Catalyst-free synthesis of single crystalline ZnO nanonails with ultra-thin caps

Arrays of single-crystalline ZnO nanonails with tapering diameters and ultra-thin caps have been successfully synthesized on a silicon substrate via a simple catalyst-free thermal evaporation method. Each of the ZnO nanonails consists a nanowire (stem) on the bottom and an ultra-thin symmetrical hexagonal cap on the top. Structural characterization reveals that the synthesized ZnO nanonail has a wurtzite (WZ) structure with a preferred growth direction of [0001] in the stem and <2<(1)over bar>(1) over bar0> in the cap. Remarkably, the ultra-thin cap shows a diameter-to-thickness ratio of over 20:1, which is much higher in magnitude than those reported in previous works. Based on the systematic morphological characterization and structural analysis, a self-catalyzed vapor-liquid-solid (VLS) mechanism followed by a vapor-solid (VS) process is proposed to explain the growth of the nanonails. Optical properties are also investigated with Raman and photoluminescence (PL) techniques, which show good crystal quality of the synthesized nanonails.