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CRITICAL REVIEW
www.rsc.org/csr
Molecular spintronicsw
Stefano Sanvito*
Received 23rd February 2011
DOI: 10.1039/c1cs15047b
The electron spin made its debut in the device world only two decades ago but today our ability
of detecting the spin state of a moving electron underpins the entire magnetic data storage industry.
This technological revolution has been driven by a constant improvement in our understanding on
how spins can be injected, manipulated and detected in the solid state, a eld which is collectively
named Spintronics. Recently a number of pioneering experiments and theoretical works suggest that
organic materials can oer similar and perhaps superior performances in making spin-devices than
the more conventional inorganic metals and semiconductors. Furthermore they can pave the way
for radically new device concepts. This is Molecular Spintronics, a blossoming research area aimed
at exploring how the unique properties of the organic world can marry the requirements of
spin-devices. Importantly, after a rst phase, where most of the research was focussed on exporting
the concepts of inorganic spintronics to organic materials, the eld has moved to a more mature
age, where the exploitation of the unique properties of molecules has begun to emerge. Molecular
spintronics now collects a diverse and interdisciplinary community ranging from device physicists
to synthetic chemists to surface scientists. In this critical review, I will survey this fascinating,
rapidly evolving, eld with a particular eye on new directions and opportunities. The main
dierences and challenges with respect to standard spintronics will be discussed and
so will be the potential cross-fertilization with other elds (177 references).
School of Physics and CRANN, Trinity College, Dublin 2, Ireland.
E-mail: sanvitos@tcd.ie; Fax: +353-1-6711759;
Tel: +353-1-8963065
w Part of the molecule-based magnets themed issue.
1. Introduction
Most electronic devices, either for logic or sensing applications,
operate on the principle of detecting the variation of an
electrical current with an external stimulus. This can be the
gate potential in a transistor or the presence of the object to
detect in a sensor. Regardless of its nature the stimulus acts to
produce a change in the device electrostatic prole. When the
stimulus has a magnetic origin, then the detection is more
complicated, simply because a magnetic eld is less ecient
then an electric one at driving the electron motion. For
example it takes a magnetic eld of 103 T to produce a Lorentz
force equal to that of an electric eld of 0.1 V nm1 (assuming
that the electron moves at 105 m s1). This means that for
magnetic detection a property dierent from the electrical
charge must be used. This is the spin.
The importance of the spin degree of freedom for the electron
motion in transition metal magnets was acknowledged a long
time ago by Mott,1 who rst expressed the two uids
concept. This establishes that the current in a magnet is carried
by two uids (interacting), characterized by electrons having
opposite spin directions. Such a concept was exploited only
50 years later with the discovery of the giant magneto-resistance
(GMR) eect in magnetic multilayers,2,3 which eectively
demonstrated that the electrical resistance of a magnetic device
can be modied by changing its magnetic texture. This signied
the beginning of the eld of magneto-electronics or, as more
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the external world. Then, I will rst overview the most recent
advances in large-scale devices and nally move to single
molecule junctions. Throughout the discussion I will also
make connections to other research elds which share with
molecular spintronics experimental techniques and concepts.
Little discussion will be dedicated to carbon-only inorganic
macromolecules such as graphite, graphene and carbon nanotubes. For these we refer the reader to the abundant recent
literature.17
In closing this introduction I wish to mention that a number
of comprehensive reviews on dierent aspects around molecular
spintronics have appeared recently. These include spin-transport
in organic semiconductors18,19 and in single molecules,20,21
quantum computing with molecules,2224 molecular materials,25
organic radicals on surfaces,26 and spin-polarized scanning
tunnel microscopy (SP-STM).27
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R0 RH
2P1 P2
;
R0
1 P1 P2
with each other. Secondly, eqn (2) is strictly valid only for
tunneling transport and so it may be inappropriate to use it for
a spin-injection problem. Both these hypotheses have been
recently veried. In support of the rst idea a recent wellcontrolled tunneling experiment on La0.7Sr0.3MnO3/Alq3/Co
junctions with nanoscale cross-section has shown large positive
MR at low temperature,74 interpreted in terms of the particular
bonding structure between Alq3 and the electrodes. At the
same time a model requiring majority spin-injection at both
the Co and La0.7Sr0.3MnO3 electrodes, but including the
electronic structure details of the Alq3 layer and its hopping
conductance, allows one to explain the negative MR.67
Although I will return to the two issues of the sign of the
MR and of the bonding between the organic and the magnetic
electrodes in the next sections, here I wish to stress that such a
controversy unveils our incomplete understanding around the
microscopic origins of the MR in organic materials. One
crucial aspect is that constructing a level-energy diagram for
an organic/inorganic interface is usually quite challenging. Let
us see in some detail what are the problems that might arise.
The rst step in producing a level diagram is that of aligning
the Fermi level of the electrode with the valence band of
the semiconductor, or for extremely localized states, with the
molecule highest occupied molecular orbital (HOMO). This is
in itself a dicult task since chemical reactions might occur at
the interface and the level pinning might be determined by
hybrid interface states.75 Similarly interfacial electrical dipoles
may signicantly alter the vacuum level alignment76 and
so may electron charging.77 Intriguingly such diculties in
determining the alignment of the occupied states across the
junction also highlight the abundance of possibilities that the
organic world has to oer to spintronics. One can for example
envision situations where interfacial dipole engineering is
performed in order to improve the spin-injection eciency
or to produce currents with a spin-polarization superior to
that of the magnetic metals forming the device. Likewise,
dipoles can be used to engineer the magnetic properties of a
metallic surface, as already obtained by using intense electric
elds.78 Notably it was recently demonstrated that functional
group engineering can be used to manipulate also the coercive
eld of a permalloy,82 an eect that can be exploited for
the construction of future devices with tailored magnetic
properties.
The nal step in drawing the level diagram consists in
aligning the organic semiconductor conduction band (or the
lowest unoccupied molecular orbitalLUMO) with respect to
the electrodes EF. The problem here is that one cannot simply
add the optical-gap to the HOMO, since the exciton binding
energy is crucial for photon absorption but bears little relevance
for electron transport. Importantly, misplacing the LUMO
may result in an erroneous assignment of the character
(electron or hole) of the injected electrons. Sometimes, but
this analysis is rarely carried out, a combination of direct and
inverse photo-emission can help in deducing the transport
HOMOLUMO gap.83 Advanced electronic structure theory
based on rst principles methods can also be a powerful tool
in hand. However, its use is complicated by the fact that a
correct description of the quasi-particle states is guaranteed
only when many-body methods (such as the GW scheme)
Chem. Soc. Rev., 2011, 40, 33363355
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R0 RH
2P1 P2 ed=lS
:
R0
1 P1 P2 ed=lS
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Fig. 9 The IV curves for both the GS and the SFS of a Mn12
two-probe device. Note the spin-state characteristic NDRs. C. D.
Pemmaraju, I. Rungger and S. Sanvito, Phys. Rev. B, 2009, 80,
104422. Copyright (2009) by The American Physical Society.
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Fig. 11 Stark energy gain, DEGS, for the singlet and triplet state of a
magnetic molecule as a function of the applied electric eld, E. In
panel (a) we represent a molecule with inversion symmetry, while in
(b) one where the symmetry is broken by an electrical dipole. Note that
the shift of the DEGS(E) parabola by Ebias generates a shift of the
crossover eld to lower elds. J0ST is the exchange interaction energy at
zero eld. N. Baadji, M. Piacenza, T. Tugsuz, F. D. Sala, G. Maruccio
and S. Sanvito, Nature Materials, 2009, 8, 813817. Copyright (2009)
by the Nature Publishing Group.
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4. Conclusions
In this contribution I have reviewed the most recent advances
in the emerging and fascinating elds of organic and single
molecule spintronics. In particular I have highlighted the main
dierence between spintronics in extended organic semiconductors and that in single molecules. The picture emerging
is encouraging although the challenges ahead are still signicant.
Devices made with extended organic semiconductors appear
now reproducible to a good degree and may show room
temperature spin-valve magnetoresistance. Controlling the
quality and the nature of the interfaces between the organic
and the inorganic elements of the device appears to be the
critical aspect in the fabrication process. This sensitivity however
can be turned into a strength and examples of improved
magnetoresistance tuned by chemical doping of the interfaces
are rapidly appearing.
In contrast single molecule devices remain highly unstable
and dicult to reproduce. However, when made, these may
show a range of intriguing properties not shared by large area
devices. In particular the use of functional molecules where
switching activity is present may give access to electrically
controlled single molecule spin devices.
In moving forward organic and molecular spintronics have also
to face an additional challenge beyond the technical issues
mentioned above. This is the need of nding a range of specic
applications where the unique characteristics of organic materials,
namely the long spin diusion times, are fully exploited.
Acknowledgements
This work is sponsored by Science Foundation of Ireland (grant
No. 08/ERA/I1759 and 07/IN.1/I945) and by CRANN. I would
like to thank Nadjib Baadji for a critical review of the manuscript.
References
1 N. F. Mott, Proc. R. Soc. London, Ser. A, 1936, 153, 699717.
2 M. N. Baibich, J. M. Broto, A. Fert, F. Nguyen Van Dau,
F. Petro, P. Etienne, G. Creuzet, A. Friederich and
J. Chazelas, Phys. Rev. Lett., 1988, 61, 24722475.
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