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Pt–Bi films were synthesized on glass and thermally oxidized silicon substrates by e-beam evaporation and annealing. The structures were characterized using X-ray diffraction (XRD) and transmission electron microscopy/selected area electron diffraction (TEM/SAED) techniques. Single-phase PtBi was obtained at an annealing temperature of 300°C, whereas a higher annealing temperature of 400°C was required to obtain the highly textured γ-PtBi2 phase. TEM/SAED analysis showed that the films annealed at 400°C contain a dominant γ-PtBi2 phase with a small amount of β-PtBi2 and α-PtBi2 phases. Both the PtBi and γ-PtBi2 phases are highly textured in these two kinds of film: the c-axis of the hexagonal PtBi phase is mostly in the film plane, whereas the c-axis of the trigonal γ-PtBi2 phase is perpendicular to the film plane. The electrical resistivity of the film with the γ-PtBi2 phase was smaller by one order of magnitude than that of the film with the PtBi phase.