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Two-dimensional ZnO nanowall networks were grown on ZnO-coated silicon by thermal evaporation at low temperature without catalysts or additives. All of the results from scanning electronic spectroscope, X-ray diffraction and Raman scattering confirmed that the ZnO nanowalls were vertically aligned and c-axis oriented. The room-temperature photoluminescence spectra showed a dominated UV peak at 378 nm, and a much suppressed orange emission centered at similar to 590 nm. This demonstrates fairly good crystal quality and optical properties of the product. A possible three-step, zinc vapor-controlled process was proposed to explain the growth of well-aligned ZnO nanowall networks. The pre-coated ZnO template layer plays a key role during the synthesis process, which guides the growth direction of the synthesized products. (C) 2007 Elsevier B.V. All rights reserved.