The determination of ternary segregation parameters using a linear heating method
Asante, Joseph Kwaku Ofori
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In this study the segregation behaviour of the ternary system Cu(lll ), Sb, Sn is investigated experimentally, as well as with the modified Darken segregation model. The model, which describes the kinetics as well as the equilibrium of segregation, had been used successfully in various studies of binary systems. A computer program based on this model was developed for ternary systems. A Cu(lll) single crystal was doped with low concentrations of 0,180 at% Sb and 0.133 at% Sn using evaporation and diffusion process.' The experimental results were gathered with the Auger electron spectroscopy technique. This technique was combined with a linear temperature ramp that makes it possible to obtain the segregation parameters in a single run. The traditional method requires various runs at different temperatures. The overlapping of Sb and Sn Auger peaks in the energy regions of interest necessitated the development of a method to successfully extract the true contributions of the elements from the measured spectra. It is clearly shown that the combination of Auger peaks is not linear and that the true contributions of Sb and Sn can be calculated if the peaks overlap in two energy regions and the standard spectra are available. The segregation profiles resulted from the Auger data show clearly the sequential segregation of the two elements (Sn and Sb). From the equilibrium conditions, it is also concluded that an interaction energy between Sb and Sn is present. By simulating the experimental results, using the theoretical Darken model, values for the segregation parameters can be obtained. The initial values for the fits are found mathematically (highenergy regions) and manually (low energy regions). The calculated profiles fit the experimental results very well. The present study confirms that Sn segregate first to the surface with Do = 1.58x10-5 m²s-¹ and E = 170 kJ/mol. Sb with a lower dimsion coefficient (Do = 1.93x10-8 m²s-¹ and E = 150 kJ/mol) segregates at higher temperatures. A further increase in temperature results in the stronger segregate Sb, (with a higher segregation energy ∆G = -74.6 kJ/mol) to displace the Sn (∆G = -59.0 kJ/mol) from the surface. From the simulations, it is clear that the maximum surface coverage for Sn is determined mainly by the attractive interaction (ΩSnCu = -8.25 kJ/mol) between Sn and Cu. The desegregation rate of Sn in this system is determined by the segregation rate of Sb. The segregation profile of Sb is similar to that in a binary system (Cu,Sb) with the desegregation rate of Sb much slower than the segregation rate. The study also shows definite attractive interaction between Sb and Cu (ΩSbCu= -17.05 kJ/mol) This trend was not observed in the studies of binary systems. There is, however, repulsive interaction between the segregates (ΩSnSb = 3.62 kJ/mol). The repeatability of the segregation parameters at different heating rates shows that this experimental method can be used successfully.