Vertically well-aligned ZnO nanoridge, nanorod, nanorod-nanowall junction, and nanotip arrays have been successfully synthesized on Si (100) substrates using a pulsed laser deposition prepared ZnO film as seed layer by thermal evaporation method. Experimental results illustrated that the growth of different morphologies of ZnO nanostructures was strongly dependent upon substrate temperature. X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies showed that the ZnO nanostructures were single crystals with a wurtzite structure. Compared with those of the other nanostructures, the photoluminescence (PL) spectrum of nanorod-nanowall junctions showed the largest intensity ratio of ultraviolet (UV) to yellow-green emission and the smallest full-width at half-maximum (FWHM) of the UV peak, reflecting the high optical quality and nearly defect free of crystal structure. The vertical alignment of the nanowire array on the substrate is attributed to the epitaxial growth of the nanostructures from the ZnO buffer layer. The growth mechanism was also discussed in detail. (c) 2006 Elsevier B.V. All rights reserved.