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The effect of long-range order on intermolecular interactions in organic semiconductors: zinc octaethyl porphyrin molecular thin film model systems

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Abstract

In order to optimize the performance of devices based on porphyrin thin films it is of great importance to gain a physical understanding of the various factors which affect their charge transport and light-harvesting properties. In this work, we have employed a multi-technique approach to study vacuum deposited zinc octaethyl porphyrin (ZnOEP) thin films with different degrees of long-range order as model systems. An asymmetrical stretching of the skeletal carbon atoms of the porphyrin conformer has been observed and attributed to ordered molecular stacking and intermolecular interactions. For ordered films, a detailed fitting analysis of the X-ray absorption near edge structure (XANES) using the MXAN code establishes a symmetry reduction in the molecular conformer involving the skeletal carbon atoms of the porphyrin ring; this highlights the consequences of increased π–π stacking of ZnOEP molecules adopting the triclinic structure. The observed asymmetrical stretching of the π conjugation network of the porphyrin structure can have significant implications for charge transport and light harvesting, significantly influencing the performance of porphyrin based devices.

Graphical abstract: The effect of long-range order on intermolecular interactions in organic semiconductors: zinc octaethyl porphyrin molecular thin film model systems

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Publication details

The article was received on 17 Feb 2019, accepted on 25 Sep 2019 and first published on 10 Oct 2019


Article type: Paper
DOI: 10.1039/C9CP00954J
Phys. Chem. Chem. Phys., 2019, Advance Article

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    The effect of long-range order on intermolecular interactions in organic semiconductors: zinc octaethyl porphyrin molecular thin film model systems

    A. Kumar, D. Naumenko, G. Rossi, E. Magnano, S. Nappini, F. Bondino, E. Segoloni, L. Amidani, F. d’Acapito, F. Boscherini, L. Barba, E. Pace, M. Benfatto, S. Casassa and M. Pedio, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C9CP00954J

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