In this work we study the adsorption of Cs on S-covered Si(100)-(2 × 1) and Si(100)-(1 × 1) surfaces, as well as the adsorption of S on Cs-covered Si(100)-(2 × 1). The experiment was performed in an ultrahigh vacuum (UHV) chamber with low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and work function (WF) measurements. Predeposited S increases the binding energy and the maximum amount of Cs that can be deposited on the surface. The presence of S inhibits the pattern of the characteristic WF curve of Cs on clean Si(100)-(2 × 1), i.e. an initial decrease to a minimum value, Φmin, followed by an increase toward the value Φmax of metallic Cs. The WF, instead, decreases to a value close to that of saturated Cs on clean Si(100)-(2 × 1), where it forms a plateau. This is characteristic of the covalent bonding of Cs with the semiconductor substrate. Independently of the sequence of Cs and S deposition, (a) the transition Si(100)-(2 × 1) → Si(100)-(1 × 1) occurs when ΘS > 0.5 ML, and (b) the sites of Cs and S remain the same, with the Cs atoms residing between the S atoms. Heating of the S/Cs/Si composite surfaces to ~ 650 K causes a reorganization of the Cs and S adatoms in a tendency to form a Cs–S complex. The issue of site preference for Cs and S adatoms has been discussed in detail in the structural models provided.
