density functional theory; pinning effect; self-assembled monolayers; single molecule junctions; Contact geometry; Different mechanisms; Electronic polarization effect; Energy level alignment; Interfacial hybridization; Non-equilibrium Green's function; Single-molecule junctions; Surface coverages; Statistics and Probability; Numerical Analysis; Modeling and Simulation; Multidisciplinary
Abstract :
[en] We present a detailed theoretical characterization of the energetic alignment between the HOMO level of a series of thiolated oligophenylenes of increasing chain size, and the Fermi level of gold electrodes, using density functional theory (DFT) calculations for molecular self-assembled monolayers (SAMs) chemisorbed on an Au (111) surface, and the nonequilibrium Green's function (NEGF) formalism coupled to DFT for single molecule junctions. The additional role of the dynamic electronic polarization effects neglected in standard DFT calculations is also discussed. Interestingly, whereas the HOMO energy varies significantly among the unsubstituted oligomers in the gas phase, their alignment with respect to the Fermi level of the electrode is almost insensitive to chain size upon chemisorption, thus pointing to a strong pinning effect. The energy at which the HOMO is pinned strongly depends on the degree of interfacial hybridization, and hence on the contact geometry, as well as on the degree of surface coverage although a different mechanism enters into play.
Disciplines :
Chemistry
Author, co-author :
Diez-Cabanes, Valentin; Laboratory for Chemistry of Novel Materials, University of Mons, Mons, Belgium
Gonzalez, Sandra Rodriguez; Laboratory for Chemistry of Novel Materials, University of Mons, Mons, Belgium
Osella, Silvio; Centre of New Technologies, University of Warsaw, Warszawa, Poland
Cornil, David ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Van Dyck, Colin ; Université de Mons - UMONS > Faculté des Sciences > Service Chimie Physique Théorique
Cornil, Jérôme ; Laboratory for Chemistry of Novel Materials, University of Mons, Mons, Belgium
Language :
English
Title :
Energy Level Alignment at Interfaces Between Au (111) and Thiolated Oligophenylenes of Increasing Chain Size: Theoretical Evidence of Pinning Effects
EC - EC - European Commission Consortium des Equipements de Calcul Intensif (CECI) F.R.S.-FNRS - Fonds de la Recherche Scientifique Tier-1 supercomputer of the Wallonie-Bruxelles Federation Walloon Region
Funding text :
The authors acknowledge the stimulating discussions with Dr. Zuoti Xie (University of Minnesota) and the technical assistance of Dr. Claudio Quarti (University of Mons). The work in Mons is supported by the European Commission via the Marie Curie project ITN iSwitch (GA no. 642196) and the Belgian National Fund for Scientific Research (F.R.S.‐FNRS). The computational resources are provided by the Consortium des Équipements de Calcul Intensif (CÉCI) funded by the Belgian National Fund for Scientific Research (F.R.S.‐FNRS) under Grant 2.5020.11; and by the Tier‐1 supercomputer of the Wallonie‐Bruxelles Federation, infrastructure funded by the Walloon Region under the grant agreement n°1117545. J.C. is an FNRS Research Director. C.V.D. thanks the support by the National Institute for Nanotechnology, which is operated as a partnership between the National Research Council, Canada, the University of Alberta, and the Government of Alberta.The authors acknowledge the stimulating discussions with Dr. Zuoti Xie (University of Minnesota) and the technical assistance of Dr. Claudio Quarti (University of Mons). The work in Mons is supported by the European Commission via the Marie Curie project ITN iSwitch (GA no. 642196) and the Belgian National Fund for Scientific Research (F.R.S.-FNRS). The computational resources are provided by the Consortium des ?quipements de Calcul Intensif (C?CI) funded by the Belgian National Fund for Scientific Research (F.R.S.-FNRS) under Grant 2.5020.11; and by the Tier-1 supercomputer of the Wallonie-Bruxelles Federation, infrastructure funded by the Walloon Region under the grant agreement n?1117545. J.C. is an FNRS Research Director. C.V.D. thanks the support by the National Institute for Nanotechnology, which is operated as a partnership between the National Research Council, Canada, the University of Alberta, and the Government of Alberta.
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