Electronic Structure of FePc and Interface Properties on Ag(111) and Au(100) F. Petraki, † H. Peisert,* ,† U. Aygü l, † F. Latteyer, † J. Uihlein, † A. Vollmer, ‡ and T. Chasse ́ † † IPTC, University of Tuebingen, Morgenstelle 18, 72076 Tuebingen, Germany ‡ Helmholtz Centre Berlin for Materials and Energy, Electron storage ring BESSY II, Albert-Einstein-Str. 15, 12489 Berlin, Germany ABSTRACT: The electronic structure of iron phthalocyanine (FePc) and interface properties on Ag(111) and Au(100) are investigated by photoexcited electron spectroscopies: photoemission (XPS and UPS) and X-ray absorption spectroscopy (XAS or NEXAFS). Valence band structures with Fe character were identified using resonant photoemission. The strength and nature of the interaction at the interface depend clearly on the substrate. A strong interaction of the central metal atom of the phthalocyanine occurs on Ag(111), whereas no significant changes of the electronic situation were found for FePc on Au(100). Resonant photoemission data show that for FePc on Ag(111) the formed interface states close to the Fermi level are determined by the interaction between Fe 3d states and substrate related states. On the other hand, also the nitrogen atom of FePc is involved in the interaction. 1. INTRODUCTION The recently increasing research efforts devoted to transition metal phthalocyanines (TMPcs) derives from their unique optical, electronic, and magnetic properties. Metal phthalocya- nines can be applied in a variety of devices. Most recently, opto- electronic devices such as light-emitting diodes, field-effect transistors, and solar cells are in the focus of research (e.g., refs 1 and 2). In addition, magnetic properties of the TMPcs are studied intensely, driven, e.g., by possible future applications in spintronic nanodevices such as spin valves. 3-7 However, the electronic configuration and thus the magnetic properties of the central metal atom of the TMPc is not completely understood and has been intensively debated during the last years. 8-17 Moreover, at interfaces, the electronic configuration may change, which is in particular important for spintronic devices, since the electron (spin) injection occurs at these interfaces. Recent studies have shown that the strength and nature of the interaction between Pcs and metallic substrates (Au, Ag) depend clearly on the central metal atom of the Pc. In particular, for open shell molecules such as CoPc, charge transfer from the central metal atom of the Pc at the interface to the substrate occurs as a direct consequence of the adsorption of the molecule. This is concluded from change of both photoemission (XPS) and X-ray absorption (XAS) spectra directly at the interface. 18,19 On the other hand, changes in XPS and XAS spectra are weaker for MnPc on Au and Ag, but nevertheless charge transfer processes at the interface are likely. 20,21 In order to predict more general inside in the interaction of TMPs to Au and Ag, we focus in the present work on iron phthalocyanine (FePc), where the electronic configuration of the central metal ion Fe 2+ is d 6 , i.e., between Co 2+ and Mn 2+ . 2. EXPERIMENTAL SECTION The measurements were performed at the third generation synchrotron radiation source BESSY II (Berlin) using the Optics-beamline and the endstation SURICAT. The photon energies were calibrated comparing the binding energy (BE) of Au 4f 7/2 and Ag 3d 5/2 peaks excited by first- and second-order light. The energy resolution for XPS and XAS was set to ≈100 meV at a photon energy of 400 eV. The absorption was monitored indirectly by measuring the total electron yield (TEY), i.e., sample current. The spectra were normalized to have the same absorption edge step height well above threshold. The energy resolution in the case of resonant photoemission (ResPES) was set to about 200 meV. As substrates, we used Au(100) and Ag(111) single crystals, cleaned by argon ion sputtering and annealing. The cleanliness was checked by X-ray photoemission spectroscopy (XPS). FePc powder was carefully cleaned by vacuum sublimation prior use. Thin films of FePc were evaporated in ultrahigh vacuum (base pressure <1 × 10 -8 mbar) from a temperature-controlled cell with evaporation rates between 0.1 and 0.5 nm/min. The nominal film thickness was estimated from both a quartz microbalance and from XPS intensity ratios using element and energy dependent sensitivity factors from ref 22 and assuming layer-like growth. 3. RESULTS AND DISCUSSION I. Bulk Electronic Structure. Polarization dependent X-ray absorption spectroscopy (XAS), also called near edge X-ray absorption fine structure (NEXAFS) spectroscopy, probes the absorption of the X-rays due to excitations from a core level into lower unoccupied states as a function of energy. The Received: March 7, 2012 Revised: April 27, 2012 Published: April 30, 2012 Article pubs.acs.org/JPCC © 2012 American Chemical Society 11110 dx.doi.org/10.1021/jp302233e | J. Phys. Chem. C 2012, 116, 11110-11116