The role of surface diffusion in the growth mechanism of III-nitride nanowires and nanotubes.

The spontaneous growth of GaN nanowires (NWs) in absence of catalyst is controlled by the Ga flux impinging both directly on the top and on the side walls and diffusing to the top. The presence of diffusion barriers on the top surface and at the frontier between the top and the sidewalls, however, causes an inhomogeneous distribution of Ga adatoms at the NW top surface resulting in a GaN accumulation in its periphery. The increased nucleation rate in the periphery promotes the spontaneous formation of superlattices in InGaN and AlGaN NWs. In the case of AlN NWs, the presence of Mg can enhance the otherwise short Al diffusion length along the sidewalls inducing the formation of AlN nanotubes.

Growth of zinc-blende GaN on muscovite mica by molecular beam epitaxy.

The mechanisms of plasma-assisted molecular beam epitaxial growth of GaN on muscovite mica were investigated. Using a battery of techniques, including scanning and transmission electron microscopy, atomic force microscopy, cathodoluminescence, Raman spectroscopy and x-ray diffraction, it was possible to establish that, in spite of the lattice symmetry mismatch, GaN grows in epitaxial relationship with mica, with the [11-20] GaN direction parallel to [010] direction of mica. GaN layers could be easily detached from the substrate via the delamination of the upper layers of the mica itself, discarding the hypothesis of a van der Waals growth mode. Mixture of wurtzite (hexagonal) and zinc blende (ZB) (cubic) crystallographic phases was found in the GaN layers with ratios highly dependent on the growth conditions. Interestingly, almost pure ZB GaN epitaxial layers could be obtained at high growth temperature, suggesting the existence of a specific GaN nucleation mechanism on mica and opening a new way to the growth of the thermodynamically less stable ZB GaN phase.

Nonanuclear Spin-Crossover Complex Containing Iron(II) and Iron(III) Based on a 2,6-Bis(pyrazol-1-yl)pyridine Ligand Functionalized with a Carboxylate Group.

The synthesis and magnetostructural characterization of [Fe(III)3(µ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](ClO4)13·(CH3)2CO)6·(solvate) (2) are reported. This compound is obtained as a secondary product during synthesis of the mononuclear complex [Fe(II)(bppCOOH)2](ClO4)2 (1). The single-crystal X-ray diffraction structure of 2 shows that it contains the nonanuclear cluster of the formula [Fe(III)3(µ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](13+), which is formed by a central Fe(III)3O core coordinated to six partially deprotonated [Fe(II)(bppCOOH)(bppCOO)](+) complexes. Raman spectroscopy studies on single crystals of 1 and 2 have been performed to elucidate the spin and oxidation states of iron in 2. These studies and magnetic characterization indicate that most of the iron(II) complexes of 2 remain in the low-spin (LS) state and present a gradual and incomplete spin crossover above 300 K. On the other hand, the Fe(III) trimer shows the expected antiferromagnetic behavior. From the structural point of view, 2 represents the first example in which bppCOO(-) acts as a bridging ligand, thus forming a polynuclear magnetic complex.