Interface formation and growth of a thin film of ZnPcCl8/Ag(111) studied by photoelectron spectroscopy
ABSTRACT We have investigated the electronic properties of a thin film of ZnPcCl8 molecules deposited on Ag(1 1 1) using ultra-violet photoelectron spectroscopy. Close to one monolayer the electronic structure differs sensibly from that of the thick film. The appearance of a density of states close to the Fermi level is interpreted as the sign of the molecule–substrate interaction via a charge transfer mechanism. An increase of the work function at the early stages of adsorption confirms that electrons are transferred from the metal to the molecular orbitals creating an interface dipole. As the coverage is increased the weak interaction between molecules of successive layers causes the electronic properties to evolve gradually towards those of the thick film. Finally, the impact of the interface electronic properties on the intermolecular interaction is discussed.
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ABSTRACT: The autonomous ordering and assembly of atoms and molecules on atomically well-defined surfaces allow creating a wide range of surface nanostructures, opening an alternative 'bottom-up' route to the traditional 'top-down' fabrication methods of the microelectronics industry now approaching their fundamental limits. This review summarises some recent efforts of our team to grow molecular arrays on metal, insulating or semiconductor surfaces. In a fundamental approach, two-dimensional surface arrays of nanometre size have been obtained under ultrahigh vacuum by evaporation of molecules, functionalised to favour the intermolecular links rather than molecule-substrate ones. Intermolecular links such as hydrogen bonds, covalent or coordination bonding were profitably used to create various molecular networks. Alternatively, we also investigated molecular self-assembly from the solution whose architectures are mainly fixed by the molecule-substrate adsorption forces. Molecular assemblies were characterised using Scanning Near-Field Microscopies (Scanning Tunnelling Microscopy, non-contact-Atomic Force Microscopy), whereas electronic and vibrational properties were investigated by surface spectroscopy such as Ultra-Violet and X-ray Photoelectron Spectroscopy, infrared or Surface-Enhanced Raman Spectroscopy.International Journal of Nanotechnology 01/2012; 9(3-7):325-354. DOI:10.1504/IJNT.2012.045337 · 1.14 Impact Factor
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ABSTRACT: Phthalocyanines (Pcs) are capable of converting sunlight into electric energy when adsorbed on TiO2 in a dye-sensitized solar cell. Of special interest in this type of cell is the energy level alignment as well as how molecules adsorb on the surface as it determines the output of the cell. We investigated the FePc−TiO2(110) interface using scanning tunneling microscopy, synchrotron-based photoelectron spectroscopy, and X-ray absorption spectroscopy. We found a strong coupling of the first-layer FePc to the substrate resulting in an alteration of the electronic structure and charge transfer from the molecules. The FePc in the second layer is not severely affected by the bonding to the surface and has bulk-like electronic properties. The growth of FePc thin films proceeds in a layer plus island mode, and the molecular plane is parallel to the surface. The energy level alignment at the interface is determined, and the lowest unoccupied molecular orbital is found above the conduction band minimum of the oxide substrate.The Journal of Physical Chemistry C 03/2008; 112(15). DOI:10.1021/jp711311s · 4.84 Impact Factor
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ABSTRACT: Using light-polarization-dependent angle-resolved photoemission, the metal-organic molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm)(2), i.e., C24H36N2O4Cu, Cu(II)) is observed to adopt a preferential orientation that depends on the film thickness and substrate when adsorbed on Co(111) and Cu(111). In addition, the final-state binding energies change with film thickness, suggesting the substrates affect the screening or charging in the photoemission final state. For Cu(CNdpm)(2) deposited on Co(111), the induced spin polarization was found to depend strongly on the molecular orbital contributions.The Journal of Physical Chemistry C 09/2008; 112(35):13656-13662. DOI:10.1021/jp804251b · 4.84 Impact Factor