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 Adsorption Geometry and Electron Transfer of Zn-tetraphenyl-porphyrin on different substrates

The importance of substrate and interfaces has been exploited in this experimental study on the interaction of one single layer of Zn-tetraphenyl-porphyrin with Ag(110) and Si(111). Photoemission, near-edge X-ray absorption, and resonant photoemission were used to investigate the bonding nature, the adsorption geometry as well as the dynamics of electron transfer between the molecules and the metal or semiconductor surfaces. ChemPhysChem, 11: 2248.

We report on the preparation of a conformationally controlled Zn-tetraphenyl-porphyrin (ZnTPP) single layer on two possible substrates, Ag(110) and Si(111).The ZnTPP molecule is characterized by four phenyl groups bonded to the macrocycle and a central Zn atom. As substrates we have chosen silver, normally used as contact in photovoltaic or transistor devices, and silicon, worldwide employed in semiconductor industry. The substrate can influence the thin film morphology, the distortion of the molecules and the electronic charge transfer as a consequence.

The molecular orientation with respect to the substrate was monitored using angular dependent near edge x-ray absorption fine-structure spectroscopy (NEXAFS), while the electronic properties of the filled states were investigated using x-ray and ultraviolet photoemission (XPS and UPS). 
Depending on the substrate, the adsorption orientation is mainly mastered by the coupling of the phenyl legs or the macrocycle with the surface. The ResPES behavior indicates that for the phenyl rings the charge transfer into the substrate is less favorable than on the Ag(110) case and comparable to the multilayer case. Core level photoemission indicates that the molecule is interacting with the substrate using a macrocycle pyrrole ring, while the phenyl rings are rotated in such a way to minimize the interaction with the substrate.

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Substrate Influence for the Zn-tetraphenyl-porphyrin Adsorption Geometry and the Interface-Induced Electron Transfer

Carla Castellarin-Cudia Dr.1, Patrizia Borghetti2, Giovanni Di Santo Dr.1, Mattia Fanetti Dr.1, Rosanna Larciprete Dr.1,3, Cinzia Cepek Dr.4, Paolo Vilmercati Dr.1, Luigi Sangaletti Prof.2, Alberto Verdini Dr.4, Albano Cossaro Dr.4, Luca Floreano Dr.4, Alberto Morgante Prof.4, Andrea Goldoni Dr.1

ChemPhysChem Volume 11, Issue 10, 2248, July 12, 2010
Article first published online: 10 JUN 2010
DOI: 10.1002/cphc.201000017

Last Updated on Monday, 29 September 2014 18:21