Interest in nanowires continues to grow, fuelled in part by applications in nanotechnology^{1, 2, 3, 4, 5}. The ability to engineer nanowire properties makes them especially promising in nanoelectronics^{6, 7, 8, 9}. Most silicon nanowires are grown using the vapour–liquid–solid (VLS) mechanism, in which the nanowire grows from a gold/silicon catalyst droplet during silicon chemical vapour deposition^{10, 11, 12, 13}. Despite over 40 years of study, many aspects of VLS growth are not well understood. For example, in the conventional picture the catalyst droplet does not change during growth, and the nanowire sidewalls consist of clean silicon facets^{10, 11, 12, 13}. Here we demonstrate that these assumptions are false for silicon nanowires grown on Si(111) under conditions where all of the experimental parameters (surface structure, gas cleanliness, and background contaminants) are carefully controlled. We show that gold diffusion during growth determines the length, shape, and sidewall properties of the nanowires. Gold from the catalyst droplets wets the nanowire sidewalls, eventually consuming the droplets and terminating VLS growth. Gold diffusion from the smaller droplets to the larger ones (Ostwald ripening) leads to nanowire diameters that change during growth. These results show that the silicon nanowire growth is fundamentally limited by gold diffusion: smooth, arbitrarily long nanowires cannot be grown without eliminating gold migration.

1. IBM Research Division, T. J. Watson Research Center, Yorktown Heights, New York 10598, USA

Correspondence to: J. B. Hannon¹ Correspondence and requests for materials should be addressed to J.B.H. (Email: jbhannon@us.ibm.com).

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