Electrocrystallization of Sb and the compound semiconductor ZnSb has been investigated by in situ SPM methods at the electrified ionic liquid/Au(111) interface at an elevated temperature of 50 degrees C for the first time employing the ionic liquid ZnCl2-[C(4)mim]Cl-+(-) (45:55). Prior to the underpotential deposition (UPD) process of Sb, ZnCl3- anions adsorb on the gold surface at the open-circuit potential (OCP). An ordered region - showing the characteristic of a Moire-like pattern - coexists with a disordered region indicative of an interfacial phase transition. When the potential is reduced to -0.40 V versus Pt/Pt(II), 2D electrocrystallization of Sb starts showing a typical (root 3 x root 3) structure of the first monolayer. Further decreasing the potential to -0.5 V a second layer of Sb islands occurs. Stepping the potential from the UPD region to -0.60 V, the OPD of Sb sets in showing randomly dispersed clusters of homogeneous size. Near the ZnSb deposition potential, at similar to-0.95 V, a nearly homogeneous distribution of clusters of spherical shape with diameters up to 15 nm is found. Their corresponding STS curves exhibit an obvious semiconducting behaviour with a gap-energy of similar to-0.6 +/- 0.2 eV. Experiments at deposition conditions on the Sb-rich or Zn-rich side relative to the ZnSb deposition potential show an obvious doping effect - in the case of Zn excess - which is revealed by the corresponding normalized conductance (NC) spectra. (c) 2007 Elsevier Ltd. All rights reserved.