Surfactant-Directed Fabrication of Supercrystals from the Assembly of Polyhedral Au–Pd Core–Shell Nanocrystals and Their Electrical and Optical Properties

Au–Pd core–shell nanocrystals with cubic, truncated cubic, cuboctahedral, truncated octahedral, and octahedral structures have been employed to form micrometer-sized polyhedral supercrystals by both the droplet evaporation method and novel surfactant diffusion methods. Observation of cross-sectional samples indicates shape preservation of interior nanocrystals within a supercrystal. Low-angle X-ray diffraction techniques and electron microscopy have been used to confirm the presence of surfactant between contacting nanocrystals. By diluting the nanocrystal concentration or increasing the solution temperature, supercrystal size can be tuned gradually to well below 1 μm using the surfactant diffusion method. Rectangular supercrystal microbars were obtained by increasing the amounts of cubic nanocrystals and surfactant used. Au–Ag core–shell cubes and PbS cubes with sizes of 30–40 nm have also been fabricated into supercrystals, showing the generality of the surfactant diffusion approach to form supercrystals with diverse composition. Electrical conductivity measurements on single Au–Pd supercrystals reveal loss of metallic conductivity due to the presence of insulating surfactant. Cubic Au–Pd supercrystals show infrared absorption at 3.2 μm due to extensive plasmon coupling. Mie-type resonances centered at 9.8 μm for the Au–Pd supercrystals disappear once the Pd shells are converted into PdH after hydrogen absorption.