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XAFS study of the thermal behaviour of gold bulk and clusters

T Comaschi1, A Balerna2 and S Mobilio1,2,3

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Materials showing negative thermal expansion (NTE) coefficient over large temperature ranges are nowadays of great interest for their possible applications. Small nanoparticles show changes in their properties with respect to the corresponding bulk, mainly due to the high surface to volume ratio and to the confinement of electrons in a small volume. In the present paper we report a x-ray absorption fine structure (XAFS) study on the thermal expansion coefficient of an Au foil and of Au nanoparticles of very small dimensions ranging from 2.4 nm and 5.0 nm. Their L3 edge has been investigated in the temperature range 20K – 300K and a very accurate data analysis has been performed taking into account the presence of asymmetry effects. All clusters showed a thermal trend of the first shell distance significantly different from that of the bulk. The larger clusters were characterized by a reduction of the thermal expansion coefficient with respect to bulk; in the smallest samples the crossover from a thermal expansion to a NTE effect was observed. A simple model, based on the contribution of localized states induced by the finite size of the clusters, qualitatively accounts for the observed behaviour.


PACS

78.70.Dm X-ray absorption spectra

61.46.Bc Structure of clusters (e.g., metcars; not fragments of crystals; free or loosely aggregated or loosely attached to a substrate)

65.80.+n Thermal properties of small particles, nanocrystals, nanotubes

61.46.Df Structure of nanocrystals and nanoparticles ("colloidal" quantum dots but not gate-isolated embedded quantum dots)

Subjects

Condensed matter: electrical, magnetic and optical

Nanoscale science and low-D systems

Dates

Issue 1 (2009)



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