We present results on surface freezing of Ga-based alloys, GaBi, GaPb and GaTl, above the liquidus line between the Ga-rich eutectic and the monotectic point. Spectroscopic ellipsometry (0.8 eV ≤hν≤4.2 eV) and kinetic single wavelength ellipsometry (2.75 eV) have been employed to probe the changes of the interfacial electronic structures on surface freezing. To minimize thermal gradients across the sample a heatable cap that covers the sample and crucible was developed. The surface freezing temperature, TSF, for the spontaneous formation of a solid-like film on top of the Ga-rich liquid on cooling the sample from the homogeneous phase region was found to be independent of the temperature difference between the upper and lower furnace (ΔT: +10 to −10 K) and only weakly dependent on the cooling rate (: 2.5–20 K h−1). In the case of GaPb the solid film consists of solid Pb with a thickness h≥400 Å. Comparing with GaBi we draw analogous conclusions for GaPb and GaTl and suggest that the surface freezing transition precedes the bulk phase transition along the liquidus line as the alloy is cooled.

A surface solidification transition in Ga‐rich Ga‐Tl alloys is observed employing spectroscopic and single wavelength kinetic ellipsometry. This transition occurs a few Kelvin above the liquidus line extending from the eutectic to the monotectic point. Between the respective temperatures (Teut=29.70 °C, Tmono=287 °C) solid Tl undergoes its α‐β‐transition in the alloy at a metatectic temperature of 223 °C. In this brief communication the peculiarities of the solid surface film formation associated with this α‐β‐transition is reported. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)