1 s2.0 S2468217916300442 Main
1 s2.0 S2468217916300442 Main
1 s2.0 S2468217916300442 Main
net/publication/322887089
CITATIONS READS
39 763
6 authors, including:
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by T. D. Nguyen on 31 May 2016.
Rugang Geng, Timothy Tyler Daugherty, Kevin Do, Hoang Luong, Tho Duc Nguyen
PII: S2468-2179(16)30044-2
DOI: 10.1016/j.jsamd.2016.05.002
Reference: JSAMD 17
Please cite this article as: R. Geng, T.T. Daugherty, K. Do, H. Luong, T.D. Nguyen, A Review on
Organic Spintronic Materials and Devices: I. Magnetic Field Effect on Organic Light Emitting Diodes,
Journal of Science: Advanced Materials and Devices (2016), doi: 10.1016/j.jsamd.2016.05.002.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Title: A Review on Organic Spintronic Materials and Devices: I. Magnetic Field Effect on
PT
Rugang Geng, Timothy Tyler Daugherty, Kevin Do, Hoang Luong, Tho Duc Nguyen*
RI
Department of Physics and Astronomy, The University of Georgia, Athens, GA 30602, USA
E-mail: ngtho@uga.edu
U SC
AN
M
Acknowledgements
We acknowledge the University of Georgia start-up funds and Faculty Research Grant
D
Title: A Review on Organic Spintronic Materials and Devices: I. Magnetic Field Effect on
PT
Keywords: Organic spintronics; Organic light emitting diodes; Spin dynamics; Organic
RI
magnetoresistance; Magnetic field effect
Organic spintronics is an emerging and potential platform for future electronics and
SC
display due to the intriguing properties of organic semiconductors (OSCs). For the past decade,
studies have focused on three types of organic spintronic devices: (i) magnetic field effect (MFE)
U
in organic light emitting diodes (OLEDs), where spin mixing between singlet and triplet polaron
AN
pairs (PP) can be influenced by an external magnetic field leading to organic magnetoresistive
effect (OMAR); (ii) magnetoresistance (MR) in organic spin valves (OSVs), where spin injection,
M
transport, manipulation, and detection have been demonstrated; and (iii) bipolar OSV or spin-
D
OLEDs, where spin polarized electrons and holes are simultaneously injected into the OSC layer,
TE
this first of two review papers, we present major experimental results on OMAR studies and
EP
semiconductors. During the discussion, we highlight some of the outstanding challenges in this
C
promising research field. Finally, we provide an outlook on the future of organic spintronics.
AC
1. Introduction
attention for over three decades.[1, 2] It has already revolutionized magnetic hard-disk technology
and will continue to play a central role in the development of new information technology. The
1
ACCEPTED MANUSCRIPT
concept of electron spin was originally introduced by Wolfgang Pauli in 1924 after the crucial
experimental discovery of the quantization of the intrinsic angular momentum, or spin, of silver
atoms by Walther Gerlach and Otto Stern in 1922.[3, 4] Similar properties were later found in
various atomic nuclei.[5] However, the potential of using the electron’s spin degree of freedom in
PT
electronic devices was not realized until in 1975 by Jullière through the discovery of the tunneling
RI
magnetoresistance (TMR) in the ferromagnet (FM)/insulator/superconductor magnetic tunnel
junction (MTJ).[1, 6-8] It was only a couple of years after Tedrow et al. showed spin polarization
SC
in the ferromagnetic/insulator tunnel barrier.[7, 8] In the late eighties, Fert[9] and Grünberg[10]
independently showed the diffusion of spin polarized carriers through a non-magnetic (NM) metal
U
layer in contact with FM layers for an in-plane current and called this effect the giant
AN
magnetoresistance (GMR), the discovery for which they were awarded a Nobel Prize in 2007.
The explanation of GMR in the FM/NM/FM layered structure was based upon spin dependent
M
scattering. This discovery revolutionized modern information storage and paved a way for future
D
spin-logic devices. After these innovative discoveries, research in this field accelerated
TE
impressively and advanced to a range of different materials and a number of techniques to verify
the successful injection and transport of the spin polarized carriers.[1, 2, 11, 12] The effect has
EP
including ferroelectric and topological insulators as the spacers.[1, 2, 13-19] The GMR effect was
extensively studied using non-magnetic metallic interlayers and potential applications such as
electric switching, magnetic recording, and sensors were suggested and employed.[1, 2, 17]
2
ACCEPTED MANUSCRIPT
characterized by short spin relaxation times (~ picosecond) and are not suitable for coherent spin
manipulation.[1, 2, 20] To overcome these limitations, the spintronics community moved its
attention towards hybrid devices with semiconductors sandwiched in between the FM layers and
PT
Organic semiconductors have appeared as one of the newest spacers for spintronic
RI
devices; having been employed for just about a decade. However, the OSC-based research on
other electronic devices such as organic light emitting diodes (OLEDs),[24-26] organic solar
SC
cells,[27, 28] and organic field effect transistors[29, 30] has been of central interest for over three
decades. In fact, OLEDs have already revolutionized the modern display industry, and spin-
U
dependent devices such as organic spin valves (OSVs), OLED-based magnetic sensors, and spin-
AN
OLEDs are under intensive study to achieve their new avenues.[31-33] This increasing interest in
organic electronics is due to several distinctions over their inorganic counterparts[20-22, 34, 35]
M
including its rich physics, flexible chemistry, cost efficiency, and potential applications in new
D
generations of electronic devices. Electronically, the band theory explains the electronic transport
TE
in inorganic semiconductors, while charge transport in OSCs is much more complicated. This is
electrons caused by conjugation over all or part of the molecule. When being doped by a proper
dopant, these materials have conductivity levels ranging from insulators to conductors.[36] Since
C
the intermolecular (van der Waals) forces in organic materials are much weaker than the covalent
AC
and ionic bonds of inorganic crystals, organic materials are less rigid than inorganic substances. A
moving charge carrier in OSCs is, therefore, able to locally distort its host material. Since strong
electron-phonon coupling occurs in organic materials, the electron can be treated as a quasi-
particle, namely a polaron. Since the OSC is highly disordered, polaron transport is governed by a
3
ACCEPTED MANUSCRIPT
process called hopping with very low mobility.[37] This might be a favorable condition for a
large polaron pair recombination rate without the need of using a p-n semiconducting junction
structure.[24-26] Spintronically, the inorganic semiconductors contain heavy atoms giving rise to
a large spin-orbit coupling (SOC), which is a response of the electron spin degree of freedom to
PT
its orbital environment. The strength of the SOC in solids depends upon the nature of the orbital
RI
wavefunctions of electrons and the material’s structure.[38] In the case of the hydrogen-like
electron wavefunction, the SOC is proportional to the fourth order of the atomic number. If the
SC
probability of finding an electron around the nuclei is taken into account, the effective strength is
estimated to vary with the second order of the atomic number.[39] Therefore, the OSCs (usually
U
small molecules or -conjugated polymers, see Figure 1) possess a weaker SOC as they are
AN
composed of light molecular weight materials such as carbon and hydrogen. The transport from π-
M
orbital electrons also further suppresses the SOC and the hyperfine interaction (HFI), which is the
interaction between the spins of an electron and nuclei, in these materials.[20, 40] Therefore, a net
D
of the spin scattering sources in the OSCs is very weak so that their spin relaxation time (in the µs
TE
range) is several orders of magnitude larger than in inorganics (in the ns range).[2] This makes the
OSCs promising candidates for coherent spin manipulation logic devices, such as spin
EP
in a lateral structure was designed and tested by Dediu et al. in 2002.[21] They observed a large
C
change in resistance of the structure at room temperature due to an applied magnetic field that
AC
suggested an injection of spins into T6 (see Figure 1 for its structure) OSCs. In 2004, Xiong et
al.[22] demonstrated the first spin valve effect in vertical organic spin-valve (OSV) devices by
sandwiching Alq3 (see Figure 1 for its structure) in between LSMO and thin cobalt (Co) layers.
Following these novel works, much effort has been made in proving[42-44] and disproving[45-
4
ACCEPTED MANUSCRIPT
47] the possibility of spin injection in OSCs, optimizing their injection and detection efficiency,
and understanding the spin transport properties in the hybrid devices of metallic FM electrodes
and OSC interlayers.[20, 34, 35, 42, 48-51] In addition to the spin valve effect, a different type of
MR effect in the OLED devices, the so-called organic magnetoresistance (OMAR), has also been
PT
observed in a range of OSCs.[52-61] In contrast to MR in OSVs, which is thought to give the
RI
largest MR response when spin-related interactions in the organic interlayer are minimized,
OMAR in OLEDs is an intrinsic property found in most OSC materials and it relies on the
SC
existence of HFI and/or SOC fields and their randomization.[53, 55, 62-67]. These interactions
induce electron spin flips, leading to the interconversion between singlet and triplet polaron pairs
U
(either excitons or bipolarons), which have a direct effect on the electroluminescence (EL) and
AN
conductivity of the device. Recent experiment on OLEDs made by an OSC blend predicts that the
M
difference in g-value of positive and negative polarons located in the donor and acceptor,
respectively, might cause spin mixing between singlet and triplet states.[68, 69] OMAR in
D
OLEDs may be considered as an example of a much broader research field that deals with
TE
magnetic-field-effects (MFE) in Physics[70], Chemistry and Biology[71, 72]. Recently, there has
been interest in the bipolar OSV or spin-OLED structure, where spin polarized electrons and
EP
holes are injected from the FM cathode and FM anode, respectively. The EL of the device
depends on the relative magnetization of the electrodes. In ideal conditions, the device can reach
C
50% EL internal quantum efficiency (IQE) for parallel magnetization states and 0% EL IQE for
AC
the anti-parallel magnetization states. Excellent reviews on the different aspects of organic
spintronic devices can be found in the literature.[20, 32, 35, 40, 50, 52, 73-78]
In this report, we review the progress of OMAR study in OLEDs over a decade long period
with an outlook in this promising field. In particular, we give basic operating principle of organic
5
ACCEPTED MANUSCRIPT
light emitting diodes, the experimental advances over the period, and the major models well
established in this field. Finally, we give an outlook for the advancement of the research in this
PT
2. Organic light emitting diodes
RI
electrodes, the anode (cathode) made by high (low) work-function materials, all deposited onto
SC
a glass substrate (Figure 2a). Figure 2b shows work functions of common metals and the highest
occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)
U
energy levels of polyfluorene (PFO) (see figure 1 for its structure). During operation, a voltage is
AN
applied across the device. A current of negative/positive polaron (P-/P+) flows through the device,
as electrons (holes) are injected into the LUMO (HOMO) of the organic layer at the cathode
M
(anode). Since organic materials normally possess a small electrical permittivity, the strong
electrostatic forces between the P- and P+ bring them together. These materials first form a
D
polaron pair (PP) exciton; a loosely bound state of the P- and P+ with negligible exchange
TE
interaction at the distance of several nanometers. Because polarons are fermions with spin ½,
either in up-spin (↑) or down spin (↓) state, a PP may be in a singlet state PPS (↑↓ − ↓↑) or
EP
a triplet state PPT of either ↑↑ , ↓↓, or (↑↓ + ↓↑), depending on how the spins of P+ (the first
C
arrow) and P- (the second arrow) have been combined. Statistically, three triplet PP will be
AC
formed for each singlet PP. The free carriers and PP excitations are in dynamic equilibrium in the
recombination via intrachain excitons. The steady state PP density depends on the PPS and PPT,
the “effective rate constant”, k, which is the sum of the formation, the dissociation and
recombination rate constants, as well as the triplet-singlet mixing via the intersystem crossing
6
ACCEPTED MANUSCRIPT
(ISC) interaction. If the effective rates kS for PPS and kT for PPT are not identical to each other,
any disturbance of the singlet-triplet mixing rate, such as by triplet-triplet annihilation, triplet-
polaron interaction, hyperfine interaction from adjacent hydrogens, [72] spin orbit field[79] from
incorporated heavy metals, or an applied magnetic field, B, would perturb the dynamical steady
PT
state equilibrium that results in a change of emission efficiency and polaron density. In principle,
RI
there are three distinct mechanisms for the emission efficiency: (i) direct fluorescence from the
singlet exciton that limits the IQE to about 25% depending on the singlet radiative recombination
SC
rate and the ISC rate; (ii) phosphorescence from triplet excitons using incorporated heavy metals
that give IQE up to 100%; and (iii) delayed fluorescence that can be from either triplet-triplet
U
annihilation or thermally-assisted up-conversion of triplet to singlet excitons. The triplet-triplet
AN
annihilation gives weak delayed fluorescence due to a small portion of triplet-triplet pairs
annihilating to excited singlet excitons, while the thermally-assisted up-conversion would give
M
up to 100% IQE depending on the energy gap between singlet and triplet excitons relative to the
D
thermal energy. The first two emission mechanisms have been explored in the past three decades.
TE
Recently, highly efficient OLEDs with thermally activated delayed florescence (TADF) have
been reported by Adachi’s group.[80] In TADF materials, there is little overlap between the
EP
orbital wavefunctions of localized positive polarons in the HOMO level of a donor and localized
negative polarons in the LUMO level of an acceptor whose locations can be designed in a single
C
molecule (in the case of exciton-based TADF materials) or different molecules (in the case of
AC
exciplex-based TADF materials). Consequently, the singlet and triplet excitons/exciplexes have
small energy gaps due to a small exchange energy, J, of typically less than 200 meV.[81] In
principle, the smaller the J value, the larger the TADF intensity. Therefore, thermal energy plays
an important role to increase the up-conversion rate from triplet to singlet excitons. The internal
7
ACCEPTED MANUSCRIPT
EL quantum efficiency of such OLEDs can reach 100% without the need of using incorporated
heavy metals. [80] Figure 2c shows four main steps of the working principle of an OLED.
PT
In 2003, Kalinowski et al. showed that electroluminescence (EL) and current density can
be modulated by a few percent in OLEDs made of small molecules, such as Alq3, by application
RI
of a small magnetic field of about 100 mT.[62, 82] Later, Wohlgenannt et al., demonstrated a
SC
very large magnetoresistance of up to 30% at the same characteristic magnetic field in PFO-based
OLEDs.[83] The effect was dubbed organic magnetoresistance (OMAR). In this section, the term
U
MFE or OMAR will be used interchangeably for both magneto-conductance (MC) and magneto-
AN
electroluminesscence (MEL). It is worth noting that the magnetic field effect on photocurrent of
several percent in poly(phenylene vinylenes) and its derivatives, an analogous effect with OMAR,
M
was observed by Frankevich et al. in 1992.[84] In such devices, the electron density and the hole
density are assumed to be the same. The MC and MEL responses are defined, respectively, via
D
I ( B ) − I (B = 0 )
MC ( B ) = ∆ I ( B ) / I ( 0 ) =
TE
and
I (B = 0 )
EL (B ) − EL (B = 0 )
MEL = ∆ EL ( B ) / EL ( 0 ) = , (1)
EL (B = 0 )
EP
where ∆I and ∆EL are the field induced changes in the current and EL intensity, respectively.
C
Figure 3 shows the large MEL and MC (essentially an inverse of OMAR) magnitudes of an Alq3-
AC
based OLED.[85] The MEL (MC) response may reach up to 60% (30%) at B ~100 mT. It is
surprising that a small magnetic field, with Zeeman splitting on the order of ~µeV, can
significantly alter the EL and conductivity of the device at room temperature where thermal
energy, ~26 meV, is dominate. Therefore, MFE must be caused by effects on spins in a thermal
nonequilibrium situation. Recently, there has been interest in studying the magnetic field effect in
8
ACCEPTED MANUSCRIPT
TADF-based OLEDs.[69, 86] The MEL and MC of about 4000% and 1000%, respectively, have
been achieved in such OLEDs in a certain device operation.[69] This makes MFE in OLEDs very
Now, we briefly summarize the main experimental results of MFE in the following
PT
sections:
RI
(i) Since OMAR in the conventional OLEDs is generally insensitive to OSC thickness,
OMAR is an effect associated with the bulk resistance of the layer, rather than the OSC/electrode
SC
interfacial resistance.[54] However, a recent study of OMAR on TADF-based OLEDs shows an
order of magnitude increment in OMAR magnitude when the thickness increases from 50 nm to
the ambient temperature.[54] We note that recently Wagemans et al.[49] found that OMAR in
M
OLEDs has a tiny variation when magnetic field B changes from perpendicular direction to
D
parallel direction to the device current. This tiny change and its mechanism will not be discussed
TE
in this review.
(iii) OMAR can be of positive or negative sign, depending on material and/or operating
EP
conditions of the devices.[54, 59, 83, 87] Figure 4 shows the magnetoresistance reversal of
OLEDs made with RRP3HT and T6 (see Figure 1 for their chemical structures), where the sign of
C
the magnetoresistance is dependent on temperature (Figure 4a) and applied voltage (Figure 4b).
AC
(iv) The magnitude OMAR can be an order of magnitude larger when trap states are
5a).[88, 89] The signature of the presence of trap states is the strong reduction in device
conductivity and electroluminescence intensity. In this case, the polarons are more localized,
9
ACCEPTED MANUSCRIPT
leading to the longer excited state lifetimes that would allow more time for spin mixing between
singlet and triplet states. Interestingly, in the TADF materials, where the positive and negative
polarons are strongly localized in the donor and acceptor units, respectively, a much larger MEL
and MC of about 100% has been observed (Figure 5b).[86] When the device is electrically
PT
conditioned, the stronger polaron localization significantly enhances OMAR up to a few thousand
RI
percent (Figure 5c).[69] We note that in most cases, a larger OMAR magnitude is always
SC
(v) OMAR generally obeys the empirical laws ∆I(B)/I ≈ B2/(B2 + B02) (Lorentzian shape)
or ∆I(B)/I ≈ B2/(|B| + B0)2 (non-Lorentzian shape) depending on the material and applied
U
voltages[54], where B0 of about 5 mT scales with HFI/SOC strength (Figure 6).[48, 63, 65] In
AN
many other cases, such as described in Figure 4 and the curve (Rolfe et al) in Figure 6, the OMAR
response cannot be fit by a single empirical law. This scenario was discussed before by Wang et
M
al.[60] In addition, Gillin et al. found that OMAR can be better fit by the sum of two or three
D
Lorentzian functions.[90, 91] This suggests that there may be more than one OMAR mechanism
TE
involved in the effect depending on OSC materials, device fabrication and operating
condition.[60, 90]
EP
(vi) In a conventional polymer, the magnetic field value, B1/2, at HWHM of the OMAR
scales by the HFI strength of the material.[48] Figure 7a shows the MEL response of two OLED
C
devices based on H- and D-DOOPPVs (see Figure 1 for the chemical structures) with the same
AC
thickness df, measured at the same bias voltage, V; a very similar MC response was also measured
simultaneously (Figure 7b). The MEL and MC responses are narrower in the D-DOOPPV device;
in fact, the field, B1/2, for the MEL in the H-DOOPPV device is about twice as large as in the D-
DOOPPV device.[48] Interestingly, B1/2 increases with V (inset of Figure 7a).[60] In fact, B1/2
10
ACCEPTED MANUSCRIPT
increases almost linearly with the device electric field, E=(V-Vbi)/df, where Vbi is the built-in
potential in the device that is related to the onset bias voltage where EL and MEL are
observed.[58, 92] It is consistently observed that B1/2(H)>B1/2(D) for devices with the same value
of the electric field, E (inset of Figure 7a). We note that similar studies have been done using
PT
hydrogenated Alq3 (H-Alq3) and deuterated Alq3 (D-Alq3).[93, 94] However, it is surprising that
RI
MC is found to be isotope independent while the MEL response in H-Alq3 is nearly 1.5 times
wider.[93, 94] The disparity between the isotope sensitivity of the MC and MEL responses in
SC
Alq3 indicates that the HFI in the MC response is overwhelmed by another spin mixing
mechanism such as the polaron-triplet scattering, which does not have a direct effect from
U
HFI.[94] The other possibility is that OSC strength originated by the Al atom in Alq3 materials
AN
might be comparable with the HFI strength, which further complicates the effect. This scenario is
supported by the observation of phosphorescence in Alq3 films.[95] It is worth noting that the MC
M
in fullerene-based OLEDs was not observable due to the absence of nuclear spins.[96] In
D
addition, Malisa et al. recently observed a direct coupling between the electrical current and
TE
nuclear spins in OLEDs.[97] This additional evidence clear doubts about the crucial role of HFI
(vii) Relatively small and negative MC was found in unipolar devices that usually do not
show EL at low applied voltages.[58, 60, 63] Figure 8a shows normalized MC of an electron-only
C
device and a hole-only device made with MEH-PPV (see Figure 1 for its structure). Its chemical
AC
structure is shown in Figure 1. The MC magnitude in the unipolar device is relatively smaller than
that in the bipolar device. In addition, the MC of the electron-only device shows much larger
11
ACCEPTED MANUSCRIPT
(viii) The magnetic field response of OMAR universally shows a sign reversal
(characterized by Bm, where OMAR is minimum) at ultra-small |B| < 1–2 mT due to the interplay
of the hyperfine and Zeeman interactions on carrier spins[63]. Figure 9a and 9b show that the
MEL and MC have yet another component at low B, dubbed "ultra-small-field MEL/MC" or
PT
USMEL/USMC, which has an opposite sign to that of the positive MEL (MC) at higher magnetic
RI
fields. A similar low-field component was also observed in some biochemical reactions[98] and
anthracene crystals[99] with likely the same underlying mechanism as in OLED devices. The
SC
USMEL (USMC) component might also be due to the HFI, since its width is isotope dependent; it
is observed that the dip in the USMEL response occurs at Bm ~ 0.7 mT in H-DOOPPV, whereas it
magnetic field response, USMC(B), of hole-only and electron-only MEH-PPV unipolar devices.
M
Similar responses were also measured for DOOPPV devices.[64] The high-field MC in unipolar
D
devices is negative (Figure 8a)[60] and thus the USMFE response here appears as a ‘negative-to-
TE
positive’ sign reversal with a maximum at Bm ~ 0.8 mT for the electron-only device and Bm ~ 0.1
mT for the hole-only device (Figure 8b). Importantly, the HWHM is smaller in the hole-only
EP
device compared to that in the electron-only device. This is consistent with smaller aHF for hole-
polaron than for electron-polaron in MEH-PPV, which is in agreement with recent measurements
C
using transient spin response.[100] We therefore conclude that Bm increases with the HWHM in
AC
unipolar devices in a similar fashion to bipolar devices.[63] This finding suggests that one can
obtain the effective HFI of electrons or holes separately in OSC by MFE in unipolar devices
12
ACCEPTED MANUSCRIPT
We note that OMAR has been studied in OSCs containing heavy metals.[53, 55, 101]
Since the SOC in this case is quite large compared to HFI strength, the OMAR response is
normally quenched and its HWHM is significantly broader.[53, 55, 101] In addition to intrinsic
SOC, recent study shows that the curvature-enhanced SOC might also play an important role on
PT
electron spin dynamics in organic substances.[102] In the following section, we only focus our
RI
discussion on OMAR mechanisms in conventional OSCs only where HFI dominates.
SC
4. Advances in modeling of magnetic field effect in OLEDs
In general, the current density of the device, j, can be written using the Drude model of
U
electrical conductivity:
AN
=
= , (2)
where e is elementary charge, n is density of negative and positive polarons, µ is carrier mobility,
M
σ is the conductivity, and E is the electric field inside the device, which is insensitive to applied
magnetic field. Therefore, the large magneto-current (or magneto–conductivity) can be explained
D
by a magnetic field dependent carrier density, n, and/or magnetic field dependent mobility, µ.
TE
Based on this general argument, various models have been put forth to explain OMAR in
OLED devices.[55, 57, 59, 60, 63, 103] Four models have been proposed to explain OMAR at the
EP
(i) The bipolaron mechanism, which treats the spin-dependent formation of doubly
AC
occupied sites (bipolarons) during the hopping transport through the organic film;[57, 104, 105]
(ii) The loosely-bound PP pair model; where the interconversion between singlet and
triplet density via HFI-based intersystem crossing (ISC) is affected by an applied magnetic
field.[55, 62, 63] The single density increases by the suppression of the triplet density and vice
13
ACCEPTED MANUSCRIPT
versa. As a result, it affects device conductivity via e-h pair dissociation and EL via singlet
radiative recombination. This model supports the assumption that the magnetic field enhances the
(iii) The triplet-exciton polaron quenching model (TPQ), which relies on the spin-
PT
dependent reaction between a triplet exciton and a polaron (either a free or trapped).[56, 59] The
RI
applied magnetic field can affect the triplet exciton density via the ISC process. Furthermore, it
can influence the spin mixing between the triplet excitons and polarons, therefore changing the
SC
mobility[103] and density[59] of mobile polarons in the device.
(iv) The ∆g mechanism relies on the different gyromagnetic (g) factor between positive
U
polaron (g+) and negative polaron (g-). Since the negative and positive polarons precess with
AN
different Larmor frequencies, the singlet and triplet state mixing rate is proportional to (g+-g-
)·B=∆g·B. [60] The ∆g mechanism becomes more effective at high magnetic field.[68] The model
M
explains OMAR based on the MFE on the charge density of the device.
D
In general, the first three models are built on the role of the HFI between the spin (s=
TE
½) of the injected charge carriers and the proton nuclear spins located at the chemical
backbone of the active layer. The last three mechanisms are based on exciton formation, where
EP
mechanisms is that the spin mixing between pairs, either PP, bipolarons or triplet PPs, becomes
C
less (more) effective as the magnetic field increases (decreases) for the HFI-based mechanisms
AC
(∆g mechanism), thereby inducing OMAR. In the following sections, the fundamental ideas
14
ACCEPTED MANUSCRIPT
Bobbert et al.[57] considered the effect of a magnetic field on the hopping probability of a
polaron from a localized state at site α to another nearest localized state at site β, which is already
occupied by a like-charge polaron (Figure 10). In the previous section, we pointed out that
PT
oppositely charged polarons can form excitons and may eventually recombine to emit light.
RI
However, two like-charge polarons can form a bipolaron; a state where the correlation energy
between the pair and the lattice deformation lowers the formation energy. The on-site charge
SC
exchange interaction requires that the bipolaron is a spin singlet. The bipolaron formation will be
“spin-blocked” if the two polarons have the same spin component along the common quantization
U
axis. In addition, these polarons are exposed to a local hyperfine field produced by the adjacent
AN
nuclear spins, which can be treated as a randomly oriented classical field Bhf. The total field at a
site α is then Btotal;α = B + Bhf;α ,where B is the applied magnetic field (Figure 10). The hopping
M
therefore occurs between energy eigenstates corresponding to the local net magnetic fields
D
randomly oriented at the two sites where the spin precession frequency is assumed to be larger
TE
= − . , (3)
EP
ℏ
where Sα/β are the classical spin vectors pointing along Btotal;α/β, and ℏ is Planck's constant. A
C
straightforward analysis of this formula shows that for B = 0 the pairs have an average singlet
AC
probability P = 1/4, whereas for large field this probability is either equal to zero or one-half for
parallel and antiparallel pairs, respectively. Note that the notion of parallel and antiparallel pairs
has its usual meaning only for large B; whereas for small B, Bobbert et al. denote "parallel" as a
pair whose spins both point "up" or both "down" along the local field axes.
15
ACCEPTED MANUSCRIPT
We will now formulate rate equations to describe the hopping transport. Bobbert et al.[57]
assumed that the low energy site, β, can permanently hold at least one polaron. A bipolaron can be
formed by the hopping of a polaron to an adjacent site, known as the "branching" site, with a rate
→ (Figure 10a) or → (Figure 10b), depending on the orientation of its spin. The model
PT
assumes that the electric field is large enough such that dissociation does not occur to but, at a
RI
rate → to other sites, which it considers to be part of the "environment". The model assumes
that polarons enter with a rate → by hopping from sites in the environment with equal
SC
"parallel" and "antiparallel" spins leading to an influx rate → !/2 into both spin channels, where
U
p is a measure for the average number of polarons in the environment. The model also considers
the possibility that a polaron at directly hops back to an empty site in the environment with a
AN
rate → . Neglecting a double occupancy of and single occupancy of simultaneously with
double occupancy of $, the corresponding rate equations can be straightforwardly written down:
M
%
→ ! − (→ + → )! = 0 (4)
D
→ ! − (→ + → )! = 0 (5)
TE
These equations can be solved for the probability ! of double occupancy of $, i.e. the presence
of a bipolaron:
C
'(→)
! = +(, )! , (7)
'*→(
AC
1
. ./ 0
with + (, ) = 23
1 , (8)
/ ./ 0 0
3 3
where the B dependence has been absorbed in the function f(B) and 4 = → /→ is the
“branching” ratio. In general, the conductivity of the device is proportional to the probability !
16
ACCEPTED MANUSCRIPT
or f(B). Averaging over the directions of the hyperfine fields, one obtains the results for <
+(,) > plotted in Figure 10c for various values of b. For small b the line shape is governed by
< ( ) >. For large b, a strong dependence on B develops, which now becomes governed by
< 1/( ) >. These line shapes can be fitted very well with the empirical law, , % /(|,| + ,9 )%
PT
for large b and , % /(, % + ,9% ) for small b. The fitting parameters are shown in Figure 10c. For
RI
intermediate values of b, the line shapes cannot be fit well by either empirical formula. In
principle, the bipolaron model can explain the line shape of OMAR response.
SC
Bobbert et al. demonstrates this mechanism by employing Monte-Carlo simulations of
nearest neighbor hopping on a 303 cubic grid of sites with lattice constant a and periodic
U
boundary conditions. The site energies were drawn randomly from a Gaussian density of state and
AN
a randomly oriented hyperfine field of strength Bhf was attributed to each site. The Miller
Abrahams form was used for the hopping rate r, with ~ exp>? − @ A /BC, where Ef and Ei are
M
the initial and final energies of the configurations before and after hopping. This term includes an
D
energy a picked up or lost due to hops with or against the applied electric field E, with e being
TE
the electronic charge. The short range and long range Coulomb repulsions were also taken into
account in the hopping rate. The simulation result shows good agreement in OMAR sign change,
EP
In principle, the bipolaron model can explain various experimental OMAR responses as
AC
described in the previous section. In this model, the magnetic field effect on OLEDs can be
considered as a combination of two independent effects on electrons and holes.[58] The model
states that the observation of OMAR is independent of device emission. However, in reality
OMAR appears to be large only when the device has a good emission. In addition, bipolaron
17
ACCEPTED MANUSCRIPT
density has not been spectroscopically observed in OLEDs due to the low current density in the
device. Finally, it is not clear how the USMFE be explained by this model.
There are several PP models used to explain the time evolution of singlet and triplet
PT
excitons in organic substances of different configurations, such as in organic solution/films[71]
RI
and in OLEDs.[62, 63, 87, 106] Here, we present the complete model proposed by Ehrenfreund et
al.[106], which is based on the time evolution of the PP spin sublevels in a magnetic field.[63,
SC
106] For bipolar devices, the PP species is the polaron-pair, whereas for unipolar devices the PP
species is a π-dimer (i.e. bi-radical, or bipolaron[57, 60]). It is assumed that the PP excitations are
U
immobile, hence PP diffusion is ignored, but the overall rate of PP decay (e.g. through exciton
AN
recombination and/or dissociation into free polarons that contribute to the device current) is taken
into account. The steady state singlet fraction of the PP population ("singlet yield", ΦS) is then
M
calculated from the coherent time evolution of PP wavefunctions subject to the above
D
interactions. The calculated MC (MEL) response is then expressed as a weighted average of the
TE
singlet (ΦS) and triplet (ΦT) PP yields in an external magnetic field, B. The spin Hamiltonian, H,
includes exchange interaction (EX), HFI and Zeeman terms: H = HZ+HHF+Hex; where
EP
~ ~
H HF = ∑i =1 ∑ j =1[ S i ⋅ Aij ⋅ I j ] is the HFI term, A is the hyperfine tensor describing the HFI
2 Ni
C
between polaron (i) with spin Si (=½) and Ni neighboring nuclei, each with spin Ij, having an
AC
isotropic aHF constant; HZ = g1µBBS1z+ g2µBBS2z is the electronic Zeeman interaction component;
gi is the g-factor of each of the polarons in the PP species (we chose here g1 = g2); µB is the Bohr
magneton; Hex=JS1· S2 is the isotropic exchange interaction; and B is along the z-axis. All
parameters in the Hamiltonian H are given in units of magnetic field (mT). An example of the PP
spin sublevels using the Hamiltonian H for N1=N2=1, and I=½ (overall 16 wavefunctions) is
18
ACCEPTED MANUSCRIPT
shown in Figure 11a. Note the multi-level crossings that occur at B=0. Other level crossings
appear at larger field, BLC, but those are between mostly triplet sublevels that rarely change the
singlet-triplet intermixing rate and related PPS and PPT populations. The same PP spin sublevels
PT
The relevant time evolution of the singlet-triplet intermixing that determines the steady
RI
state PPS population is obtained in the model via the time dependent density matrix, ρ(t). Solving
the spin Hamiltonian, H, for the energies En and wavefunctions Ψn, we express the time evolution
SC
of the singlet population ρS(t) as [71, 72]
U
4
ρ S (t ) = Tr [ ρ (t ) P S ] = ∑ | PmnS | 2 cos ω mn t ,
M
m , n =1
(9)
M
AN
where PSmn are the matrix elements of the PPS projection operator, ωmn=(En-Em)/ħ, and M is the
number of spin configurations included in the PP species (for I=½ M=2N+2). In the absence of a
M
spin decay mechanism, Eq. (9) yields for the PPS steady state population (apart from the rapidly
D
restricted to degenerate levels for which ωmn(B)=0. Here, the first term contributes to MFEM(B)
response, whereas the second term contributes to the MFELC(B) response that modulates
EP
<ρS(t=∞)> primarily at B=0, where the singlet-triplet degeneracy is relatively high. The MFEM(B)
response is monotonous due to the direct influence of B, and hence Zeeman effect in between the
C
singlet-triplet PP spin mixing causing large field MFE. The MFELC(B) component is caused by
AC
singlet-triplet level crossing and therefore has an opposite sign with respect to the regular
MFEM(B) response, which results in a strong MFE(B) modulation response at B=BLC. The
19
ACCEPTED MANUSCRIPT
When allowing for PP spin decay, ρS(t) in Eq. (9) should then be revised to reflect the
disappearance of PP with time. Furthermore, for MFE to occur, the decay rates of the singlet and
triplet configuration must be different from one another. Thus, in a decaying system the
population in each of the M levels would decay at a different rate γn for n=1,…,M. Under these
PT
conditions, Eq. (9) for the singlet fraction is given by[71]
RI
4
ρ S ( t ) = Tr[ ρ (t ) P S ] = ∑ | PmnS |2 cos(ω mn t )e − γ nm t ,
M
m , n =1
(10)
M
SC
where DEF = DE + DF . Eq. (10) expresses that the singlet (or triplet) time evolution contains both
a coherent character through the cos(GEF t) factor and an exponential decay factor. The measured
U
MFE, that is MC and MEL, may be calculated using Eq. (10). For instance, if the dissociation
AN
yields are kSD and kTD for the singlet and triplet configurations, respectively, then the time
dependent dissociated fraction of either the singlet or triplet is k α D ρ α ( t ) (α=S,T) and thus the
M
∞ 4 k γ
Φα D = ∫ kα D ρα (t )dt =
0
∑
M n ,m
Pnα,mσ m,n (0) 2 α D nm2 .
γ nm + ωnm
(11)
TE
The total dissociation yield is Φ D = Φ S D + Φ TD and the MC(B) response is then given by
EP
ΦD ( B) − ΦD (0)
MC( B) = . (12)
ΦD (0)
C
For a slow decay such that k<<aHF/ħ, the abrupt MFELC(B) obtained at B=0 in the
AC
absence of the spin decay is now spread over a field range of the order of ħk/gµ B, after which
ΦS(B) increases again due to the more dominant MFEM(B) component at large B.
For the MEL response, the final expression depends on the radiative recombination path
of the singlet excitons (SE) and the detailed relaxation route from PP to the SE. As a result, PPT
(PPS) may transform not only to TE (SE) but also to SE (TE). Let us denote the effective SE (TE)
20
ACCEPTED MANUSCRIPT
generation rates, from the PPα (α=S,T) configuration, as kα,SE (kα,TE). Then, similar to MC, we
can define the “SE generation yield”, ΦSE = ΦS ,SE + ΦT ,SE where Φα ,SE is given by Eq. (11) in
which kαD is replaced by kα,SE . Since the EL is proportional to the SE density, the MEL response
PT
is still given by Eq. (12), in which Φ D is replaced by Φ SE .
Figure 12 shows the singlet yield and resulting MEL(B) response of the H-DOOPPV-
RI
based OLED. More importantly, the calculated MEL response captures the experimental USMEL
SC
response comprising of a negative component having minimum at Bm ~ 0.5 mT that changes sign
to positive MEL with an approximate B2/(B02+B2) shape with B0 ≈ 4.5 mT. The high field shape,
U
namely B2/(B02+B2), is a generic feature in this model. For small values of the exchange
AN
interaction, B0 is determined primarily by the HFI constant aHF; also the USMEL response is a
strong function of the decay constant, k. The negative component with Bmin appears only for
M
relatively long decay times (e.g., ħk/aHF ≤ 0.1). For Jex/aHF > 1 the characteristic USMEL response
is no longer distinguishable. More details about the calculation can be found in the literature.[48,
D
63, 106]
TE
In general, the PP model is widely used to explain the magnetic field effect in physics[70],
EP
chemistry and biology[71, 72] and of course OMAR in OLEDs.[55, 63, 82, 87] The general
notion is that OMAR is large when both electrons and holes (or emission) are present in the
C
device. We note that the direct observation of ISC in TADF materials in solid state has been
AC
recently achieved.[107] This further strengthens the model possibility for OMAR. Nevertheless, it
is not clear how this model can explain the MFE in unipolar devices where only one type of
carriers exists. Since the impurity of OSCs is normally high, it is generally believed that the
injected carriers can pair with opposite-sign charges from impurity and therefore the model is still
21
ACCEPTED MANUSCRIPT
Desai et al.[103] and Hu et al.[59] suggested the role played by triplets on the conducting
charges of devices in order to explain OMAR. The model was first proposed by Ern and Merrifiel
who used it to explain the MFE on triplet exciton quenching in organic crystals.[108] An exciton
PT
can transfer its energy to the ground state by interacting with either a free or trapped charge
RI
carrier. This interaction is more likely to happen with a triplet exciton because triplet lifetimes are
a few orders of magnitude longer than singlet lifetimes. Therefore, the triplet density is dominant
SC
over the singlet density and is more likely to collide with charges.
Desai et al.[56] used the model for the organic material Alq3 in particular. Once turn-on
U
has been reached in an OLED, triplets are generated and, due to their long lifetime (estimated to
AN
be 25µs in Alq3), they will diffuse throughout the active layer until they spontaneously recombine
or are quenched at the interfaces. Since triplets are neutral, the diffusion will be relatively slow
M
and results in a large concentration of triplets being present in devices. Hence, their equilibrium
D
concentration would be expected to increase with increasing current density. Based on the work
TE
by Ern and Merrifield[108], the triplets charge interaction with an estimated interaction radius of
I1 I
∗
C + H1 ↔ KC … H1 M → H1 +N9O (13)
C
where T1 is the triplet state, H1 is the spin 1/2 paramagnetic center, KC … H1 M is a pair state, and
AC
k1 is the rate of formation or backscattering from the pair state. The right hand side of the equation
shows that the pair state can also dissociate into a free carrier and singlet ground state with a rate
constant k2, while releasing energy via phonons. The left-hand side of this equation describes a
scattering event between a free carrier and a triplet, which will result in a decrease in the carrier
mobility. In principle, k1 depends on the density of polarons and triplet density while k2 depends
22
ACCEPTED MANUSCRIPT
on the local magnetic field, including randomly oriented hyperfine fields. One can see as the
concentration of triplets decreases, the probability of scattering events decreases (smaller k1) and
hence the mobility should increase. Based on Desai et al.[56], since MEL is normally found to be
positive, the magnetic field enhances the singlet density while diminishing the triplet density via
PT
ISC. Consequently, the triplet charge interaction becomes less effective and thereby enhances the
RI
mobility of the OLED leading to positive MFE.
SC
positive: (i) Since the singlet excitons have a smaller ionic nature than triplet excitons, when EL
increases, the dissociation of singlet excitons into free charges also increases. This leads to
U
positive MEL and MC. In addition, triplet excitons can collide and transfer their energy to trapped
AN
polarons to increase free polaron density by detrapping the trapped polarons, leading to positive
MC. (ii) The negative MC comes from the argument that magnetic fields can slow down the
M
triplet-charge interaction process (smaller k2 in Eq.13) leading to smaller free polarons releasing
D
from this reaction. By controlling the negative to positive polaron density ratio in OLEDs, Hu et
TE
al. effectively changed the sign of MC inside the devices. We note that recently using
microscopic and numerical device simulations, Janssen et al. showed that this model can
EP
In principle, the model can be used to explain the OMAR sign change and line shape of
C
OMAR. However, this model predicts that OMAR should increase with increasing current density
AC
or triplet charge collision. This is, in fact, not the case as OMAR has its largest value at relative
low current density.[83] In addition, Geng et al. shows that OMAR magnitude decreases when the
photo-excited exciton density increases, contrary with the model prediction.[61, 111]
23
ACCEPTED MANUSCRIPT
4.4 Δg mechanism
The Δg mechanism was first proposed by Wang et al.[112] to explain the MFE in MEH-
PPV/fullerene blend OLEDs. The blend is normally used in organic photovoltaics in which the
charge separation is one of important factors for the operation of the device. The magnetic field
PT
acts on charge transfer states (exciplex) where an electron localized at the fullerene acceptor has
RI
different g factor (g-) than a hole (g+) localized in MEH-PPV donor. Based on the Δg mechanism,
the singlet and triplet spin mixing rate is proportional to the difference of the electron and hole
SC
Larmor frequency, which can be described as ΔgµBB. In principle, spin mixing needs to satisfy
U
both conservation of spin momentum and energy. The spin can be conserved by either exchange
AN
with nuclear spin (HFI of PP mechanism) or local magnetic field via Δg mechanism. The energy
of the singlet and triplet states can be modified by emitting or absorbing phonons as in the case of
M
TADF. At low magnetic field, since the Zeeman splitting is small, the spin mixing is more
effective and can be governed by both HFI and the Δg mechanism. At high magnetic field, the
D
Zeeman energy is large and the spin mixing by HFI becomes less influential, while the spin
TE
mixing rate caused by the Δg mechanism increases. Consequently, the dependence of MFE on the
magnetic field becomes less effective at high field. Figure 13a shows that the interconversion
EP
between singlet and triplet states is limited by the Zeeman splitting while Figure 13b describes the
C
MFE caused by Δg mechanism. If applied magnetic field is large, there are only spin mixing
AC
between singlet, S and triplet, T0 (with zero projection spin in the quantization axis) is effective.
The detailed calculation when Δg term is included into the PP Hamiltonian can be found in the
literature.[68, 69] The model has been considered as a main mechanism for the giant OMAR
of the same TADF blend shows compelling evidence that PP mechanism is still a dominant
24
ACCEPTED MANUSCRIPT
mechanism in such compound.[113] Since the Δg model is the newest among OMAR models,
PT
We summarized all prominent experimental results of OMAR in OLEDs and organic
unipolar devices. We addressed four different mechanisms for explaining OMAR effect. There is
RI
not yet a consensus on the best model for OMAR in organic devices since none of the models can
SC
be used to explain all cases of OMAR response. Therefore, MFE in OLEDs is still an attractive
topic for debate. Nevertheless, it is widely accepted that random hyperfine fields play a central
U
role in the MFE effect, which exists in all the models except the Δg mechanism. The multiple
AN
components in the OMAR response might imply that more than one mechanism occurs
simultaneously. Since MFE in OLEDs is large at room temperature, it has a great potential for
M
magnetic sensor and lighting applications. The recent discovery of giant OMAR in TADF-based
OLEDs is very promising for the advancement of such applications in the near future. So far,
D
MFE studies using TADF materials are very limited. The OMAR mechanism behind this
TE
astonishing effect is still unclear due to lack of experimental evidence. For example, it is not clear
EP
how the OMAR response occurs when the exchange energy gradually changes. Finally, all
OMAR studies thus far are done in large area OLEDs of about 1 mm2, where the capacitance of
C
the device is large leading to slow response time of the device. OMAR studies on nanoscale
AC
OLEDs would simplify the spin dynamics in OLEDs for a better understanding of OMAR. In
addition, owning to a much smaller capacitance, a nanometer OMAR device might have a fast
response time for critical applications such as fast light sources for fiber-optic
telecommunications.
25
ACCEPTED MANUSCRIPT
Figure Captions
Figure 1. Chemical structure of some organic semiconductors including small molecules and -
PT
hexylthiophene-2,5-diyl)(RRP3HT), poly(9,9-dioctylfluorenyl-2,7-diyl(PFO), deuterated
RI
poly(dioctyloxy)phenylenevinylene(D-DOOPPV), protonated poly(dioctyloxy)phenylenevinylene
(H-DOOPPV).
SC
Figure. 2. (a) Device layout of a typical OLED. (b) Work functions of common metals used in
U
making electrodes and typical HOMO, LUMO energies of an organic semiconductor,
AN
polyfluorene (PFO). The left metals are typically used as hole injection electrodes, while the right
ones are usually used as electron injection electrodes. (c) Working principle of OLED: four
M
important processes are shown: (1) charge injection; (2) charge transport; (3) recombination of
positive and negative polarons to form loosely bound PP; and (4) exciton formation and emission.
D
TE
26
ACCEPTED MANUSCRIPT
PPV based OLEDs with electrical conditioning. [88] (b) MC and MEL in an exciplex based
OLEDs [86] and (c) MC and MEL after conditioning.[69] Reproduced with permission.
PT
Figure 6. Normalized OMAR traces fitted by using different empirical laws. The solid curves are
RI
fits using Lorentzian function of forms B2/(|B| + B0)2 (red lines), [65] B2/(B2 + B02) (blue
lines),[65] and triple Lorentzian function (olive line).[91] Reproduced with permission.
SC
Figure 7. Isotope dependence of (a) magneto-electroluminescence (MEL) and (b) maneto-
U
conductivity (MC) responses in OLEDs based on D- and H-DOOPPVs measured at bias voltage
AN
V=2.5 volt and at room temperature.[48] Inset in (a) shows the field, B1/2 for the two polymers,
plotted versus the applied bias voltage, V, with linear fits, where V is given in terms of the
M
internal electric field in the polymer layer, E=[V-Vbi]/df. Reproduced with permission.
D
TE
Figure 8. Normalized MC(B)/USMC(B) response for (a) |B|<30 mT, and (b) |B|<2 mT in hole-
and electron-only unipolar diodes based on MEH-PPV, measured at room temperature and V=3 V
EP
and 20 V, respectively. The USMC(B) responses are somewhat shifted in (b) for clarity.[63]
Figure 9. Room temperature MEL (MC) response of D- and H-DOOPPVs (solid and dash lines,
respectively) measured at bias voltage V=2.5 V, plotted for |B|<3 mT.[48, 63] Reproduced with
permission.
27
ACCEPTED MANUSCRIPT
Figure 10. Bipolaron model as described in the main text, with the red arrow indicating the spin
of a polaron present at β (arbitrarily chosen opposite to the local magnetic field) and the red
arrows at site α shows the spin of a possible additional polaron for (a) anti-parallel spin hopping
and (b) parallel spin hopping. (c) Hyperfine field average of the function f(B) of Eq. (8) for
PT
various branching ratios b. The lower three red lines show Lorentzian fits, the upper two blue
RI
lines fit to the non-Lorentzian empirical law. The fitting parameters B0 are shown.[57]
SC
Figure 11. (a) Energy levels (E) of the 16 spin sublevels of a polaron-pair where each of the two
U
polarons couples to a single proton in the H-DOOPPV (nuclear spin, I=½), based on the spin
AN
Hamiltonian that includes HF (a), exchange (Jex) and Zeeman interactions, as a function of the
applied magnetic field, B for the case Jex<<a. Both E and B are given in units of a. (b) Same as in
M
(a) but for the 36 spin sublevels of a polaron-pair coupled to two 2H nuclei in the D-DOOPPV
D
Figure 12. Calculated magnetic field response of the singlet yield (a) and magneto-conductance
EP
(b) for a two-proton PP, where g1 = g2 = g ~2, a1 = a2 =a, with a/gµB =3.5 mT, J = 0, δTS = 0.96
and ħk/a = 2x10-3. The resulting MEL response HWHM is ~4.5 mT, and Bmin ~ 0.5 mT.[48]
C
Figure 13. (a) Schematic of Δg mechanism where the spin mixing rate, ΔgµBB between singlet
and triplet manifold are shown. (b) General behavior of MFE with applied magnetic field.
28
ACCEPTED MANUSCRIPT
References
[1] S.A. Wolf, D.D. Awschalom, R.A. Buhrman, J.M. Daughton, S. von Molnar, M.L. Roukes,
A.Y. Chtchelkanova, D.M. Treger, Spintronics: A spin-based electronics vision for the future,
Science, 294 (2001) 1488-1495.
[2] Zutic I., J. Fabian, a.S. Das-Sarma, Spintronics: Fundamentals and applications, Revew of
Modern Physics, 76 (2004) 323-410.
PT
[3] W. Gerlach, O. Stern, Das magnetische Moment des Silberatoms, Z. Physik, 9 (1922) 353-
355.
[4] W. Gerlach, O. Stern, Der experimentelle Nachweis der Richtungsquantelung im Magnetfeld,
RI
Z. Physik, 9 (1922) 349-352.
[5] I.I. Rabi, J.R. Zacharias, S. Millman, P. Kusch, A New Method of Measuring Nuclear
Magnetic Moment, Physical Review, 53 (1938) 318-318.
SC
[6] M. Julliere, Tunneling between Ferromagnetic-Films, Phys. Lett. A, 54 (1975) 225-226.
[7] P.M. Tedrow, R. Meservey, Spin Polarization of Electrons Tunneling from Films of Fe, Co,
Ni, and Gd, Phys Rev B, 7 (1973) 318-326.
[8] C. Chappert, A. Fert, F.N. Van Dau, The emergence of spin electronics in data storage, Nature
U
Materials, 6 (2007) 813-823.
[9] M. Baibich, J.M. Broto, A. Fert, F. NguyenVanDan, F. Petroff, P. Etienne, G. Creuzert, A.
AN
Friederich, J. Chazelas, Giant Magnetoresistance of (001)Fe/(001)Cr Magnetic Superlattices,
Physical Review Letters, 61 (1988) 2472-2475.
[10] G. Binasch, P. Grunberg, F. Saurenbach, W. Zinn, Enhanced Magnetoresistance in Layered
Magnetic-Structures with Antiferromagnetic Interlayer Exchange, Phys Rev B, 39 (1989) 4828-
M
4830.
[11] Y. Tian, S. Yan, Giant magnetoresistance: history, development and beyond, Sci. China
Phys. Mech. Astron., 56 (2013) 2-14.
D
[12] S.S.P. Parkin, Giant Magnetoresistance in Magnetic Nanostructures, Annu Rev Mater Sci, 25
(1995) 357-388.
TE
E.Y. Tsymbal, Magnetic Tunnel Junctions with Ferroelectric Barriers: Prediction of Four
Resistance States from First Principles, Nano Letters, 9 (2009) 427-432.
[15] G. Schmidt, Concepts for spin injection into semiconductors - a review, J Phys D Appl Phys,
38 (2005) R107-R122.
C
[16] F.J. Jedema, A.T. Filip, B.J. van Wees, Electrical spin injection and accumulation at room
temperature in an all-metal mesoscopic spin valve, Nature, 410 (2001) 345-348.
AC
[17] C.N.R. Rao, A.K. Cheetham, Giant Magnetoresistance in Transition Metal Oxides, Science,
272 (1996) 369-370.
[18] A.A. Baker, A.I. Figueroa, L.J. Collins-McIntyre, G. van der Laan, T. Hesjedal, Spin
pumping in Ferromagnet-Topological Insulator-Ferromagnet Heterostructures, Scientific Reports,
5 (2015) 7907.
[19] S.Z. Peng, Y. Zhang, M.X. Wang, Y.G. Zhang, W. Zhao, J.G. Webster, Magnetic Tunnel
Junctions for Spintronics: Principles and Applications, Wiley Encyclopedia of Electrical and
Electronics Engineering, John Wiley & Sons, Inc.1999.
29
ACCEPTED MANUSCRIPT
[20] W.J.M. Naber, S. Faez, W.G. van der Wiel, Organic spintronics, J. Phys. D, 40 (2007) R205-
R228.
[21] V. Dediu, M. Murgia, F.C. Matacotta, C. Taliani, S. Barbanera, Room temperature spin
polarized injection in organic semiconductor, Solid State Commun, 122 (2002) 181-184.
[22] Z.H. Xiong, D. Wu, Z.V. Vardeny, J. Shi, Giant magnetoresistance in organic spin-valves,
Nature, 427 (2004) 821-824.
[23] X. Lou, C. Adelmann, S.A. Crooker, E.S. Garlid, J. Zhang, K.S.M. Reddy, S.D. Flexner, C.J.
PT
Palmstrom, P.A. Crowell, Electrical detection of spin transport in lateral ferromagnet-
semiconductor devices, Nature Physics, 3 (2007) 197-202.
[24] J.H. Burroughes, D.D.C. Bradley, A.R. Brown, R.N. Marks, K. Mackay, R.H. Friend, P.L.
RI
Burn, A.B. Holmes, Light-Emitting-Diodes Based on Conjugated Polymers, Nature, 347 (1990)
539-541.
[25] C.W. Tang, S.A. VanSlyke, Organic electroluminescent diodes, Applied Physics Letters, 51
SC
(1987) 913-915.
[26] B.W. D'Andrade, S.R. Forrest, White organic light-emitting devices for solid-state lighting,
Adv Mater, 16 (2004) 1585-1595.
[27] C.W. Tang, 2-Layer Organic Photovoltaic Cell, Applied Physics Letters, 48 (1986) 183-185.
U
[28] A.J. Heeger, 25th Anniversary Article: Bulk Heterojunction Solar Cells: Understanding the
Mechanism of Operation, Adv Mater, 26 (2014) 10-28.
AN
[29] A. Tsumura, H. Koezuka, T. Ando, Macromolecular electronic device: Field effect
transistor with a polythiophene thin film, Applied Physics Letters, 49 (1986) 1210-1212.
[30] C.D. Dimitrakopoulos, P.R.L. Malenfant, Organic thin film transistors for large area
M
[35] F. Wang, Z.V. Vardeny, Recent advances in organic spin-valve devices, Synthetic Metals,
160 (2010) 210-215.
[36] H. Shirakawa, E.J. Louis, A.G. MacDiarmid, C.K. Chiang, A.J. Heeger, Synthesis of
electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH), Journal of
C
30
ACCEPTED MANUSCRIPT
[42] A.J. Drew, J. Hoppler, L. Schulz, F.L. Pratt, P. Desai, P. Shakya, T. Kreouzis, W.P. Gillin,
A. Suter, N.A. Morley, V.K. Malik, A. Dubroka, K.W. Kim, H. Bouyanfif, F. Bourqui, C.
Bernhard, R. Scheuermann, G.J. Nieuwenhuys, T. Prokscha, E. Morenzoni, Direct measurement
of the electronic spin diffusion length in a fully functional organic spin valve by low-energy muon
spin rotation, Nature Materials, 8 (2009) 109-114.
[43] M. Cinchetti, K. Heimer, J. Wüstenberg, O. Andreyev, M. Bauer, S. Lach, C. Ziegler, Y.
Gao, M. Aeschlimann, Determination of spin injection and transport in a ferromagnet/organic
PT
semiconductor heterojunction by two-photon photoemission, Nature Materials, 8 (2009) 115-119.
[44] J.F. Ren, J.Y. Fu, D.S. Liu, L.M. Mei, S.J. Xie, Diffusion theory of spin injection into
organic polymers, Journal of Physics: Condensed Matter, 17 (2005) 2341.
RI
[45] Z.G. Yu, Suppression of the Hanle Effect in Organic Spintronic Devices, Physical Review
Letters, 111 (2013) 016601.
[46] W. Xu, G.J. Szulczewski, P. LeClair, I. Navarrete, R. Schad, G.X. Miao, H. Guo, A. Gupta,
SC
Tunneling magnetoresistance observed in La0.67Sr0.33MnO3/organic molecule/Co junctions,
Applied Physics Letters, 90 (2007) 072506.
[47] M. Grünewald, R. Göckeritz, N. Homonnay, F. Würthner, L.W. Molenkamp, G. Schmidt,
Vertical organic spin valves in perpendicular magnetic fields, Phys Rev B, 88 (2013) 085319.
U
[48] T.D. Nguyen, G. Hukic-Markosian, F. Wang, L. Wojcik, X. Li, E. Ehrenfreund, Z.V.
Vardeny, Isotope effect in spin response of [pi]-conjugated polymer films and devices, Nature
AN
Materials, 9 (2010) 345-352.
[49] W. Wagemans, B. Koopmans, Spin transport and magnetoresistance in organic
semiconductors, Phys Status Solidi B, 248 (2011) 1029-1041.
[50] D.L. Sun, E. Ehrenfreund, Z.V. Vardeny, The first decade of organic spintronics research,
M
thin film devices, physica status solidi (RRL) – Rapid Research Letters, 6 (2012) 229-242.
[53] T.D. Nguyen, Y. Sheng, J. Rybicki, G. Veeraraghavan, M. Wohlgenannt, Magnetoresistance
in [small pi]-conjugated organic sandwich devices with varying hyperfine and spin-orbit coupling
EP
strengths, and varying dopant concentrations, Journal of Materials Chemistry, 17 (2007) 1995-
2001.
[54] O. Mermer, G. Veeraraghavan, T.L. Francis, Y. Sheng, D.T. Nguyen, M. Wohlgenannt, A.
Kohler, M.K. Al-Suti, M.S. Khan, Large magnetoresistance in nonmagnetic pi-conjugated
C
31
ACCEPTED MANUSCRIPT
[59] B. Hu, Y. Wu, Tuning magnetoresistance between positive and negative values in organic
semiconductors, Nature Materials, 6 (2007) 985-991.
[60] F.J. Wang, H. Bassler, Z.V. Vardeny, Magnetic Field Effects in pi-Conjugated Polymer-
Fullerene Blends: Evidence for Multiple Components, Physical Review Letters, 101 (2008)
236805.
[61] R. Geng, N.T. Mayhew, T.D. Nguyen, Tunable magneto-conductance and magneto-
electroluminescence in polymer light-emitting electrochemical planar devices, Applied Physics
PT
Letters, 103 (2013) 243307.
[62] J. Kalinowski, J. Szmytkowski, W. Stampor, Magnetic hyperfine modulation of charge
photogeneration in solid films of Alq3, Chemical Physics Letters, 378 (2003) 380-387.
RI
[63] T.D. Nguyen, B.R. Gautam, E. Ehrenfreund, Z.V. Vardeny, Magnetoconductance Response
in Unipolar and Bipolar Organic Diodes at Ultrasmall Fields, Physical Review Letters, 105 (2010)
166804.
SC
[64] T.D. Nguyen, G. Hukic-Markosian, F.J. Wang, L. Wojcik, X.G. Li, E. Ehrenfreund, Z.V.
Vardeny, The hyperfine interaction role in the spin response of pi-conjugated polymer films and
spin valve devices, Synthetic Metals, 161 (2011) 598-603.
[65] Y. Sheng, T.D. Nguyen, G. Veeraraghavan, Ö. Mermer, M. Wohlgenannt, S. Qiu, U. Scherf,
U
Hyperfine interaction and magnetoresistance in organic semiconductors, Phys Rev B, 74 (2006)
045213.
AN
[66] P. Shakya, P. Desai, M. Somerton, G. Gannaway, T. Kreouzis, W.P. Gillin, The magnetic
field effect on the transport and efficiency of group III tris(8-hydroxyquinoline) organic light
emitting diodes, J Appl Phys, 103 (2008) 103715.
[67] L. Nuccio, M. Willis, L. Schulz, S. Fratini, F. Messina, M. D'Amico, F.L. Pratt, J.S. Lord, I.
M
Response of Exciplex Light Emission due to Correlated Spin-Charge Dynamics, Physical Review
X, 6 (2016) 011011.
[70] R.P. Groff, A. Suna, P. Avakian, R.E. Merrifield, Magnetic hyperfine modulation of dye-
sensitized delayed fluorescence in organic crystals, Phys Rev B, 9 (1974) 2655-2660.
C
[71] C.R. Timmel, Effects of weak magnetic fields on free radical recombination reactions, Mol.
Phys., 95 (1998) 71-89.
AC
[72] H. Hayashi, Introduction to Dynamic Spin Chemistry; Magnetic Field Effects on Chemical
and Biochemical Reactions, World Scientific Publishing, World Scientific Lecture and Course
Notes in Chemistry, 2004.
[73] V.N. Prigodin, J.W. Yoo, H.W. Jang, C. Kao, C.B. Eom, A.J. Epstein, New advances in
organic spintronics, J Phys Conf Ser, 292 (2011) 012001.
[74] J.M. Lupton, D.R. McCamey, C. Boehme, Coherent Spin Manipulation in Molecular
Semiconductors: Getting a Handle on Organic Spintronics, ChemPhysChem, 11 (2010) 3040-
3058.
32
ACCEPTED MANUSCRIPT
[75] T.D. Nguyen, E. Ehrenfreund, Z.V. Vardeny, The development of organic spin valves from
unipolar to bipolar operation, MRS Bulletin, 39 (2014) 585-589.
[76] A.J. Drew, G. Szulczewski, L. Nuccio, W.P. Gillin, The role of interfaces in organic spin
valves revealed through spectroscopic and transport measurements, physica status solidi (b), 249
(2012) 9-17.
[77] J. Devkota, R. Geng, R.C. Subedi, T.D. Nguyen, Organic Spin Valves: A Review, Advanced
Functional Materials, (2016) n/a-n/a.
PT
[78] B. Hu, L. Yan, M. Shao, Magnetic-Field Effects in Organic Semiconducting Materials and
Devices, Adv Mater, 21 (2009) 1500-1516.
[79] M.A. Baldo, D.F. O'Brien, Y. You, A. Shoustikov, S. Sibley, M.E. Thompson, S.R. Forrest,
RI
Highly efficient phosphorescent emission from organic electroluminescent devices, Nature, 395
(1998) 151-154.
[80] H. Uoyama, K. Goushi, K. Shizu, H. Nomura, C. Adachi, Highly efficient organic light-
SC
emitting diodes from delayed fluorescence, Nature, 492 (2012) 234-238.
[81] F.B. Dias, K.N. Bourdakos, V. Jankus, K.C. Moss, K.T. Kamtekar, V. Bhalla, J. Santos,
M.R. Bryce, A.P. Monkman, Triplet Harvesting with 100% Efficiency by Way of Thermally
Activated Delayed Fluorescence in Charge Transfer OLED Emitters, Adv Mater, 25 (2013) 3707-
U
3714.
[82] J. Kalinowski, M. Cocchi, D. Virgili, V. Fattori, P.D. Marco, Magnetic field effects on
AN
organic electrophosphorescence, Phys. Rev. B, 70 (2004) 205303-205309.
[83] T.L. Francis, O. Mermer, G. Veeraraghavan, M. Wohlgenannt, Large magneto-resistance at
room-temperature in small-molecular weight organic semiconductor sandwich devices, New J.
Phys., 6 (2004) 185-192.
M
[84] E.L. Frankevich, A.A. Lymarev, I. Sokolik, F.E. Karasz, S. Blumstengel, R.H. Baughman,
H.H. Hörhold, Polaron-pair generation in poly(phenylene vinylenes), Phys Rev B, 46 (1992)
9320-9324.
D
B, 77 (2008) 235209-235215.
[86] Y. Ling, Y. Lei, Q. Zhang, L. Chen, Q. Song, Z. Xiong, Large magneto-conductance and
magneto-electroluminescence in exciplex-based organic light-emitting diodes at room
EP
Performance of Organic Spintronic Devices Using X-Ray Generated Traps, Physical Review
Letters, 109 (2012) 076603.
[90] S. Zhang, A.J. Drew, T. Kreouzis, W.P. Gillin, Modelling of organic magnetoresistance as a
function of temperature using the triplet polaron interaction, Synthetic Metals, 161 (2011) 628-
631.
[91] N.J. Rolfe, M. Heeney, P.B. Wyatt, A.J. Drew, T. Kreouzis, W.P. Gillin, The effect of
deuteration on organic magnetoresistance, Synthetic Metals, 161 (2011) 608-612.
33
ACCEPTED MANUSCRIPT
PT
the spin response of aluminum tris(8-hydroxyquinoline) based devices, Phys Rev B, 85 (2012)
245437.
[95] M. Cölle, C. Gärditz, Delayed fluorescence and phosphorescence of tris-(8-
RI
hydroxyquinoline)aluminum (Alq3) and their temperature dependence, Journal of Luminescence,
110 (2004) 200-206.
[96] T.D. Nguyen, Y. Sheng, M. Wohlgenannt, T.D. Anthopoulos, On the role of hydrogen in
SC
organic magnetoresistance: A study of C60 devices, Synthetic Metals, 157 (2007) 930-934.
[97] H. Malissa, M. Kavand, D.P. Waters, K.J. van Schooten, P.L. Burn, Z.V. Vardeny, B. Saam,
J.M. Lupton, C. Boehme, Room-temperature coupling between electrical current and nuclear
spins in OLEDs, Science, 345 (2014) 1487-1490.
U
[98] B. Brocklehurst, K.A. McLauchlan, Free radical mechanism for the effects of environmental
electromagnetic fields on biological systems, Int. J. Radiat. Biol., 69 (1996) 3-24.
AN
[99] R. Belaid, T. Barhoumi, L. Hachani, L. Hassine, H. Bouchriha, Magnetic field effect on
recombination light in anthracene crystal, Synth. Metals, 131 (2002) 23-30.
[100] D.R. McCamey, K.J. van Schooten, W.J. Baker, S.Y. Lee, S.Y. Paik, J.M. Lupton, C.
Boehme, Hyperfine-Field-Mediated Spin Beating in Electrostatically Bound Charge Carrier Pairs,
M
[102] S. Liang, R. Geng, B. Yang, W. Zhao, R. Chandra Subedi, X. Li, X. Han, T.D. Nguyen,
Curvature-enhanced Spin-orbit Coupling and Spinterface Effect in Fullerene-based Spin Valves,
TE
[104] N.J. Harmon, M.E. Flatté, Spin-Flip Induced Magnetoresistance in Positionally Disordered
Organic Solids, Physical Review Letters, 108 (2012) 186602-186605.
[105] R.N. Mahato, H. Lülf, M.H. Siekman, S.P. Kersten, P.A. Bobbert, M.P. de Jong, L. De
Cola, W.G. van der Wiel, Ultrahigh Magnetoresistance at Room Temperature in Molecular Wires,
C
34
ACCEPTED MANUSCRIPT
[110] P. Janssen, M. Cox, S.H.W. Wouters, M. Kemerink, M.M. Wienk, B. Koopmans, Tuning
organic magnetoresistance in polymer-fullerene blends by controlling spin reaction pathways, Nat
Comm, (2013).
[111] R. Geng, R.C. Subedi, S. Liang, T.D. Nguyen, Discernment of possible organic magnetic
field effect machanisms using polymer light-emitting electrochemical cells, SPIN, 04 (2014)
1440010.
[112] F. Wang, H. Bassler, Z.V. Vardeny, Studies of magnetoresistance in polymer/fullerene
PT
blends, Phys. Rev. Lett., 101 (2008) 236805-236808.
[113] E. Hontz, W. Chang, D.N. Congreve, V. Bulović, M.A. Baldo, T. Van Voorhis, The Role of
Electron–Hole Separation in Thermally Activated Delayed Fluorescence in Donor–Acceptor
RI
Blends, The Journal of Physical Chemistry C, 119 (2015) 25591-25597.
U SC
AN
M
D
TE
C EP
AC
35
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC