progress article

Published online: 24 august 2009 | doi: 10.1038/nmat2510

spin routes in organic semiconductors

V. alek dediu1*, luis e. hueso2, ilaria bergenti1 and Carlo taliani1

Organic semiconductors are characterized by a very low spin–orbit interaction, which, together with their chemical flexibility
and relatively low production costs, makes them an ideal materials system for spintronics applications. The first experiments
on spin injection and transport occurred only a few years ago, and since then considerable progress has been made in improving
performance as well as in understanding the mechanisms affecting spin-related phenomena. Nevertheless, several challenges
remain in both device performance and fundamental understanding before organic semiconductors can compete with inorganic
semiconductors or metals in the development of realistic spintronics applications. In this article we summarize the main experi-
mental results and their connections with devices such as light-emitting diodes and electronic memory devices, and we outline
the scientific and technological issues that make organic spintronics a young but exciting field.

R
esearch in organic semiconductors (OSCs) has progressed
impressively over the past few decades1. The greatest success
has undoubtedly been achieved in the field of optoelectronics.
Display products based on hybrid light-emitting diodes with
organic emitters (OLEDs) have become available to consumers, and
organic photovoltaic devices are challenging existing commercial
applications. These accomplishments generate a strong demand for
other mainstream products based on new hybrid organic–inorganic
devices. Considerable improvements have already been achieved
in the field of organic field-effect transistors (OFETs), and funda-
mental research in the use of organic electric memories for data-
storage applications has also progressed.
Organic semiconductors have recently caught the attention of
the spintronics community, and significant efforts are being made
towards their integration in this field2,3. Spintronics is a branch of
electronics that takes full advantage of not only the charge, but also
the spin of the electron. Spintronics encompasses different topics,
and it involves the generation of a non-equilibrium spin polariza-
tion in various materials and devices, as well as its manipulation and
detection4–7. Among the most fascinating examples of spintronic
applications are giant magnetoresistance (MR) and tunnelling
magnetoresistance (TMR). In both cases, a considerable variation of
the electrical resistance can be achieved by switching the magnetiza-
tion of the device’s electrodes from parallel to antiparallel8–10.
The most attractive aspect for spintronic applications in OSCs
is the weakness of the spin-scattering mechanism, implying that
the spin polarization of the carriers can be maintained for a very
long time. This property is due to the very low spin–orbit coupling
in OSCs: carbon has a low atomic number (Z), and the strength
of the spin–orbit interaction is proportional to Z4. Noticeably,
spin-relaxation times in excess of 10 μs were obtained by different
resonance techniques11,12 years before the first organic spintronic
experiments; these values exceeded the characteristic times detected
in inorganic materials by orders of magnitude5,13.
It is difficult at this stage to predict whether research efforts in
organic spintronics will lead to their implementation into actual
devices. At present, organic spintronics can be regarded as a fasci-
nating puzzle in which many pieces are still missing. The electronic
properties of OSCs are radically different from those of such band
semiconductors as Si or GaAs. Consequently, their spin properties
are also different. In band semiconductors, the spin injection and
transport are commonly described by considering either ballistic
or diffusive motion of spin-polarized carriers in delocalized band
states. The spin-flipping processes proceed mainly via spin–orbit
interaction, which are able to transfer the scattering of the angular
momentum into spin scattering. Organic semiconductors are not
characterized by band conductivity, nor do they feature a significant
spin–orbit interaction. The electrical carriers propagate in OSCs
by incoherent hopping between strongly localized states that can
be approximated to very narrow bands only at low temperatures.
Unveiling the fundamental aspects of these materials is therefore
what makes the field simultaneously challenging and exciting, with
the hope that improvements in understanding and technology will
allow OSCs to compete with and overtake other materials in the
field of spintronics, or at least in some selected niche applications.
In this review we focus on the main achievements and questions
arising from spin injection and transport in OSC materials. We
begin by presenting and discussing the concepts and facts that are
widely accepted by the community, and conclude by addressing the
most controversial issues and open questions.
To the best of our knowledge, no communication on fully organic
spintronic devices has appeared yet, as only hybrid structures with
magnetic inorganic electrodes and organic active layers have been
investigated. Nevertheless, for the sake of simplicity, we will call
such devices organic spintronic devices (OSPDs).
electrical injection and detection
In the following discussion on the electrically operated OSPDs, it
is necessary to distinguish between two different cases: tunnelling
devices characterized by zero residence time of charges/spins in the
organic barrier, and injection devices in which there is a net flow of
spin-polarized carriers directly into the electronic levels of the OSC.
Although tunnelling devices can feature large MR values and are
useful as 0–1 switching elements, or as magnetic sensors, injection
devices are characterized by a finite lifetime of the generated spin
polarization in the OSC, and offer such possibilities as spin manipu-
lation, control of the exciton statistics in the OSC, and so on. These
options may well open the way to magnetically controlled OFETs
or OLEDs.
The electrical properties of OSCs are rather complex and in
principle may vary depending on the specific material used, but we
can nevertheless summarize most of the common features. OSCs are
mainly families of π-conjugated molecules, merging a considerable
delocalization of carriers inside the molecule with weak van der Waals

ISMN-CNR, via Gobetti 101, 40129 Bologna, Italy. 2CIC nanoGUNE Consolider, Tolosa Hiribidea 76, E-20018 Donostia - San Sebastian and IKERBASQUE,
1

Basque Foundation for Science, E-48011 Bilbao, Spain. *e-mail: V.Dediu@bo.ismn.cnr.it

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progress article NaTure maTerIals doi: 10.1038/nmat2510
a b
0

6T
LSMO LSMO –0.2

R(H)–R(0) (GΩ)
–0.4

–0.6 S S S
w = 70–500 nm S S S
V
–0.8
I

–1.0
100 200 300 400
Channel length (nm)

c d e
26.0
11 K 40 0

22.5 P P 30 P P

∆R/R (%)
Co –1
I∆R/RI (%)

20
OS
R (kΩ)

N
20.0 O O
Al
N N 10 LSMO
O
Substrate –2 T = 40 K
17.5 0
AP AP AP AP
–10
–1,500 -750 0 750 1,500 –3.0 –1.5 0 1.5 3.0
Magnetic field (Oe) Magnetic field (kOe)

Figure 1 | Organic spintronic devices. a, Lateral spin device as published by Dediu et al.20. In this device, two ferromagnetic LSMO electrodes patterned by
electron-beam lithography were separated by 70–500 nm and bridged by a 6T channel. b, Magnetoresistance (H = 0.3 T, where H is the magnetic field)
of the lateral spin device depicted in a as a function of the channel length. The error bars indicate the possible local deviations from the nominal channel
length. c, Magnetoresistance loop of a LSMO (100 nm)/Alq3 (130 nm)/Co (3.5 nm) spin-valve device measured at 11 K (ref. 23). As indicated in the figure,
an antiparallel (AP) configuration of the magnetization of the electrodes corresponds to a low-resistance state. d, Schematic of a typical vertical inorganic–
organic spin valve. In this case, LSMO is the bottom electrode and Co is the top one. A typical MR measurement is performed by applying a bias voltage to
the metallic ferromagnetic electrodes and the current is measured as a function of the in-plane external magnetic field. e, Magnetoresistance loop of a LSMO
(20 nm)/6T (100 nm)/Al2O3 (2 nm)/Co (20 nm) vertical spin-valve device measured at 40 K. Figure reproduced with permission: c, © 2004 NPG.

intermolecular interactions, which considerably limit the carrier
mobility. The injection of carriers into OSCs is best described14 in
terms of thermal and field-assisted charge tunnelling across the inor-
ganic/organic interface, followed by carrier diffusion into the bulk of
the OSC. Furthermore, the carriers propagate by random site-to-site
hopping between pseudo-localized states that are distributed within
an energy interval of approximately 0.1 eV. Two conducting chan-
nels are usually considered active: the lowest unoccupied molecular
level (LUMO) for n-type and the highest occupied molecular level
(HOMO) for p-type carriers; however, defects and interface states
may also have to be considered depending on the material and its
structural quality. Another important issue is the strong electron–
phonon interaction leading to the carriers having a polaronic char-
acter (for more extensive reading we suggest a recent review 15).
In principle, any discussion of spintronics effects requires an
accurate definition of the spin polarization of the carriers. For
inorganic surfaces or interfaces featuring band-like behaviour,
it has been shown16 that the spin polarization may be defined in
different ways, depending on the specific experimental or theoreti-
cal approach adopted. The simplest definition, which considers just
the density of states (N) at the Fermi level (EF), is that spin polari-
zation is equal to (N↑ − N↓)/(N↑ + N↓), and it is mostly valid for
static cases such as, for example, spectroscopic characterization. The
symbol ↑(↓) indicates majority (minority) spin orientation in a fer-
romagnetic material with respect to the direction of magnetization.
In experiments that involve current across interfaces, the definition
of spin polarization may require the substitution of N by Nv (bal-
listic regime) or by Nv 2 (diffusive regime), depending on the specific
interface and transport mechanism considered16. Here, v is the Fermi
velocity in the spin-polarized material, and Nv and Nv 2 are defined
by integration over the Brillouin zone. It has not yet been possible to
establish which particular definition is applicable for ferromagnetic/
organic interfaces. The injection of charge/spins across such inter-
faces corresponds to a transition from extended (band character)
states into almost fully localized ones, which accounts for a dra-
matic symmetry breaking and leads to the failure of the common
models used for purely inorganic interfaces17. Similarly, the exten-
sion of the band-symmetry model developed for TMR (inorganic)
devices should be treated with caution when applied to inorganic
spintronics18,19: the symmetry breaking mentioned above consti-
tutes a serious barrier and requires a considerable modification of
these models.
The first report on experimental injection in OSPDs was
published as recently as 2002 (ref. 20). The authors designed a lateral
device that combined ferromagnetic electrodes and OSC conducting
channels 100–500 nm in length (Fig. 1a). The selected ferromagnetic
material was a highly polarized manganite (La0.7Sr0.3MnO3, or
LSMO). This material was already well known for its spin-injection
properties and has proved to be highly successful in diverse inor-
ganic spintronic devices, such as tunnel junctions19 and artificial
grain-boundary devices21. Sexithiophene (6T), a rigid conjugated-
oligomer rod, and a pioneer in organic thin-film transistors22, was
chosen for the spin-transport channel. A strong magnetoresistive
response was recorded up to room temperature in 100-nm and
200-nm channels (Fig. 1b), and was explained as a result of the
conservation of the spin polarization of the injected carriers. Using
the time-of-flight approach, a spin-relaxation time of the order of
1 μs was found. This work designated organic materials as extremely

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NaTure maTerIals doi: 10.1038/nmat2510 progress article
Table 1 | main properties of organic semiconductors investigated in organic spintronics.
organic semiconductors spin-polarized electrodes spin-diffusion length ls (nm) Carrier mobility electronic and
and time τs (s) optical properties
6T LSMO/ Ls ≈ 70 (refs 20, 75) 10−1 cm2 V−1 s−1 HOMO = 4.9 eV
S S S LSMO τs ≈ 10−6 p-type LUMO = 2.3 eV
S S S

Alq3 LSMO/Co (refs 25, 27–29) Ls ≈ 100 (ref. 27) ls ≈ 45 (ref. 23) 10−5 cm2 V−1 s−1 HOMO = 5.7 eV
Fe/Co (refs 32, 68) τs ≈ 26 × 10−6 n-type LUMO = 2.7 eV
N Co/Ni (ref. 76) τs ≈ 10−3 light emitter
O O
Al
N
N O

α-NPD LSMO/Co (ref. 25) 10−5 cm2 V−1 s−1 HOMO = 5.4 eV
p-type LUMO = 2.3 eV
N N

CVB LSMO/Co (ref. 25) 10−3 cm2 V−1 s−1 HOMO = 5.5 eV
LUMO = 2.5 eV
Blue dopant for OLED
N

RRP3HT LSMO/Co (ref. 28) Ls ≈ 80 (ref. 28) 10−1 cm2 V−1 s−1 HOMO = 5.1 eV
C 6H13 C 6H13 Fe50Co50 /Ni81Fe19 (ref. 31) p-type LUMO = 3.5 eV
S
S S n
C 6H13

Tetraphenylporphyrin (TPP) LSMO/Co (ref. 29) 10−5 cm2 V−1 s−1 Red emitter for OLED
n-type

N
NH HN
N

Pentacene Co:TiO2/Fe (ref. 77) 10−1 cm2 V−1 s−1 HOMO = 4.9 eV
p-type LUMO = 2.7 eV

Rubrene Co/Fe (ref. 39) Ls ≈ 13.3 1 cm2 V−1 s−1 HOMO = 5.2 eV
p-type LUMO = 3.0 eV

CuPc Co (ref. 42) 10−2 cm2 V−1 s−1 HOMO = 5.3 eV

p-type LUMO = 3.6 eV

N N N

N Cu N

N N N

attractive candidates for long-distance spin transport, although
still leaving some important questions unanswered. For example,
the experiment20 did not provide a straightforward demonstration
that the MR was related to the magnetization of the electrodes, and
hence to its spin polarization, as no comparison between parallel
and antiparallel magnetization of electrodes was available.
Following this encouraging report, an important step forward
was the fabrication of a vertical spin-valve device consisting of
LSMO and cobalt electrodes, sandwiching a thick (100–200 nm)
layer of tris(8-hydroxyquinoline)aluminium(iii) (Alq3) (Fig. 1c,d)23.
Alq3 has been a popular OSC since the early stages of xerographic
and optoelectronics applications24. The spin valve showed MR up

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progress article
to a temperature around 200 K, and for voltages below 1 V. Unlike
standard spin-valve devices, in which lower resistance corresponds
to parallel electrode magnetization, the LSMO/Alq3/Co devices
showed lower resistance for an antiparallel magnetization configura-
tion. Several other groups have subsequently confirmed this so-called
inverse spin-valve effect in LSMO/Alq3/Co devices25–29. The result is
one of the most widely reproduced effects in organic spintronics and
is discussed in detail below. Alq3 is by far the most successfully used
OSC in the field of spintronics in spite of its very low mobility: about
10–5 cm2 V–1 s–1 for electrons and less than 10–6 cm2 V–1 s–1 for holes30.
Although the full relevance of the mobility has yet to be understood
for OSPDs, the wide use of Alq3 is probably due to the high-quality
thin films that can be grown on various ferromagnetic substrates by
standard ultrahigh vacuum (UHV) evaporation.
Electrical detection of spin injection and transport has also been
pursued in other OSCs (see Table 1). A comparative study of various
OSCs — Alq3, N,N-bis(1-naphthalenyl)-N,N-bis(phenylbenzidine)
(α-NPD) and 4,4′-bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl
(CVB; ref. 25) — with a fixed set of magnetic electrodes (LSMO
and Co) has produced quite similar results for each of the materials
studied: inverse spin-valve effect (around 10% at low temperatures)
and fast decrease of the MR with increasing temperature, vanish-
ing between 210–240 K. The same electrodes have been used as
injectors for other OSCs, such as tetraphenylporphyrin (TPP)29.
More recently we have succeeded in confirming 6T as an efficient
spin-transport layer, achieving a very sharp (inverse) spin-valve
effect in a vertical device (Fig. 1e). In spite of considerably dissimilar
resistance values owing to radically different geometries, both pla-
nar and vertical devices based on 6T showed reproducible resistiv-
ity values in the range 1–5 × 106 Ωcm, as expected for the so-called
naturally doped sexithiophene22.
The experiments described above were performed using UHV
conditions for the OSC growth. Spin-coated polymers such as
regio-random and regio-regular poly(3-hexylthiophene) (RRaP3HT
and RRP3HT, respectively), have also shown noticeable MR28,31. In
these reports, the spin-valve effect was positive and a small value
was recorded even at room temperature.
Unfortunately, MR measurements provide mainly qualitative
information. In the absence of well-defined models for spin injection
and transport in OSCs, it is difficult to reach any conclusion on the
exact values of the polarization or its decay inside the organic material.
Nevertheless, the investigation of the temperature dependence of the
NaTure maTerIals doi: 10.1038/nmat2510
MR and a careful analysis of its sign can provide important hints for
the basic physics underlying the device behaviour.
For the discussion on the temperature dependence of the MR,
we concentrate on the most archetypal device: LSMO/Alq3/Co
(refs 25–29). A few groups have investigated in detail the tempera-
ture dependence in these devices, and initially a maximum work-
ing temperature in the 210–250 K region was reported — see for
example the blue28 and red25 markers in Fig. 2a. An attempt to
surpass this temperature range was performed by substituting
LSMO with a high-temperature ferromagnetic element such as Fe.
Unfortunately, the temperature at which MR was recorded was even
lower 32, leaving open the question about room-temperature opera-
tion of Alq3-based spintronic devices.
Very recently, room-temperature MR in LSMO/Alq3/Al2O3/
Co devices was demonstrated27 by improving the quality of both
injecting interfaces, especially the top one, in which a thin insulating
layer was added (see the green circles in Fig. 2a). Although the room-
temperature MR was quite weak, most likely due to the vicinity to
the LSMO Curie temperature TC, this result indicated Alq3 as a
valuable OSC for room-temperature applications.
A surprising and very indicative result has been found by
studying the MR as function of temperature: MR decreased with
temperature following exactly the surface magnetization of LSMO
and vanishing at its TC (refs 25, 27). This behaviour indicates that
the temperature dependence of these devices is completely domi-
nated by the injection process, and the corresponding temperature
dependence of the spin-transport losses inside OSCs must be very
weak. The surface magnetization in LSMO can be described27 by the
empirical law proposed by Park et al.33 and featuring a dependence
close to (1 − T/TC)2 at intermediate temperatures. By comparing the
LSMO surface magnetization and the MR of the devices, it can be
concluded that the temperature dependence of the spin-transport
losses in Alq3 is much weaker than T2. Furthermore, the presence of
an injection-dominated electronic-transport regime could partially
explain the random thickness dependence of the MR reported in
some articles29,34.
The inversion of the spin-valve effect for LSMO/Alq3/Co
devices has been detected in devices made from the following:
LSMO/Alq3/Co (refs 23,28,29,34), LSMO/Alq3/Al2O3/Co (ref. 27)
and LSMO/Alq3/LiF/Co (ref. 26). This shows that the effect is
independent of the material combination at the top interface.
Noticeably, the available knowledge on the spin polarization at both

a b
1.0 Interfacial dipole Interfacial dipole
R R R R R R
4.9 eV ∆ ~1 eV 5.0 eV ∆ ~1.4 eV
S S S S S S

0.5 R = C6H13
Normalized MR

LUMO
0.0 LUMO
EF ∆i EF ∆i
0.0

N HOMO
–0.5 O O HOMO
Al
N N
O

–1.0 LSMO Alq3 Co Alq3

0 50 100 150 200 250 300
Temperature (K)

Figure 2 | magnetoresistance of lsmO/Co vertical OsPDs. a, Temperature dependence of the normalized MR of different vertical OSPD devices with
LSMO and Co as magnetic electrodes. Positive MR (upper panel) for a device with a 100-nm-thick RRP3HT interlayer28. Magnetoresistance for devices
with Alq3 as an organic interlayer as reported by different authors (bottom panel): (blue) 130-nm-thick Alq3 device28; (red) 160-nm-thick Alq3 device25;
(green) 100-nm-thick Alq3 device27. Arrows indicate the temperature at which the corresponding MR signal goes to zero. b, Schematic band diagram for
both LSMO/Alq3 and Co/Alq3 interfaces (Zhan et al.52). Δi represents the lowest injection barrier.

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NaTure maTerIals doi: 10.1038/nmat2510 progress article
interfaces seriously contradicts the negative-MR data. It has been MR was observed to switch from positive to negative for different
demonstrated that Co injects majority (up) spins for both Co/Alq3 voltage values, but also from sample to sample at the same voltage.
and Co/Al2O3/Alq3 interfaces35, via spin-sign-sensitive experi- Although evidence of the spin-polarized tunnelling through an
ments on Zeeman effects in superconductor/barrier/Co structures. organic monolayer was given, it has also been noticed that such
Manganites such as LSMO are widely accepted as majority (spin up) devices are subject to strong intrinsic and extrinsic noises.
injectors. If the above statements are correct, for parallel magnetiza- MR has been detected also in devices with a Langmuir–Blodgett
tions both electrodes inject spins of the same dominant sign, but monolayer film as the tunnel barrier 37,38. However, the presence of
this orientation provides higher resistance than antiparallel elec- a continuous organic monolayer confined between the two ferro-
trodes injecting spins of opposite signs. magnetic electrodes was not convincingly demonstrated, leaving the
A recently proposed model27 accepts the positive sign of the nature of the observed magnetoresistive effects open to question.
spin polarization for carriers coming from both LSMO and Co. An important step forward for organic spin tunnelling was the
The inversion of the MR is thought to be due to the presence of a fabrication of devices by direct in situ UHV organic vapour deposi-
narrow (< 0.1 eV) conducting level lying above the Fermi levels of tion with shadow masking (Fig. 3a,b). Vertical tunnelling devices
the electrodes. The spin-up electrons injected in this level propagate (Co/Al2O3/Alq3/NiFe (ref. 35) and Co/Al2O3/rubrene/Fe (ref. 39))
by hopping through the whole OSC thickness and, when they reach made use of a hybrid inorganic–organic ultrathin barrier to produce
the second electrode, tunnel into the spin-down (minority) states of positive (non-inverse) TMR when the electrode magnetizations
the Co (LSMO), which dominate at energies above EF. This model were switched from parallel to antiparallel. TMR around 15% was
holds only for materials with n-type or at least mixed conductivity, recorded at 4.2 K (ref. 39), and importantly, both OSCs showed
and cannot be applied for pure p-type OSCs. A direct determination significant (that is, a few percent) TMR at room temperature, open-
of the sign of the spin polarization injected across the LSMO/Alq3 ing the door to possible commercial applications. Another impor-
interface would either confirm the model or indicate the need to tant aspect is that Al2O3/Alq3 devices had tunnel barriers well inside
find an alternative explanation. the typical quantum mechanical tunnelling regime (0.6–1.6 nm);
however, the Al2O3/rubrene hybrid barriers were considerably
spin tunnelling in osPds thicker, as rubrene layers ranged from 4.6–15 nm. These thicknesses
While the interest in spin injection and long-distance spin transport that are larger than the standard tunnelling-regime numbers prob-
in organic semiconductors was growing, several groups also started to ably indicate the existence of spin injection in the rubrene layers.
explore the possibilities of these materials as spin-tunnel barriers. Recently, very large positive TMR up to 300% was detected at 2 K
Spin-polarized tunnelling in OSPDs has been initially demon- in a LSMO/Alq3/Co nanosized tunnel junction (C. Barraud et al.,
strated in quite complex geometries. Petta et al.36 fabricated Ni/octa- unpublished results).
nethiol/Ni vertical tunnelling devices in a nanopore geometry with The experiments reported above clearly show spin-polarized
an octanethiol self-assembled monolayer. These devices showed MR tunnelling across organic and/or organic–inorganic hybrid barriers.
up to 16% at 4.2 K, which vanished at about 30 K. The sign of the We must also note that there have been reports across thick (~100 nm)

a c
Py

3
Alq

2
SiO
Co

ive
Nat

Si

Nickel Sulphur Carbon Hydrogen

5 nm

b d
3
RJ(T)/RJ(T = 300 K)

8
300 K 40.0
77 K
2 600
MR (%)

4.2 K 400
6 1 20.0 200
0 100 200 300
T(K) 0
TMR (%)

I (µA)

–2 –1 0 1 2
0
4 N
0 Parallel configuration
AI –20.0 Antiparallel configuration
0 N
2 N
0

–40.0
–2 –1 0 1 2
0 V (V)
–100 –50 0 50 100 150
Magnetic field (Oe)

Figure 3 | Tunnelling mr. a, High-resolution transmission electron microscopy (HRTEM) image of a magnetic tunnel junction with a thin (few nm) Alq3
barrier. b, TMR of an organic tunnel junction similar to the one presented in a. The inset shows the temperature dependence of the resistance of the
junction35. The value for the spin polarization of the tunnel current across an Alq3 barrier is positive, with values around 30% for Co, Permalloy (Py) and Fe.
RJ represents the junction resistance. c, Schematic representation of a tricene molecule attached to a (001) Ni surface13. d, Theoretical calculation of the
current–voltage (I–V) characteristic of a tricene–nickel spin-valve. The inset shows the calculated MR ratio with values up to 600%13. Figures reproduced
with permission: a,b, © 2007 APS; c,d, © 2005 NPG.

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progress article
organic layers whose results have been interpreted in a tunnelling
framework, essentially by claiming transport only through defects
in the organic layer 29,40. Although the control of spin tunnelling
across organic layers is still relatively poor, it is also clear that there
is a great margin for improvement, especially in the fields of inter-
face control and engineering, and for single-molecule studies.
beyond magnetoresistance
Although the main experimental efforts in the field of organic
spintronics have so far been dedicated to electrical devices, other
approaches have also been investigated. Soon after the first electrical
spin-transport experiment in OSCs, the potential of organic
materials as spin-transfer media was highlighted by time-resolved
Faraday rotation spectroscopy 41. Spin transfer was optically detected
between CdSe quantum dots (QDs) connected via dithiol molecules
(a combination of 3.4-nm and 7-nm QDs were prepared). The spin-
polarized light coming from the 7.0-nm QDs caused a coherent
spin-dynamic transfer in spatially separated and spectrally different
3.4-nm QDs. This coherent spin transfer through molecular bridges
was found to persist up to room temperature with an efficiency of
approximately 20%.
Two powerful techniques introduced recently in the field of
organic spintronics, two-photon photoemission spectroscopy and a
muon spin-rotation technique (see Fig. 4), have succeeded in reveal-
ing the profile distribution of the spin polarization inside OSCs.
NaTure maTerIals doi: 10.1038/nmat2510
Two-photon photoemission spectroscopy experiments are
performed with just a few OSC monolayers grown on top of an
intrinsically spin-polarized ferromagnetic material42. Spin-polarized
electrons from the metal are excited by the first energy pulse into
an intermediate energy state. Some of the electrons propagate into
the OSC where, with a certain probability, they can be excited by
the second photon causing the photoemission. The analysis of the
average spin polarization of the photoemitted electrons allows for
the definition of the exact scattered intensity along both the space
and the energy profiles. The spin-polarized injection efficiency from
Co into the first monolayer of the copper phthalocyanine (CuPc)
was estimated to be close to 100% (that is, no losses with respect
to the starting value)42. Noticeably, a weak decay of the polariza-
tion was registered for up to 16 monolayers (40% spin polarization
remaining), although we must note that this experimental technique
is less accurate for relatively thick layers. A further improvement of
the method may be achieved by decreasing the energy at which the
electron is photoinjected, as the energy currently available consid-
erably exceeds the LUMO level (hot electrons) resulting in higher
spin-scattering rates than in transport measurements.
In a second report, electrical injection was combined with low-
energy muon spin rotation to study the spin-diffusion length (ls)
inside Alq3 in a standard vertical spin-valve device43. The stopping
distribution of the spin-polarized muons was varied in the range
3–200 nm by controlling the implantation energy. A quantitative

100 Efinal
Normalized spin polarization (%)

Evac

80

LUMO
60 EF
HOMO

Cobalt CuPc
40
0 4 8 12 16
CuPc coverage (Monolayers)

b 40
V–
s

I– LiF
30 p
Spin-diffusion length (nm)

I+
FM2: NiFe
20
V+
Alq3

10
TPD
FM1: FeCo �10kV
Substrate
0 20 40 60 80 100 0V
Temperature (K)

Figure 4 | Non-electrical spin-injection experiments. a, Normalized spin polarization as a function of CuPc thickness on a Co/CuPc junction. The values,
obtained by two-photon photoemission spectroscopy42, show a spin-injection efficiency of 85% from the Co substrate into the CuPc unoccupied molecular
orbitals. In the two-photon photoemission experiment (shown right), CuPc electrons are excited from the Co by an initial light pulse in intermediate
states lying between the Fermi and the vacuum level of the heterojunction. A second photon gives to some of those excited electrons enough energy to be
photoemitted. The error bars show the standard deviation of the detected photoemission yield. b, Temperature dependence of the spin-diffusion length in
Alq3 extracted from the muon spin-relaxation experiments reported in ref. 43. Error bars represent one standard deviation for the spin-diffusion length are
an estimate based on the scatter in the data for the MR measurements. A schematic representation of the device is shown on the right. B, magnetic field;
p, muon momentum; s, initial muon polarization; FM1, FM2, ferromagnetic contacts. Figures reproduced with permission: a,b, © 2009 NPG.

712 nature materials | VOL 8 | SEPTEMBER 2009 | www.nature.com/naturematerials

© 2009 Macmillan Publishers Limited. All rights reserved

NaTure maTerIals doi: 10.1038/nmat2510
analysis determined the spin-diffusion length and its temperature
dependence. On the one hand, the diffusion length reached a low-
temperature value of 35 nm: a lower value than the one estimated
from electrical measurements (> 100 nm), a discrepancy that could
nevertheless be explained, bearing in mind the imperfect injection
efficiency of the device being studied. On the other hand, the weak
temperature dependence of the ls is in good qualitative agreement
with independent MR characterizations in Alq3-based devices27,
and is also in agreement with a recently proposed mechanism for
the hyperfine-driven spin scattering in OSCs (see below).
Electroluminescence, another important OSC property, has
had a crucial role in the development of inorganic spintronics. The
detection of circularly polarized light from semiconductors (direct
optical transitions with integer variation of the spin state) has
demonstrated unambiguously the existence of a finite spin polariza-
tion in ferromagnetic/GaAs structures44–46. In OLEDs the situation
is different because, owing to low spin–orbit coupling, the domi-
nant electroluminescence channel involves singlet–singlet transi-
tions1. In OLEDs, the singlet/triplet ratio is determined by quantum
statistics to be 1:3 when taking into account a similar formation
probability for one singlet and three triplet states (Fig. 5a). The injec-
tion of carriers with a controlled spin state could therefore allow the
amplification of the singlet (triplet) exciton density (see Fig. 5b),
leading to a significant increase of electroluminescence efficiency 47.
Although these considerations are mathematically straightforward,
experimental efficiency amplification has not been reported in the
literature, despite several attempts48,49. This negative result is pos-
sibly due to the fact that light emission can only be detected for
an applied voltage in excess of a few volts, whereas spin injection
in organic materials has been demonstrated so far for voltages not
exceeding 1 V23,47. Although this limitation does not seem to be a
fundamental obstacle, it has to be yet understood whether it can be
circumvented experimentally.
Possibly the most interesting result related to charge–photon
conversion has come so far from a completely different approach,
namely a coherent spin manipulation demonstrated by electron
spin resonance (ESR)50 in an OLED. The authors succeeded in
achieving a magnetically guided transfer between singlet and triplet
polaron pairs caused by the spin precession around an additional
magnetic field perpendicular to the Zeeman splitting field. The
polaron pairs are generally considered as precursors for the exciton
formation, as they can either split into a separate electron–hole pair
or stick together as an exciton. The two conversion channels give
completely different inputs into the photoconductivity, and moni-
toring the exciton channel provides a way to control the polaron-
pair dynamics and transformations. A periodical modification of
the singlet-to-triplet polaron-pair transfer (Rabi oscillations) was
observed in the conjugated polymer MEH-PPV. The OSC studied
showed an extremely long spin-coherence time50 of about 0.5 μs,
pointing to very interesting application possibilities.
Last but not least, we should not forget photoelectron experi-
ments, which have been crucial for a deeper understanding of
the energy levels at the interface between ferromagnetic and
organic materials (Fig. 2b). In particular, both X-ray and ultra-
violet spectroscopies have been systematically used to explore
different combinations of materials. For LSMO/Alq3, Co/Alq3
and Co/CuPc, it has been found that strong electrical dipoles are
present at the interfaces28,51–56. These interfacial dipoles can alter
the non-interacting equilibrium energy levels by more than 1 eV.
A detailed quantification of these energy shifts is crucial for the
understanding of the electronic transport properties (includ-
ing, of course, the MR) of hybrid ferromagnetic–organic devices.
Recently, Grobosch et al.56 have questioned whether interfacial
energy values measured in UHV conditions can be used to explain
the electronic transport behaviour of actual devices measured in
standard laboratory conditions.
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© 2009 Macmillan Publishers Limited. All rights reserved
progress article
a b
Singlet state Triplet states
e
HTL h e
S0
1
ETL
h h e
Anode Cathode 2 S0
h e
3 S0
Figure 5 | spin-OleD. a, Schematic structure of a bilayered OLED.
Electrons and holes are injected respectively by the cathode and the anode
into the electron-transport layer (ETL) and the hole-transport layer (HTL).
Exciton formation and recombination take place at the interface between
the two organic layers. b, Spin statistics of the carrier recombination for the
case of case of spin-polarized carrier injection: (1) One singlet and three
triplet exciton states are expected for random orientation; the singlet state
is responsible for light emission whereas triplet states usually deactivate
without emitting radiation with a 25% (1:3) efficiency. (2) Parallel spin
states for electrons and holes produce only a non-emitting triplet state.
(3) Antiparallel spin states for electrons and holes generate singlet and
triplet states in a 1:1 ratio.
theoretical models
In parallel with the experimental efforts described above, consider-
able and fruitful work has also been performed on the theoretical
side. A number of articles have been published in the field, reveal-
ing some of the most important properties of ferromagnetic/OSC
interfaces and advancing predictions for both spin injection and
transport in various OSPD configurations. Most of the models and
results are closely connected to realistic experimental configura-
tions, thus providing very useful information for cross-checking
experimental results and stimulating new ideas.
Considerable attention has been dedicated to the description of
tunnelling devices with a single molecule (or a few) placed between
two spin-polarized electrodes13,57,58. Very interesting results have
been obtained by applying density functional theory combined
with non-equilibrium Green’s functions to calculate the transport
characteristics13,59 (Fig. 3c,d). Rocha et al.13 considered two pro-
totypical molecules, 8-alkane-dithiolate (octane-dithiolate) and
1,4-3-phenyl-dithiolate (tricene-dithiolate), sandwiched between
nickel contacts. Very large MR values have been calculated for both
cases: about 100% for the octane-dithiolate and up to 600% for
the tricene-dithiolate molecule. These extremely high MR values
seem to have found experimental confirmation in recent work
(C. Barraud et al., unpublished results).
The question about the optimal interface state for reaching an
efficient spin injection and detection (MR intensity) is a topic under
discussion. A few authors have indicated that an ohmic contact
would be more efficient for spin injection into OSCs60. In contrast,
it has been suggested in many other papers that spin injection into
OSCs can only be achieved across an interfacial tunnel or Schottky
barrier 61,62. In all the cases in which spin injection into OSCs has
been demonstrated, the organic/inorganic interfaces presented
713
progress article
natural Schottky-like barriers, thus showing that experimentally
this kind of interfacial contact seems more adequate for the realiza-
tion of OSPDs.
A Su–Schrieffer–Heeger model was applied by Xie et al.63 to study
the importance of the electron–lattice interactions, considering inter-
faces featuring strong polaronic effects on both sides. The authors
showed that under certain biases, spin-polarized injection can be
achieved for direct manganite/OSC interfaces, whereas substitution
of the manganite with a conventional (non-polaronic) ferromagnetic
metal resulted in the absence of a spin-polarized flow.
Understanding and describing the processes responsible for the
attenuation of the spin polarization induced in OSCs is of para-
mount importance for the development of the field. OSCs have very
small spin–orbit coupling, so other alternative mechanisms need
to be considered. Recently, Bobbert et al.64 advanced the idea that
the precession of the carrier spins in the random hyperfine fields
of hydrogen nuclei represents the dominant source of spin scat-
tering in OSCs. A large number of hydrogen atoms with relatively
large hyperfine fields (around 5 mT) are normally present in organic
molecules. This scattering mechanism is amplified in materials with
strongly localized carriers, where the interaction (that is, precession)
time is long enough. The authors have derived the ls in a typical
OSC as a function of various parameters. Among the results that we
would like to mention is a very weak dependence of ls on tempera-
ture, which is in good agreement with recent experimental data27.
It was also shown that, surprisingly, the spin-scattering strength is
much less sensitive to disorder than the carrier mobility, a result that
could shed light on the apparent discrepancy between low mobility
and long spin-diffusion lengths in OSCs.
It has to be noted that so far we have not commented on the
intrinsic organic magnetoresistance (OMAR) effects in OSCs65.
Large MR values exceeding 10% at room temperature have been
measured in various OSCs. Specially relevant for applications, this
effect is usually detected at voltages exceeding the operation range
of OSPDs (from 1 to 10 V)66. Strictly speaking, OMAR is not a
spintronics effect, as it involves neither spin-polarized signals nor
spin manipulation, and it would require an independent review.
On the other hand, all the spin-scattering effects present in OSCs
strongly contribute to both OMAR and spin transport, showing that
a common investigation would represent an efficient approach. For
example, spin scattering by the hyperfine fields of hydrogen nuclei
is among the most realistic mechanisms capable of activating MR
effects in OSCs67 and, in parallel, seems to provide the most impor-
tant scattering channel for the generated spin polarization64.
open questions and perspectives
One of the most frequent discussion topics in the community is
related to the reproducibility of the published experimental results,
as this sets a benchmark for the acquired knowledge. In this respect
we focus again just on Alq3, as this is certainly the most popular
OSC for spintronic applications. As we have explained in previous
sections, there are several published studies that have used Alq3
as the active layer in OSPDs, and this compound also shows the
highest MR values, both in injection23 and in tunnelling devices
(C. Barraud et al., unpublished results). It is worth stressing that
the inverse MR in manganite (LSMO)/Alq3/Co injection devices is
an established result that is corroborated by several experimental
reports. Magnetoresistance, however, is always positive in Alq3
tunnelling devices, irrespective of the composition of the electrodes.
Furthermore, positive MR has recently been confirmed in Alq3-based
injection devices in which both electrodes are ferromagnetic
metals68. In light of such complex results, a comprehensive theory
capable of explaining all of them is particularly needed.
Another question that remains unanswered regarding MR is
the discrepancy among the actual absolute values reported by dif-
ferent groups, as well as the relationship between MR and device
714
© 2009 Macmillan Publishers Limited. All rights reserved
NaTure maTerIals doi: 10.1038/nmat2510
resistance. For example, quite often MR clearly presents different
components, not all of them related to spin effects. Values of MR as
high as 80% that have been reported for LSMO/RRP3HT/Co spin
valves69 could be partially attributed to OMAR by as much as 35%,
leaving the spin-mediated MR value at around 40%. By comparing
the available MR data reproduced in various laboratories25,27–29,34, it
is possible to note that approximate average values for Alq3-based
injection devices are about 30–40% at 10 K, 15% at 100 K and below
1% at 300 K, with operating voltages limited to within a ± 1 V inter-
val. Reported resistance values for Alq3-based devices are usually
spread, mainly owing to different device geometries. An accurate
comparative assessment is often prevented by the lack of informa-
tion on such important device parameters as I–V curves, mobility,
injection barriers and operating voltages, among others. In the case
of Alq3 tunnel junctions, more data is needed to perform valid sta-
tistical analysis, as is also the case for OSPDs with any other OSC.
All these considerations indicate that the organic spintronics
community should make an effort to elaborate common metrology
rules to be able to allow direct comparisons between different
experiments and to progress into a deeper understanding of
spintronic effects.
A surprising fact is the predominance of the LSMO manganite
as spin-injector electrode. In addition to its widespread use, it has
provided the highest detected MR and room-temperature operation
of a spin valve. At present, there is no clear evidence that LSMO
offers a qualitatively different solution for OSPDs from a standard
ferromagnet, and its widespread use may be justified simply by its
high spin-polarization and its chemical stability. In fact, spectro-
scopic investigations do not indicate any conceptual difference
between the LSMO/Alq3 (ref. 51) and Co/Alq3 (ref. 52) interfaces.
Nevertheless, a direct characterization of the spin-transfer efficiency
across a LSMO/OSC interface has not been performed yet, leaving
the question open about the true potential of LSMO in OSPDs.
In parallel with spin-transport studies, simpler charge transport
in OSPDs also needs a deeper understanding. The study of charge
transport in organic electronic or optoelectronic devices usually
involves detailed investigations of the role of shallow and/or deep
trap levels, transitions from injection-limited to space-charge-
limited current and other standard models. A similar analysis for
OSPDs is still lacking. This absence is probably motivated by the
small voltage range in which spin effects usually take place (± 1 V),
and this reduced part of the I–V curves does not provide enough
information to explain the transport mechanism involved. At
present it is difficult to determine whether and how spin injection
and transport are related to very relevant parameters, such as natu-
ral defects of the OSC or traps. Detailed high-frequency investiga-
tions could shed light on these important relationships.
The spin-transport properties of OSCs have been frequently
questioned due to the markedly low carrier mobilities, especially
in comparison with other inorganic semiconductors, such as GaAs.
Nevertheless, we would like to point out that a simple estimate
shows that there is no contradiction between the experimentally
reported values of spin-diffusion length/time and the mobility
values. Standard organic spin valves have a typical channel length of
around 100 nm and operate between 0.1–1 V; considering a mobility
of about 10–3–10–4 cm2 V−1 s−1, one obtains spin-relaxation times in
the region of microseconds, in agreement with those measured for
many π-conjugated OSCs70,71. With the present mobility and spin-
relaxation times, it seems realistic to achieve long spin-diffusion
lengths on the order of the micrometre. Spin transport at longer
distances might, however, require either a considerable increase in
the mobility or in the spin-relaxation times.
Organic chemistry could also have an important role in the
development of the field. Purpose-designed molecules would
help us to control important factors such as mobility, spin-orbit
coupling, injection barrier or semiconductor gap energies. Some
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NaTure maTerIals doi: 10.1038/nmat2510
of the molecules needed are probably already available, but more
interdisciplinary teams are needed to take advantage of the tradi-
tional interaction between chemistry and physics.
Even with an enormous advance in new-molecule synthe-
sis, it seems clear that mobilities as high as 0.1–1 cm2 V−1 s−1 are
unlikely to be achieved in vertical devices. To overcome this limita-
tion, a dedicated effort must be made in the field of lateral struc-
tures20,72, in which higher mobilities can be obtained from both
a higher structural order and the presence of a electrostatic gate.
Moreover, lateral structures open the way for the fabrication of fas-
cinating devices (such as spin transistors) that could provide the
spin-manipulation option.
An interesting application in which OSCs could have a significant
impact is that of multifunctional materials and devices. In general
terms, these are devices that react either simultaneously or separately
to different external stimuli, such as electric field, magnetic field and
light irradiation. The possibility of combining magnetic switching
(spin-valve effect) and non-volatile electric resistance switching in
the same device has been achieved recently 73, pointing to a unique
combination of properties in hybrid organic–inorganic devices. We
believe this combination may become a subject of extensive inves-
tigations so that new approaches can be promoted for the genera-
tion of memory elements greater than two bits per cell. Whether
the intrinsic transport properties of the OSC are critical for resis-
tive switching and whether this switching is a bulk or an interfacial
effect are issues currently under discussion74, but that are beyond
the scope of this article.
corrected after print 11 september 2009
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acknowledgements
The authors would like to acknowledge the financial support from EU-FP6-STRP
033370 OFSPIN and Organic Spintronics Srl for partial financial support.
nature materials | VOL 8 | SEPTEMBER 2009 | www.nature.com/naturematerials
corrigendum

Spin routes in organic semiconductors

V. Alek Dediu, Luis E. Hueso, Ilaria Bergenti and Carlo Taliani

Nature Materials 8, 707–716 (2009); published online: 1 September 2009; corrected after print: 11 September 2009.

In Table 1 on page 709 of the above Progress Article, the structures for the compounds poly(3-hexylthiophene) (RRP3HT), tetraphenyl­
porphyrin (TPP), pentacene, rubrene and copper phthalocyanine (CuPc) should have appeared as shown below. These errors have been
corrected in the HTML and PDF versions.

RRP3HT TPP Pentacene Rubrene CuPc

C 6H13 C 6H13 N N
N N
S
S S NH HN N Cu N
n
C 6H13 N N N N

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