Structural order in ultrathin films of the monolayer protected clusters based upon 4 nm gold nanocrystals: an experimental and theoretical study
N Bhattarai and S Khanal and D Bahena and JA Olmos-Asar and A Ponce and RL Whetten and MM Mariscal and M Jose-Yacaman, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 16, 18098-18104 (2014).
The structural order in ultrathin films of monolayer protected clusters (MPCs) is important in a number of application areas but can be difficult to demonstrate by conventional methods, particularly when the metallic core dimension, d, is in the intermediate size-range, 1.5 < d < 5.0 nm. Here, improved techniques for the synthesis of monodisperse thiolate-protected gold nanoparticles have made possible the production of dodecane-thiolate saturated similar to 4 +/- 0.5 nm Au clusters with single-crystal core structure and morphology. An ultrathin ordered film or superlattice of these nanocrystal-core MPCs is prepared and investigated using aberration corrected scanning/transmission electron microscopy (STEM) which allowed imaging of long-range hexagonally ordered superlattices of the nanocrystals, separated by the thiolate groups. The lattice constants determined by direct imaging are in good agreement with those determined by small-angle electron diffraction. The STEM image revealed the characteristic grain boundary (GB) with sigma (Sigma) 13 in the interface between two crystals. The formation and structures found are interpreted on the basis of theoretical calculations employing molecular dynamics (MD) simulations and coarse- grained (CG) approach.
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