Semiconducting nanowires offer the possibility of nearly unlimited complex bottom-up design1,2, which allows for new device concepts3,4. However, essential parameters that determine the electronic quality of the wires, and which have not been controlled yet for the III–V compound semiconductors, are the wire crystal structure and the stacking fault density5. In addition, a significant feature would be to have a constant spacing between rotational twins in the wires such that a twinning superlattice is formed, as this is predicted to induce a direct bandgap in normally indirect bandgap semiconductors6,7, such as silicon and gallium phosphide. Optically active versions of these technologically relevant semiconductors could have a significant impact on the electronics8 and optics9 industry. Here we show first that we can control the crystal structure of indium phosphide (InP) nanowires by using impurity dopants. We have found that zinc decreases the activation barrier for two-dimensional nucleation growth of zinc-blende InP and therefore promotes crystallization of the InP nanowires in the zinc-blende, instead of the commonly found wurtzite, crystal structure10. More importantly, we then demonstrate that we can, once we have enforced the zinc-blende crystal structure, induce twinning superlattices with long-range order in InP nanowires. We can tune the spacing of the superlattices by changing the wire diameter and the zinc concentration, and we present a model based on the distortion of the catalyst droplet in response to the evolution of the cross-sectional shape of the nanowires to quantitatively explain the formation of the periodic twinning.
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This research was carried out under project number MC3.05243 in the framework of the strategic research programme of the Materials Innovation Institute (M2i), the former Netherlands Institute of Metals Research, the FP6 NODE (015783) project, the Ministry of Economic Affairs in the Netherlands (NanoNed) and the European Marie Curie programme. We thank H. de Barse and F. Holthuysen for SEM imaging and P. van der Sluis, H. Wondergem and M. Decré for discussions.
Author Contributions All authors contributed to the design of experiments. G.I. was responsible for MOVPE growth, and M.A.V. for the TEM experiments. R.E.A. and M.A.V. analysed the TEM data. L.-F.F. and W.J.P.v.E. analysed the data quantitatively. R.E.A., L.-F.F., W.J.P.v.E. and E.P.A.M.B. co-wrote the paper.
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Algra, R., Verheijen, M., Borgström, M. et al. Twinning superlattices in indium phosphide nanowires. Nature 456, 369–372 (2008) doi:10.1038/nature07570
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