Copper thiocyanate (CuSCN) is a candidate as a transparent solid p-type conductor for optoelectronic and photovoltaic applications, such as solar cells. We calculate the band structure, bonding characteristics, and basic native defect configurations of hexagonal β-CuSCN. β-CuSCN is predicted to be an indirect-gap semiconductor with an unusual orbital character: although the highest valence bands have the expected character of Cu 3d levels hybridized with S 3p states, the conduction band minimum (at the K point of the hexagonal Brillouin zone) has mostly cyanide antibonding character. This quasi-molecular character results in some unusual properties, including that the electron effective masses are comparable to or even larger than the hole effective masses. Calculated results match well with the valence band spectrum of thin film CuSCN, although optical absorption measurements do not conclusively confirm the predicted indirect nature of the lowest transitions. The dominant p-type character of this material is explained in terms of copper vacancies; CN unit vacancies, which are also expected to be acceptors, are proposed as a mechanism to increase p-type conduction.

We address the issue of accurate determination of the valence band maximum (VBM) for SrTiO3(001) single crystals and epitaxial films, as well as TiO2(001) anatase and SrO epitaxial films. These measurements are of critical importance in determining valence band offsets in heterojunctions of these oxides with Si. Three different methods are analyzed: (1) fitting a Gaussian broadened theoretical density of states to the x-ray photoelectron valence band spectrum; (2) finding the intersection of a regression line that spans the linear portion of the x-ray photoelectron valence band leading edge with the background between the valence band maximum and the Fermi level; and (3) determining the energy at which high-resolution ultraviolet photoemission intensity at the leading edge goes to zero. We find that method 1 yields physically unreasonable results when used in conjunction with density functional theory because the latter does not predict the detailed shape of the valence bands in these oxides with sufficient accuracy. In contrast, methods 2 and 3 give physically reasonable results that are in good mutual agreement. The difference in VBM between method 1 and methods 2 and 3 is 0.4–0.6 eV, depending on the oxide. Methods 2 and 3 yield the most reliable VBM, provided the experiments are carried out with adequate energy resolution.

In situ X-ray photoelectron spectroscopy (XPS) was utilized to identify the chemical state of silver in a range of silver oxide thin films obtained by codeposition of silver and atomic oxygen. A highly oxidized silver species was observed at an unexpectedly low Ag 3d5/2 binding energy (BE) of 366.8 eV with an associated broad satellite at 368.2 eV; this species was assigned as Ag(III). It was found to be highly unstable in vacuum but could be regenerated by further exposure to atomic oxygen. Both BE shifts and intensity changes of the O 1s peak were found to correlate with changes in the silver oxidation state. The theoretical XPS spectrum of high spin Ag(III) was calculated for both an isolated cation and an embedded AgO6 cluster.

We report element specific structural and magnetic investigations on Zn(1-x)Co(x)O epitaxial films using synchrotron radiation. Co dopants exclusively occupy Zn sites as revealed by x-ray linear dichroism having an unprecedented degree of structural perfection. Comparative magnetic field dependent measurements by x-ray magnetic circular dichroism and conventional magnetometry consistently show purely paramagnetic behavior for isolated Co dopant atoms with a magnetic moment of 4.8 (mu B). However, the total magnetization is reduced by approximately 30%, demonstrating that Co-O-Co pairs are antiferromagnetically coupled. We find no sign of intrinsic ferromagnetic interactions for isolated or paired Co dopant atoms in Co:ZnO films.