[en] The interface of Al₂O₃ with 4H-SiC is investigated with synchrotron-based high-resolution x-ray photoelectron spectroscopy to clarify the effect of post-dielectric deposition annealing processes (rapid thermal annealing (RTA) and furnace annealing (FA)) involved in device fabrication. Our results show that post-deposition annealing of Al₂O₃/4H-SiC up to 1100 °C forms a thin interfacial layer of SiO₂ between Al₂O₃ and SiC, which possibly improves the dielectric properties of the system by reducing oxide charges and near-interface traps. Moreover, the formation of SiO₂ at the interface gives additional band offset to the dielectric system. We have also observed that the RTA and FA processes have similar results at a high temperature of 1100 °C. Therefore, we propose that high-temperature post-oxide (Al₂O₃) deposition annealing of up to 1100 °C may be used in device processing, which can improve overall dielectric properties and consequently the device performance. (paper)

[en] The d-orbital contribution from the transition metal centers of phthalocyanine brings difficulties to understand the role of the organic ligands and their molecular frontier orbitals when it adsorbs on oxide surfaces. Here we use zinc phthalocyanine (ZnPc)/TiO₂(110) as a model system where the zinc d-orbitals are located deep below the organic orbitals leaving room for a detailed study of the interaction between the organic ligand and the substrate. A charge depletion from the highest occupied molecular orbital is observed, and a consequent shift of N1s and C1s to higher binding energy in photoelectron spectroscopy (PES). A detailed comparison of peak shifts in PES and near-edge X-ray absorption fine structure spectroscopy illustrates a slightly uneven charge distribution within the molecular plane and an inhomogeneous charge transfer screening between the center and periphery of the organic ligand: faster in the periphery and slower at the center, which is different from other metal phthalocyanine, e.g., FePc/TiO₂. Our results indicate that the metal center can substantially influence the electronic properties of the organic ligand at the interface by introducing an additional charge transfer channel to the inner molecular part.

[en] The fast development of new organic sensitizers leads to the need for a better understanding of the complexity and significance of their adsorption processes on TiO₂ surfaces. We have investigated a prototype of the triphenylamine-cyanoacrylic acid (donor-acceptor) on rutile TiO₂ (110) surface with special attention on the monolayer region. This molecule belongs to the type of dye, some of which so far has delivered the record efficiency of 10%-10.3% for pure organic sensitizers [W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan, and P. Wang, Chem. Mater. 22, 1915 (2010)]. The molecular configuration of this dye on the TiO₂ surface was found to vary with coverage and adopt gradually an upright geometry, as determined from near edge x-ray absorption fine structure spectroscopy. Due to the molecular interaction within the increasingly dense packed layer, the molecular electronic structure changes systematically: all energy levels shift to higher binding energies, as shown by photoelectron spectroscopy. Furthermore, the investigation of charge delocalization within the molecule was carried out by means of resonant photoelectron spectroscopy. A fast delocalization (∼1.8 fs) occurs at the donor part while a competing process between delocalization and localization takes place at the acceptor part. This depicts the ''push-pull'' concept in donor-acceptor molecular system in time scale.

[en] The electronic structure of ZnPc, from sub-monolayers to thick films, on bare and iodated Pt(111) is studied by means of X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and scanning tunneling microscopy. Our results suggest that at low coverage ZnPc lies almost parallel to the Pt(111) substrate, in a non-planar configuration induced by Zn-Pt attraction, leading to an inhomogeneous charge distribution within the molecule and an inhomogeneous charge transfer to the molecule. ZnPc does not form a complete monolayer on the Pt surface, due to a surface-mediated intermolecular repulsion. At higher coverage ZnPc adopts a tilted geometry, due to a reduced molecule-substrate interaction. Our photoemission results illustrate that ZnPc is practically decoupled from Pt, already from the second layer. Pre-deposition of iodine on Pt hinders the Zn-Pt attraction, leading to a non-distorted first layer ZnPc in contact with Pt(111)-I(√3×√3) or Pt(111)-I(√7×√7), and a more homogeneous charge distribution and charge transfer at the interface. On increased ZnPc thickness iodine is dissolved in the organic film where it acts as an electron acceptor dopant