Catalyst-free direct vapor-phase growth of Zn1?xCuxO micro-cross structures and their optical properties

We report a simple catalyst-free vapor-phase method to fabricate Zn_1−xCu_xO micro-cross structures. Through a series of controlled experiments by changing the location of the substrate and reaction time, we have realized the continuous evolution of product morphology from nanorods into brush-like structures and micro-cross structures at different positions, together with the epitaxial growth of branched nanorods from the central stem with the time extended. The growth mechanism of the Zn_1−xCu_xO micro-cross structures has been proposed to involve the synthesis of Cu/Zn square-like core, surface oxidation, and the secondary growth of nanorod arrays. By the detailed structural analysis of the yielded Zn_1−xCu_xO samples at different locations, we have shown that the CuO phases were gradually formed in Zn_1−xCu_xO, which is significant to induce the usual ZnO hexagonal structures changing into four-folded symmetrical hierarchical micro-cross structures. Furthermore, the visible luminescence can be greatly enhanced by the introduction of Cu, and the observed inhomogeneous cathode luminescence in an individual micro-cross structure is caused by the different distributions of Cu.