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@PHDTHESIS{Zamborlini:850285,
author = {Zamborlini, Giovanni},
title = {{O}rganic-{M}etal {H}ybrid {I}nterfaces at the {M}esoscopic
{S}cale},
volume = {55},
school = {Universität Duisburg},
type = {Dissertation},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2018-04327},
isbn = {978-3-95806-328-0},
series = {Schriften des Forschungszentrums Jülich. Reihe Information
/ Information},
pages = {xi, 133 S.},
year = {2018},
note = {Universität Duisburg, Diss., 2018},
abstract = {The molecule-substrate interaction plays a key role in
controlling charge injection in organic based devices.
Charge transfer at the molecule-metal interface strongly
affects the overall physical and magnetic properties of the
system, and ultimately the device performance. This thesis
reports theoretical and experimental evidence of an
unexpectedly high charge transfer rate to nickel tetraphenyl
porphyrin (NiTPP) molecules adsorbed on Cu(100). The
exceptional charge transfer leads to the filling of the
unoccupied orbitals up to LUMO+3. As a consequence of this
strong interaction with the substrate, the resulting
adsorption geometry is highly distorted. For this reason,
scanning tunneling spectroscopy cannot reliably probe the
states related to the macrocycle. Molecular orbital
tomography, instead, provides access to the NiTPP macrocycle
electronic states and determine the reordering and filling
of the LUMOs upon adsorption. The overall energy level
alignment of the molecular states, upon adsorption on the
metal surface, is shown to be only weakly dependent on the
metal ion within the porphyrin, as well as on the symmetry
of the crystalline substrate. On the other hand, the
molecule-substrate interaction is weaker when CoTPP and
NiTPP are deposited on the Ag(110) surface in comparison to
Cu substrate, resulting in the filling of only the
degenerate LUMO and LUMO+1. The control over the
molecule-substrate interaction can also be achieved by
functionalization of the organic layer with a proper axial
ligand. We show in this work that exposure of the
NiTPP/Cu(100) to nitric oxide weakens this interaction:
while the charge transfer rate between the Ni porphyrin and
the copper surface is reduced, a new electronic state,
related to the NO-NiTPP complex, appear in the valence band.
Notably, for the first time, we propose here a
$\textit{cis}$-dinitrosyl ligation mechanism between the NO
molecules and the porphyrin layer, leading to the formation
of (NO)$_{2}$-NiTPP complex already at room temperature.},
cin = {PGI-6},
cid = {I:(DE-Juel1)PGI-6-20110106},
pnm = {522 - Controlling Spin-Based Phenomena (POF3-522)},
pid = {G:(DE-HGF)POF3-522},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
url = {https://juser.fz-juelich.de/record/850285},
}