Composition and crystallography dependence of the work function: Experiment and calculations of Pt-Al alloys

The work function (WF) of several phases of Pt-Al alloys is investigated. A first-principles study is performed to determine the dependence of the vacuum WF (VWF) on the phase, crystallographic orientation, and atomic termination. In parallel, the effective WF (EWF) of these alloys is experimentally measured using metal-oxide semiconductor devices. A detailed microstructural characterization based on x-ray diffraction and transmission electron microscopy allows the comparison between experiment and calculations. It is found that despite the formation of a complex microstructure, the calculated VWF values are in good agreement with the experimental EWF values. The possible VWF range for each phase has a relatively small (∼0.5 eV) span for different orientations and atomic terminations, and it is found that Pt atoms in the terminating plane are more dominant than Al atoms. The results demonstrate that first-principles calculations of the WF of alloys can be used to successfully predict the experimental WF and that knowledge of the microstructure is important for the accuracy of these calculations.