Nonuniformity in Lattice Contraction of Bismuth Nanoclusters Heated Near Its Melting Point

The structural properties of bismuth nanoclusters were investigated with transmission high-energy electron diffraction from room temperature up to 525 ± 6 K. The Bi nanoclusters were fabricated by thermal evaporation at room temperature on transmission electron microscope grids coated with an ultrathin carbon film, followed by thermal and femtosecond laser annealing. The annealed sample had an average cluster size of ∼14 nm along the minor axis and ∼16 nm along the major axis. The Debye temperature of the annealed nanoclusters was found to be 53 ± 6 K along the [012] direction and 86 ± 9 K along the [110] direction. At T = 464 ± 6 K, the diffraction intensity started to deviate from Debye-Waller behavior due to increased lattice anharmonicity. The onset of the melting of the Bi nanoclusters was T ∼ 500 ± 6 K, as measured by the reduction of the nanocluster size through the formation of a liquid shell detected by the width of the diffraction rings. The thermal expansion coefficient of the Bi (012) and (110) planes is positive up to ∼ 499 11 K. However, the expansion coefficient of the Bi (012) planes showed a transition from a positive to a negative value that occurs over the temperature range Tc ∼ 499 ± 11 K to 511 ± 8 K. For the Bi (110) planes, the thermal expansion coefficient is positive up to their melting point, which is 525 ± 6 K. © 2011 American Institute of Physics. [doi:10.1063/1.3565028