Effects of Nanoparticle Shape on the Morphology and Properties of Porous CdSe Assemblies (Aerogels)

We demonstrate the effect of differently shaped CdSe nanoscale building blocks (dots, rods, branched nanoparticles, and hyperbranched nanoparticles) on the morphologies, surface characteristics, and optical properties of resultant porous CdSe nanostructured aerogels. Monolithic CdSe aerogels were produced by controlled oxidative removal of surface thiolate ligands from differently shaped CdSe nanoparticles to yield a wet gel, followed by CO(2) supercritical drying. The X-ray diffraction data show that the resultant CdSe aerogels maintain the crystalline phase of the building blocks without significant grain growth. However, the transmission electron microscopy images indicate that the morphology of CdSe aerogels changes from a colloid-type morphology to a polymer-type morphology when the building block changes from dot to rod or the branched nanoparticle. The morphology of the CdSe aerogel assembled from hyperbranched nanoparticles appears to be intermediate between the colloid-type and the polymer-type. Nitrogen physisorption measurements suggest that the surface areas and porosity are a direct function of the shape of the primary building blocks, with aerogels formed from rods or branched particles exhibiting the greatest surface areas (>200 m(2)/g) and those prepared from hyperbranched nanoparticles exhibiting the least (<100 m(2)/g). Band gap measurements and photoluminescence studies show that the as-prepared CdSe aerogels retain to a large extent the intrinsic quantum confinement of the differently shaped building blocks, despite being connected into a 3D network.