Epitaxial Cobalt Oxide Films with Wurtzite Structure on Au(111).

Several‐nanometer‐thick, closed, and epitaxial cobalt(II) oxide films with wurtzite crystal structure (w‐CoO) are grown on Au(111) and their structural and electronic properties analyzed. The structural quality of the (0001¯) oriented, oxygen‐terminated, and unreconstructed films allow the application of surface‐science methods to unravel the properties of this unusual polymorph of CoO and may pave the way for future thin‐film applications. An experimental structural analysis by low‐energy electron diffraction (LEED‐IV) is presented with an excellent agreement between measured and calculated intensity spectra expressed by a Pendry R‐factor of R=0.112 and few‐picometer error bounds in the parameter values. Using scanning tunneling spectroscopy (STS) the bandgap of the semiconducting films is found to be 1.4 ± 0.2 eV. Ultraviolet photoelectron spectroscopy (UPS) confirms the presence of a gap and the position of the Fermi level (EF). The structural results of density functional theory calculations using (hybrid) functionals to treat electron correlations and van der Waals forces agree well with the experimentally determined structure of the antiferromagnetic w‐CoO films. In contrast to generalized gradient approximation (GGA)+U calculations, the Heyd–Scuseria–Ernzerhof hybrid functional reproduces the semiconducting nature correctly and predicts surface states in the gap which might pin EF in agreement with STS and UPS. [ABSTRACT FROM AUTHOR]