Multi-metallic nanoparticles constitute a new class of materials offering the opportunity to tune the properties via the composition, atomic ordering and size. In particular, supported bimetallic nanoparticles have generated intense interest in catalysis and electrocatalysis. However, traditional synthesis methods often lack precise control, yielding a mixture of monometallic and bimetallic particles with various compositions. Here we report a general strategy for synthesizing supported bimetallic nanoparticles by atomic layer deposition, where monometallic nanoparticle formation is avoided by selectively growing the secondary metal on the primary metal nanoparticle but not on the support; meanwhile, the size, composition and structure of the bimetallic nanoparticles are precisely controlled by tailoring the precursor pulse sequence. Such exquisite control is clearly demonstrated through in situ Fourier transform infrared spectroscopy of CO chemisorption by mapping the gradual atomic-scale evolution in the surface composition, and further confirmed using aberration-corrected scanning transmission electron microscopy.

This work investigates the electronic band structures of bulk Ge 1-x Sn x alloys using the empirical pseudopotential method (EPM) for Sn composition x varying from 0 to 0.2. The adjustable form factors of EPM were tuned in order to reproduce the band features that agree well with the reported experimental data. Based on the adjusted pseudopotential form factors, the band structures of Ge 1-x Sn x alloys were calculated along high symmetry lines in the Brillouin zone. The effective masses at the band edges were extracted by using a parabolic line fit. The bowing parameters of hole and electron effective masses were then derived by fitting the effective mass at different Sn compositions by a quadratic polynomial. The hole and electron effective mass were examined for bulk Ge 1-x Sn x alloys along specific directions or orientations on various crystal planes. In addition, employing the effective-mass Hamiltonian for diamond semiconductor, band edge dispersion at the C-point calculated by 8-band k.p. method was fitted to that obtained from EPM approach. The Luttinger-like parameters were also derived for Ge 1-x Sn x alloys. They were obtained by adjusting the effective-mass parameters of k.p method to fit the k.p band structure to that of the EPM. These effective masses and derived Luttinger parameters are useful for the design of optical and electronic devices based on Ge 1-x Sn x alloys. V C 2012 American Institute of Physics.

Supported precious metal single-atom catalysts have shown interesting activity and selectivity in recent studies. However, agglomeration of these highly mobile mononuclear surface species can eliminate their unique catalytic properties. Here we study a strategy for synthesizing thin film stabilized single-atom Pd1 catalysts using atomic layer deposition (ALD). The thermal stability of the Pd1 catalysts is significantly enhanced by creating a nanocavity thin film structure. In situ infrared spectroscopy and Pd K-edge X-ray absorption spectroscopy (XAS) revealed that the Pd1 was anchored on the surface through chlorine sites. The thin film stabilized Pd1 catalysts were thermally stable under both oxidation and reduction conditions. The catalytic performance in the methanol decomposition reaction is found to depend on the thickness of protecting layers. While Pd1 catalysts showed promising activity at low temperature in a methanol decomposition reaction, 14 cycle TiO2 protected Pd1 was less active at high temperature. Pd L3 edge XAS indicated that the low reactivity compared with Pd nanoparticles is due to the strong adsorption of carbon monoxide even at 250 °C. These results clearly show that the ALD nanocavities provide a basis for future design of single-atom catalysts that are highly efficient and stable.

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122̅) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO2 structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

We have developed colloidal synthesis methods to create nanoparticles (NPs) of tantalum nitride. The particle sizes and crystallinity can be controlled through the use of different organic solvents and reaction times; we demonstrate here NPs ranging in size from 2 to 23 nm. While electron microscopy and selected area diffraction demonstrate the synthesis of NPs of tantalum nitride (which may be partially oxidized), results from X-ray photoelectron spectroscopy reveal that the majority of the tantalum in our sample is present as an unidentified molecular-scale oxide species.