Structure of the liquid-vapor interface of a dilute ternary alloy: Pb and In in Ga

We report the results of experimental studies of how the competition between two solutes to segregate in the liquid-vapor interface of a dilute ternary alloy influences the composition and structure of that interface. The system studied has small amounts of Pb and In dissolved in Ga; it differs from a previous study of dilute alloys containing small amounts of Pb and Sn dissolved in Ga by the addition of a new variable, namely, the valence difference between the solute atoms Pb and In. This valence difference influences the electron density distribution in the alloy liquid-vapor interface in proportion to the excess concentrations of the solute species in the interface, and thereby should affect the structure of the interface. We find that for a ternary PbInGa alloy that contains 0.039 at. % Pb and 6.31 at. % In, the Pb that segregates in the liquid-vapor interface forms a two-dimensional hexagonal crystal phase that undergoes a first-order transition to a disordered phase at T=29.0+/-0.1 degreesC. The two-dimensional crystalline Pb forms about 0.6 of a full monolayer; the remainder of the outer stratum of the liquid-vapor interface is filled with two-dimensional liquid In. For a ternary PbInGa alloy that contains the same amount of Pb and 12.2 at. % In, the Pb that segregates in the liquid-vapor interface forms a two-dimensional liquid down to 26.0 degreesC, the lowest temperature at which data were taken. For temperatures in excess of 29.0 degreesC two-dimensional liquid Pb and two-dimensional liquid In coexist in the interface, with the fractional occupation of the monolayer by In exceeding the fractional occupation by Pb.