ABSTRACTUsing rf sputtering and post-deposition annealing in a differential scanning calorimeter (DSC), we manufactured bulk (4000 nm) films of crystalline Ge0.83Sn0.17. This Sn concentration is much greater than the solid solubility limit of Sn in Ge (x ≤ 0.01). Continued annealing thermally induces Sn phase separation from the alloy, limiting the ultimate attainable grain size in the metastable crystals. We examine, here, the mechanisms and kinetics of the processes limiting the size of the Ge0.83Sn0.17 polycrystals. From a combination of DSC, electron microprobe, and x-ray diffraction (XRD) measurements, we propose phase transformation mechanisms corresponding to crystallization of amorphous Ge0.83Sn0.17, crystallization of an as-yet unidentified phase of Sn, and phase separation of Sn from the Ge1-xSnx crystals. We were unable to observe the unidentified phase of Sn in XRD, but the phase must be present in the material to account for the quantitative discrepancies (as much as 8 at.%) in Sn percentages determined from each of the DSC, XRD, and electron microprobe measurements. Our models for the various transformation kinetics were corroborated by the subsequent phase-separated Sn melting behavior observed in the DSC: two Sn melting endotherms, one of which was 20–100°C lower than the bulk melting temperature of Sn. This depressed temperature endotherm we speculate represents liquefaction of nanometer-sized (β–Sn clusters.
Kinetics of phase separation in thermally isolated critical binary fluids