Nano Research

, Volume 2, Issue 7, pp 575–582 | Cite as

Kinetically-induced hexagonality in chemically grown silicon nanowires

Open Access
Research Article


Various silicon crystal structures with different atomic arrangements from that of diamond have been observed in chemically synthesized nanowires. The structures are typified by mixed stacking mismatches of closely packed Si dimers. Instead of viewing them as defects, we define the concept of hexagonality and describe these structures as Si polymorphs. The small transverse dimensions of a nanowire make this approach meaningful. Unique among the polymorphs are cubic symmetry diamond and hexagonal symmetry wurtzite structures. Electron diffraction studies conducted with Au as an internal reference unambiguously confirm the existence of the hexagonal symmetry Si nanowires.

Cohesive energy calculations suggest that the wurtzite polymorph is the least stable and the diamond polymorph is the most stable. Cohesive energies of intermediate polymorphs follow a linear trend with respect to their structural hexagonality. We identify the driving force in the polymorph formations as the growth kinetics. Fast longitudinal elongation during the growth freezes stacking mismatches and thus leads to a variety of Si polymorphs. The results are expected to shed new light on the importance of growth kinetics in nanomaterial syntheses and may open up ways to produce structures that are uncommon in bulk materials.


Silicon nanowires hexagonality polytypes cohesive energy chemical vapor deposition kinetics 

Supplementary material

12274_2009_9058_MOESM1_ESM.pdf (571 kb)
Supplementary material, approximately 572 KB.


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Copyright information

© Tsinghua University Press and Springer Berlin Heidelberg 2009

Authors and Affiliations

  1. 1.Department of Chemistry, Merkert Chemistry CenterBoston CollegeChestnut HillUSA

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