorganic core/shell nanoparticles

International audienceIt has been for a long time recognized that nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic structures. At first, size effects occurring in single elements have been studied. More recently, progress in chemical and physical synthesis routes permitted the preparation of more complex structures. Such structures take advantages of new adjustable parameters including stoichiometry, chemical ordering, shape and segregation opening new fields with tailored materials for biology, mechanics, optics magnetism, chemistry catalysis, solar cells and microelectronics. Among them, core/shell structures are a particular class of nanoparticles made with an inorganic core and one or several inorganic shell layer(s). In earlier work, the shell was merely used as a protective coating for the core. More recently, it has been shown that it is possible to tune the physical properties in a larger range than that of each material taken separately. The goal of the present review is to discuss the basic properties of the different types of core/shell nanoparticles including a large variety of heterostructures. We restrict ourselves on all inorganic (on inorganic/inorganic) core/shell structures. In the light of recent developments, the applications of inorganic core/shell particles are found in many fields including biology, chemistry, physics and engineering. In addition to a representative overview of the properties, general concepts based on solid state physics are considered for material selection and for identifying criteria linking the core/shell structure and its resulting properties. Chemical and physical routes for the synthesis and specific methods for the study of core/shell nanoparticle are briefly discussed