Molecular Magnets - Nanostructure and Solid State Physics - Universität Hamburg

17/10/23, 23:19 Molecular Magnets : Nanostructure and Solid State Physics : Universität Hamburg
Universität Hamburg Staff Service Portal STiNE
Nanostructure and Solid State Physics
UHH MIN Department of Physics Nanostructure and Solid State Physics Research Group Wiesendanger
Research Molecular Magnets
Molecular Magnets
In this project magnetic properties of magnetic molecules are investigated. Also, different sample
substrate systems with different electronic and magnetic properties were chosen to reveal the cou‐
pling of the molecules to each other and to the substrate. In order to leave the electronic structure of
an adsorbed molecule mostly unchanged and to observe it in its original state, atomic force mi‐
croscopy is deployed, since this method is not limited to conductive surfaces. As insulating substrates
sodium chloride (NaCl - nonmagnetic) and nickel oxide (NiO - antiferromagnetic at (001) surface) are
used in this experiment. The third substrate system which also serves as a candidate for a magnetic
coupling with magnetic molecules is the iron monolayer on tungsten (W(001)) 1. Former magnetic
exchange force microscope (MExFM) studies were performed on this system as well as on nickel oxide
and the antiferromagnetic order could be reproduced in both cases2,3. A possible magnetic coupling
from the substrate to the metallic center of a molecule is investigated. For that reason different mag‐
netic molecules, which exhibit at least one metallic center, are used (see figure 1 for structural
formula).
Copyright: AG WIesendanger
Figure 1: Structural formula of a Co-Salen (C16H14CoN2O2) and b CuNi-Salen (C18H14CuN2NiO7) or

Doublesalen.
Further magnetic investigation of single molecules or molecular nanostructures only is possible if

one is aware of the interactions between the molecules and the molecule substrate interaction.
Therefore growth studies are inevitable. Figure 2 is showing the result of the study of Co-Salen on
NaCl(001)4. In fig. 2.a compact nanocrystallites (red) and metastable nanowires (blue) are coexisting
at the same time. Structural resolution shows the well-ordered molecular unit cell consisting out of
dimers in 2.b,c and the atomic lattice of NaCl(001) in 2.d. The compact nanocrystallites are thermody‐
namically favored, meaning that post annealing or increasing the elapsed time results in dissolving
nanowires – at a certain point only nanocrystallites are left on the NaCl(001) surface. The metastable
bimodal growth mode at hand reveals a rather weak molecule substrate interaction and high mole‐
cule molecule interaction.
https://www.physik.uni-hamburg.de/en/inf/ag-wiesendanger/forschung/molecular-magnets.html 1/7
Figure 2: a 1 x 1 µm² of 5 monolayer Co-Salen on NaCl(001) with two crystalline formes of Co-Salen (red
and blue) b, c, d molecular/atomic resolution of the structures given in a.
If one changes the substrate to NiO, not only the magnetic properties are altered, but also the elec‐
tronic structure, for that reason the growth is quite different compared to Co-Salen on NaCl. Figure 3
shows the result of the growth study of Co-Salen on NiO(001). By depositing a small amount of mole‐
cules to the surface, stepedge decoration is observed (fig 3.a). But until the coverage reaches a mono‐
layer no growth occurs: The molecules diffuse rather freely above the surface terraces, without form‐
ing any nucleation (fig 3.b). If the density reaches a monolayer, a closed disordered wettinglayer
emerges. Thereupon, further growth continous with higher molecular density (fig 3.c). Showing no
crystalline growth signifies a higher molecule substrate interaction, than molecule molecule interac‐
tion. A possible explanation is the known oxygen affinity of Co-Salen5, which might bind coordina‐
tivly with an oxygen atom of the NiO and therefore could cause a higher interaction.
Figure 3: a At low coverages step edge decoration starts until all step edges are fully occupied (80 x 80
nm²). b Increasing the coverage leads to diffusing molecules at the terraces, which is revealed due to
stripes in the topogrophy data (80 x 80 nm²). c At higher coverages (5 ML) a crystalline growth of the
Co-Salen forms a lacerated layer growth with the amorphous monolayer beneath it (2 x 2 µm²).
To understand and control magnetism of molecules one has to evaluate the adsorption geometry of
the molecules. For that reason the adsorption site and orientation was determined experimentally
and theoretically approved for Co-Salen6. Knowing that the interaction above an anion of an ionic in‐
sulator to a metallic tip is always largest7, we could unambiguously assign the depressions and pro‐
trusions in the atomically resolved images to the respective ionic species and identify the adsorption
site of the central Co atom of the Co-Salen molecule to be the chloride ion on the NaCl surface and
oxygen on the NiO surface (fig. 4).
Figure 4: a Adsorption site of Co-Salen on NaCl(001) (4x4 nm²). b Adsorption site of Co-Salen on
NiO(001) (8x8 nm²).
As it is already mentioned above, the NiO(001) surface exihbits an antiferromagnetic aligment of the
nickel atoms. Due to a superexchange along the oxygen atoms the nickelatoms are antiferromagneti‐
cally coupled – the magnetic moments are parallel to the [111] axis. Since the Co-Salen is adsorbed
above the oxygen atom, the superexchange might also lead to a magnetic coupling of the central Co
atom with the Ni atoms. The result would be a stabilized out of plane magnetic moment of the Co-
Salen center, which one is able to quantify by magnetic exchange force microscopy (MExFM) and
magnetic exchange force spectroscopy (MExFS).
Figure 5: Animation of Co-Salen on NiO(001) with two magnetical out of plane moments (up = green,
down = red).
Spin-resolved scanning tunneling microscopy on Molecules
Organic as well as magnetic molecules recently attracted growing interest in scientific research, espe‐
cially in the field of molecular spintronics. Organic molecules are believed to be an advantageous ma‐
terial for transporting the spin degree of freedom, because they are built up of light elements which
lead to a low spin orbit coupling and spin relaxation times in excess of 10 ms were already observed
in the 1970's [8]. A long spin diffusion length was observed in early spin valve experiments [9,10] but
the origin of the measured giant magneto resistance in these experiments was discussed controver‐
sially [11]. In particular the morphology of the organic film, e.g. the possibility of diffusion of ferro‐
magnetic material into the organic layer and the role of the organic-ferromagnet interface motivated
additional research [12,13]. Spin-polarized scanning tunneling microscopy (SP-STM) is the ideal tool to
study the energy and spin distribution of single molecules in atomically well-defined environments
on a sub-molecular scale. Thereby, it enables characterization of a well-defined molecule-ferromag‐
net interface. Furthermore, the comparison with state-of-the-art first principles calculations, includ‐
ing van der Waals interactions, enables unprecedented insight into the physical processes determin‐
ing the transport of the molecule-ferromagnet interfaces.
To illustrate the capability of SP-STM to study the magnetic properties of organic (and magnetic) mol‐
ecules, we present here two systems, which have been studied recently in the subgroup “magnetic
molecules”. The first example, Co-phthalocyanine molecules on 2 ML of Fe on W(110), shows the spin
dependence of the tunneling current flow of molecule-ferromagnet hybrid states. The second exam‐
ple, bis(phthalocyaninato)terbium(III) on Co on Ir(111) demonstrates the ability of SP-STM to deter‐
mine and map, in real space, the spin splitting of a ligand orbital of a single molecular magnet
(SMM).
Figure 1: SP-STM topograph of cobalt phthalocyanine molecules (CoPc) on 2 ML of Fe on W110. (a) A spin-resolved overview image shows distinct height varia‐
tion (from blue to yellow) due to the TMR effect within the atomically flat 2nd layer Fe film. Thereby, the spin-up and the spin-down domain of the sample can
be identified. Moreover, individual CoPc molecules can be identified and how a spin-dependent contrast, that can best be seen in the high resolution SP-STM to‐
pographs (b): There are three different molecular orientations with respect to the underlying atomic lattice (as schematically depicted in (c) ). All three molecu‐
lar orientations can be found on both magnetic domains of the Fe. Imaging parameter: I=0.2 nA U= 50 mV
The effective integrated local spin polarization (SP) is determined by the projection of the polarization of the sample (PS) onto the polarization of the tip (PT
). The polarization is given by the normalized difference between the energy integrated density of up-states and the energy integrated density of down
states. Here is the interval of integration defined by the Fermi Energy (EF) and the applied bias voltage (eV) [EF, EF +eV]. The constant (a) is approximately 1
eV-1/2Å-1, Φ is the mean local tunneling barrier height, and is the relative apparent height difference measured between the spin-up domain ( ) and the
spin-down ( ) domain. It is important to note that the effective integrated local spin polarization is determined at the position of the tip ( ). Thereby, only
sample states which have a slow decay into the vacuum, e.g. pz or dz type states contribute significantly to the measured SP.
Figure 2: SP-STM topograph of cobalt phthalocyanine molecule in orientation A on 2 ML of Fe on W110. The model geometry (left image), SP-STM topograph of
CoPC in the spin-up case (left center image), SP-STM topograph of CoPC in the spin-down case (right center image) and the derived map of the local effective
spin polarization (right image).
The origin of this inversion of the SP was determined by comparison with density functional theory simulations (including a correction for van der Waals
forces): new metal-organic hybrid states are formed due to the bonding of molecular π orbitals and metal d-bands, due to symmetry considerations these
states have high weight in the spin-up density of the states close to the Fermi energy (while the Fe-film has high weight in the spin-down density of states
at these energies). The accuracy of the theoretical approach was determined by simulating SP-STM images for the CoPc molecule on both magnetic do‐
mains (spin-up and spin-down) as well as simulating SP maps. In order to qualitatively compare theory and experiment, we look at the normalized SP, i.e.
we divide the SP of the molecule by the SP of the Fe-film, thereby eliminating (in a first approximation) the influence of the tip polarization (which is not
explicitly accounted for in the simulations). Figure 3 shows the convincing agreement between theory and experiment.
Figure 3: Comparison of simulations based on state-of-the-art first principles calculations and experimental SP-STM images of cobalt phthalocyanine mole‐
cules on an ultra-thin Fe film. (a) Simulated SP-STM images for the different spin channels at energies as indicated. (b) experimental SPSTM images. (c) compar‐
ison of the experimental and theoretical distribution of the integrated local effective spin polarization.
Moreover, many organic molecules such as the macrocyclic phthalocyanine (Pc) can be functionalized by various metal atoms, to become paramagnetic or
superparamagnetic, that is to act as single-molecule magnets. These molecules may be, if anchored on an appropriate surface, used to store, read, or ma‐
nipulate magnetic information. Crucial toward the end of realizing functional single molecule devices is the understanding how different molecular con‐
stituents couple to their surroundings, i.e. how the coupling of the molecule to an electrode modifies intrinsic molecular properties such as charge state,
molecular orbital contribution and spin polarization. In recent measurements we were able to resolve the spin splitting of a ligand orbital of a SMM [
bis(phthalocyaninato)terbium(III), abbreviated TbPc2, anchored to a ferromagnetic Co surface. The magnitude of the spin splitting was determined through
SP-STS to be in the order of ~210 meV and it is unambiguously shown that both spin-polarized spectroscopic features stem from the same molecular or‐
bital. By taking maps of the local effective spin polarization at energies corresponding to the energy of the spin-resolved spectroscopic features it is shown
that both features have the same charge distribution, which is typical for the lowest unoccupied orbital of TbPc2 molecules, but they show opposite spin
character (see Fig 4 for an illustration).
Figure 4: SP-STM on anionic TbPc2 on nanoscale Co islands. Using SP-STM and SP-STS it was possible to
measure the spin-splitting of a molecular orbital for the first time in real space. Mapping the charge
and spin distribution clearly shows that the same orbital is probed, first in the spin-up channel, than, at
higher energies, in the spin-down channel. The magnitude of the splitting is determined to be in the or‐
der of ~210 meV, by SP-STS and is induced by the exchange-coupling of the lower PC ring to the Co
support.
Universität Hamburg Contact

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Additional Prof. Dr. Roland Wiesendanger

Head of Group
Information
Institute for Nanostructure and Solid State Physics
Jungiusstraße 11a, Room 302
20355 Hamburg
A. Kubetzka, P. Ferriani, M. Bode,
S. Heinze, G. Bihlmayer, K. von Tel: +49 40 42838-5244
Bergmann, O. Pietzsch, S. Blügel, Email: wiesendanger@physnet.uni-hamburg.de
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17/10/23, 23:19 Molecular Magnets : Nanostructure and Solid State Physics : Universität Hamburg

Universität Hamburg Staff Service Portal STiNE

Nanostructure and Solid State Physics

Figure 1: Structural formula of a Co-Salen (C16H14CoN2O2) and b CuNi-Salen (C18H14CuN2NiO7) or

Further magnetic investigation of single molecules or molecular nanostructures only is possible if

Universität Hamburg Staff Service Portal STiNE

Universität Hamburg Staff Service Portal STiNE

Spin-resolved scanning tunneling microscopy on Molecules

Universität Hamburg Contact

Additional Prof. Dr. Roland Wiesendanger

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