Oxide Nanowires For Spintronics: Materials and Devices: Cite This: Nanoscale, 2012, 4, 1529

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www.rsc.org/nanoscale FEATURE ARTICLE
Oxide nanowires for spintronics: materials and devices
Yufeng Tian, Saidur Rahman Bakaul and Tom Wu*
Received 17th November 2011, Accepted 2nd January 2012
DOI: 10.1039/c2nr11767c
Published on 06 January 2012 on http://pubs.rsc.org | doi:10.1039/C2NR11767C
Spintronics, or spin-based data storage and manipulation technology, is emerging as a very active
research area because of both new science and potential technological applications. As the
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characteristic lengths of spin-related phenomena naturally fall into the nanometre regime, researchers
start applying the techniques of bottom-up nanomaterial synthesis and assembly to spintronics. It is
envisaged that novel physics regarding spin manipulation and domain dynamics can be realized in
quantum confined nanowire-based devices. Here we review the recent breakthroughs related to the
applications of oxide nanowires in spintronics from the perspectives of both material candidates and
device fabrication. Oxide nanowires generally show excellent crystalline quality and tunable physical
properties, but more efforts are imperative as we strive to develop novel spintronic nanowires and
devices.
1. Introduction There exists the grand material challenge: so far there is no

ferromagnetic (FM) semiconductor exhibiting both strong
Since the discovery of the giant magnetoresistance (GMR) effect magnetism and high transition temperature, suitable for room
in 1988,1,2 the spin-based electronics or spintronics has emerged temperature device applications. The most thoroughly studied
into an active research area. Spin-based data storage and and best understood FM semiconductor is Mn-doped GaAs, but
manipulation possess several advantages over the conventional it suffers from low Curie temperatures capped at about 190 K.5,6
charge-based counterpart, including ultra-low power consump- A breakthrough is the theoretical prediction of above room
tion, higher data processing speed, nonvolatility, improved temperature ferromagnetism (RTFM) in Mn-doped GaN and
scalability and so on.3,4 However, there are several prominent ZnO,7 which jump-started a flurry of activities aiming to find
obstacles down this road of spin-based technology. suitable candidates in doped wide-bandgap oxides, but experi-
mentally observed magnetism is usually very weak.8,9
Transition metal oxides exhibit rich physical properties
Division of Physics and Applied Physics, School of Physical and ranging from insulators, semiconductors, to metals, and even
Mathematical Sciences, Nanyang Technological University, 21 Nanyang
Link, 637371, Singapore. E-mail: [email protected]; Fax: +65 6794 superconductors. Their bandgaps span from the visible to the
1325; Tel: +65 6514 1047 ultraviolet (UV) regimes, and their magnetic properties range
Yufeng Tian received his bach- Saidur R. Bakaul received his

elor degree from Shandong BS in Electrical and Electronic
University (China) in 2003. He Engineering from Bangladesh
worked as a visiting scholar in University of Engineering and
University of Idaho (America) Technology (2005) and his PhD
from 2007 to 2008. After in Electrical and Computer
receiving his PhD from Shan- Engineering from the National
dong University in 2009, he University of Singapore (2011).
worked as a postdoctoral scien- Since 2011, he has been working
tist in Prof. Tom Wu’s group at as a postdoctoral researcher in
Nanyang Technological Univer- the group of Prof. Tom Wu. His
sity (Singapore). His research research interests include spin-
focuses on the magnetic and tronic devices, oxide ferromag-
Yufeng Tian transport properties of various Saidur Rahman Bakaul nets and electronic transport
spintronics oxide materials and properties of superconductor
devices. ferromagnet hybrid devices.
This journal is ª The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 1529–1540 | 1529
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from diamagnetic, paramagnetic, to FM and antiferromagnetic bottom-up nanostructures are potential building blocks for the
(AFM). They can also possess notable dielectric properties both nanoscale electronics and photonic devices.15–21
in the low-k and high-k regimes, and can be ferroelectric and Here, we focus on the perspective of applying oxide nanowires
piezoelelctric. Surface chemical reactivity of oxides can be in spintronic applications. On the material aspect, we will discuss
tailored from being highly active to inert. All these functionalities the physical properties of nanowires made of wide-bandgap
stem from the strong and complex coupling between charge, oxides, colossal magnetoresistance oxides, and other half-
spin, orbital, and lattice degrees of freedom in the material metallic oxides. On the device aspect, we will review some
systems (Fig. 1).10 notable examples of spintronic devices, the advantages of
Driven by the needs for miniaturization in many areas of incorporating bottom-up nanowires, and the associated
modern technology, more-and-more attention is paid to the challenges.
nanoscale systems. This is enabled by the significant break-
throughs in deposition technologies, lithography processing, and
characterization tools, which are accompanied by new insights in 2. Materials candidates for spintronic nanowires
theory and computation (Fig. 1). It is recognized that nanoscale

2.1 Wide-bandgap dilute magnetic oxides
systems are not merely the miniature form of the bulk counter-
part, instead they can bring about many ‘‘emergent phenomena’’ Since the theoretical prediction of a hole-mediated RTFM in
such as quantum confinement and proximity effects.11 Nano- Mn-doped ZnO at a carrier concentration around 1020 cm3,7
structures including nanowires, nanotubes, nanorods, and transition metal doped wide-bandgap oxides such as ZnO, TiO2,
nanoparticles represent an exciting and rapidly expanding In2O3, SnO2, and (In, Sn)2O3 (ITO) have been regarded as
research area that crosses the borders between physics, chem- promising candidates for high Curie temperature dilute magnetic
istry, biology, engineering, and materials science.12–14 These oxides (DMOs). Although extensive experimental investigations
have been performed on both undoped and transition-metal-
doped DMOs,22–27 the complex magnetic behavior is found to
sensitively depend on the concentrations of doped cations,
carriers, defects, and synthesis details.27
In many cases, the formation of metallic clusters or magnetic
secondary phases,28 even artefacts and contaminations are
responsible for the observed magnetic signals.29 In terms of
intrinsic mechanisms, for DMOs with high carrier concentra-
tions, long-range FM order can be Ruderman–Kittel–Kasuya–
Yoshida (RKKY) or double exchange type.10,30,31 For highly
insulating DMOs, the long range FM exchange is mediated by
localized carriers in the impurity band to form bound magnetic
polarons.27,32 RTFM was also observed in undoped oxides,
known as d0 ferromagnetism, which is closely related to the
defects.33 Coey et al. proposed a general charge transfer model,
where the FM order is linked to itinerant carriers associated with
structural defects and TM dopants.34 Despite the large number of
Fig. 1 Schematic diagram showing the intricate coupling between
studies in this field, the mechanisms of ferromagnetism in DMOs
charge, spin, orbital and lattice in transition metal oxides, as well as the
close relationship between various research fronts.
remain unclear, and the present status is discussed in several
recent reviews.10,35
Nanowires are often single phase and highly crystalline, and
they are ideal single-domain building blocks for constructing
Tom Wu obtained his bachelor spintronic nanodevices. High quality ZnO,36–38 In2O3,39,40 and
degree from Zhejing University TiO241 nanowires can be routinely synthesized. Their
(China) in 1995. After receiving morphology can be well controlled by catalyst,37,42 precursor,43
his PhD from University of pressure, and geometry44 during synthesis, also by post-growth
Maryland in 2002, he worked as treatments such as annealing45 and coating.45–48 Pioneer works
a postdoctoral scientist in indicate that ferromagnetism can be stabilized in various wide-
Argonne National Laboratory. bandgap oxides nanowires or nanorods doped with transition
In 2006, he joined Nanyang metals, including ZnO doped with Co,49–52 Mn,52–54 Ni,50 Cu,55–57
Technological University (Sin- and FeCo;58 TiO2 doped with Fe,59 Co,60,61 and Cr;60 SnO2 doped
gapore) as an assistant with Co,62 Mn,63 Ni,64 and Cu,65 and even in oxide nanowires
professor. His research group doped with nonmagnetic elements, such as ZnO doped with C66
focuses on synthesizing a wide and N.67 The large surface-to-volume ratios of nanowires can
range of oxide nanomaterials greatly enhance ferromagnetism through surface defects68 or
Tom Wu and thin films, and fabricating structural/compositional inhomogeneity.55,56 As an example, the
novel field effect and memory nanostructure and magnetic properties of well aligned Cu-doped
devices. ZnO nanowires were shown in Fig. 2.
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responsible for the negative MR at high fields (Fig. 3).86

Furthermore, the magneto-transport of nanowires can be
modulated by applying a gate voltage.86
Combining the oxide nanowire channel (ZnO, In2O3 and so
on) with the ferroelectric gate dielectrics (Pb(Zr1xTix)O3, for
example) in ferroelectric transistors has been explored.88,89
Memory effects and enhanced performance were observed.
Potentially, novel nanowire-based devices with multiferroic
components can be developed.
Another notable area is p–n junctions and light emitting
diodes (LED) based on oxide nanowires.90,91 Good rectification
and blue-light-emitting LED have been demonstrated. By
replacing non-magnetic nanowires with FM nanowires and/or
combining with FM electrodes, we can envisage nanowire-based

spin LED.
2.2 Mixed-valence manganites

Mixed-valence manganites have been intensively investigated
because of the ‘‘colossal magnetoresistance’’ (CMR) and the
complex magnetic phase transitions.92 In manganites, the
magnetic, electronic, and structural degrees of freedom interact
with each other through ‘‘double exchange’’ and Jahn–Teller
interaction. As an example, the rich phase diagram of
La1xSrxMnO3 is shown in Fig. 4.93
In terms of applications, the large MR and the great tunability
of CMR oxides are promising for magnetic recording, spin valve
Fig. 2 (a) SEM image of vertically aligned Cu-doped ZnO nanowires
devices, and magnetic tunnelling junctions.94–98 For example,
grown on a sapphire substrate. (b) Magnetic hysteresis loops measured at Zhao et al. reported an electric field modulation of MR in
5 K and 300 K for Cu-doped ZnO nanowires with homogeneous (S1) and a La0.9Sr0.1MnO3 junction from 70% to 80% near room
inhomogeneous (S2) dopant distributions. Copyright 2008 Wiley-VCH, temperature.99 Complementary magnetic and electric field
reproduced from ref. 55 with permission. tunings were observed in devices with phase-separated manga-
nites as channel,100 and the transition temperature was tailored
Nanowires exhibit multiple functionalities such as gas electrically.101,102 In narrow bridges of manganites with macro-
sensing,69–71 photovoltaic devices,72,73 and transparent elec- scopic phase separation, negative differential resistance has been
trodes.74 Because of symmetry-breaking surfaces, nanowires of observed as a result of reversible metal-to-insulator transition in
SnO2 and In2O3 show UV light emission and even lasing which nanoscale filaments.103,104
are absent in the bulk counterparts.75–79 Furthermore, three
dimensional epitaxial heterostructures with tailored optical
properties were synthesized,80 and interface-related properties
can be explored.
Nanowires have been successfully incorporated into nano-
electronics,81 and naturally they are envisaged as ideal building
blocks for nanoscale spintronics. Qiu et al. showed that a metal–
semiconductor hybrid nanostructure can provide a unique
opportunity to stabilize RTFM because metal decoration can
tune the Fermi level of oxide nanowires and promote the carrier
transfer.82 Furthermore, the Curie temperature of FM semi-
conductor in laterally patterned heterostructures was manipu-
lated,83 and this nanolithography-based approach may be also
applicable to DMOs. In terms of devices, a theoretical study
suggested that the magnetic properties of DMO nanowires can
be tuned by an electrical field,84 which may enable the electric
Fig. 3 MR measured at 10 K on devices made of (a) Co-doped ZnO
control of spin polarized current. nanowire contacted by Co electrodes; (b) Co-doped ZnO nanowire
Magneto-transport properties of individual oxide nanowires contacted by Au electrodes; (c) pure ZnO nanowire contacted by Co
have been studied,85–87 where s–d exchange induced spin splitting electrodes, and (d) pure ZnO nanowires contacted by Au electrodes.
of conduction band results in low-field positive magnetoresis- Copyright 2006 American Chemical Society, reproduced from ref. 86
tance (MR), while suppression of the weak localization effect is with permission.
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evidence to confirm such spin-dependent band structures have

been obtained by using techniques like spin-resolved photo-
emission117 and point contact Andreev reflection.118 As a result of
the high spin polarization ratio (100%), half-metallic binary
oxides such as Fe3O4, CrO2, and EuO are attractive for spin-
tronics applications.119
Magnetite (Fe3O4) is probably the most studied half metal
because of it high Curie temperature (858 K), which is critical
for device applications.120 Moreover, the lack of toxicity in Fe3O4
also promises applications in medical and biological areas, such
as drug delivery and magnetic resonance imaging.121 Previously,
Fe3O4 nanowires,120,122 nanotubes,123,124 and core/shell nano-
wires125,126 have been synthesized, and their magneto-transport
properties were studied. Ferromagnetism of magnetite nanowires

remains above room temperature, and the Verwey transition
temperature is around 120 K.120 In a magnetic tunnel junction

made of Fe3O4 nanocrystals, the sign of tunnel MR was found to
Fig. 4 Phase diagram of La1xSrxMnO3. The crystal structures (Jahn–
switch from negative to positive at the Verwey transition.127 Liao
Teller distorted orthorhombic, O0 ; orthorhombic, O; orbital ordered
et al. demonstrated a spin filter effect in Fe3O4 nanowires con-
orthorhombic, O00 ; rhombohedral, R; tetragonal, T; monoclinic, Mc; and
hexagonal, H) are indicated as well as the magnetic structures (para- tacted with normal metallic electrodes, where only the minority
magnetic, PM; short range order, SR; canted spin structure, CA; anti- spin carriers can transport through the Fe3O4 nanowires due to
ferromagnetic structure (either A- or C-, or G-type), AFM; the negative spin polarization (Fig. 5).122 Furthermore, the room
ferromagnetic, FM; phase separated, PS) and the electronic state (insu- temperature positive MR can be modulated by the bias
lating, I; metallic, M). Copyright 2009 American Physical Society, voltage.122
reproduced from ref. 93 with permission. Exchange bias is widely used in the present commercial tech-
nologies such as spin valve and magnetic tunnel junctions, and it
is regarded as an effective way to overcome the super-
However, there are several obstacles related to manganites in
paramagnetic limit in magnetic storage media.128 The exchange
nanodevice applications. First, the spin polarization of manga-
coupling and exchange bias effect in Fe3O4 based branched129
nites decays rapidly with temperature. Second, the defect chem-
and core–shell nanocrystals130 have been studied, and novel
istry and the stoichiometry–property correlation in manganites
properties including higher saturation magnetization, enhanced
are quite complex.105,106 Third, the physical properties of inter-
coercivity, exchange bias, and improved thermal stability were
faces in manganite-based devices remain elusive.107,108 Finally,
observed.
there is the urgent need for developing suitable device processing
As another notable spintronic material, CrO2 has a high spin
techniques.
polarization (>95%)118 and a Curie temperature of 395 K.
Compared to the wide-bandgap oxides, bottom-up synthesis
Fascinating transport properties have been revealed in CrO2 thin
of manganite nanowires is more challenging. Nevertheless, high
films.119,131 For instance, the CrO2 based tunnelling junction
quality single crystal nanocubes109 and nanowires110 of manga-
shows an enhanced low field MR,119 and the Josephson super-
nites have been reported. But so far there has been few studies on
current through the CrO2 may have a spin triplet nature.131
spintronic devices based on individual manganite nanowires.
However, CrO2 is metastable in ambient conditions, and its
For manganites, nanowires and related heterostructures
synthesis is rather challenging. Recently, single crystal CrO2
hopefully can enhance the Curie temperature111 and the low-field
nanorods132 and nanowires133 have been reported. Spin-depen-
MR.112,113 Another promising research topic is anisotropic
dent tunnelling transport was achieved in individual CrO2
magnetoresistance (AMR) which is a result of spin-orbital
nanorod devices contacted with nonmagnetic Ti/Au metallic
interaction and has important applications in magnetic field
electrodes.132 Unfortunately, the magnitude of the spin depen-
detection and data storage.114 Significant magnetic anisotropy
dent MR decreases rapidly with increasing temperature and bias
has been observed in nanowires.110 In addition, the morphology
voltage, which may be a result of spin independent inelastic
of nanowire can be modified by annealing or growing on engi-
hopping across the contact barriers.132
neered substrates,115 which could significantly affect the proper-
EuO is an attractive material as it may be the only magnetic
ties. We look forward to more efforts on exploring the
binary oxide that could be thermodynamically stable in contact
anisotropic transport in manganite nanowires and gaining
with silicon.134 Schmehl et al. demonstrated that the spin polar-
deeper understanding on low-dimensional spin-dependent
ization ratio of EuO exceeds 90%, and the half metallic behavior
transport.
remains even when highly doped.134 More interestingly, giant
Zeeman splitting and obvious magnetic circular dichroism
(MCD) response confirm the ferromagnetic nature of polycrystal
2.3 Half-metallic binary oxides
EuO nanorods synthesized via a three step reaction process.135 In
Half-metallic ferromagnets exhibit conducting states at the addition to its strong magnetism (6.9 mB), these EuO nanorods
Fermi level for the majority spin electrons, but a semiconductor have one of the largest MCD responses of any materials,
gap for the minority spin electrons.116 Direct experimental highlighting their potential in magneto-optical applications.135
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Fig. 5 (a) MR of individual Fe3O4 nanowires measured at different temperatures. (b) Schematic of the device. (c) FM order of Fe3O4, where the
minority carriers are responsible for the transport. (d) Bias dependence of MR for the Fe3O4 nanowire-based devices. Copyright 2006 American
Chemical Society, reproduced from ref. 122 with permission.
2.4 Ferroelectric and multiferroic oxides 3. Spintronic devices based on oxide nanowires
Nanowires of perovskite ferroelectric oxides, e.g., BaTiO3, have 3.1 Fabrication techniques: top down vs. bottom up
been used in energy harvesting devices,136,137 photonics, and
nanoelectromechanical systems.138 Molten-salt method is effec- Perhaps the most realistic approach to realize practical nanowire-
tive to produce nanostructures of complex oxides, e.g., nano- based spintronic devices is the ‘‘top-down’’ technique, in which
particles, nanocubes, nanoblets, and nanoflowers.139 Using some form of lithography, such as electron beam/optical lithog-
a scanned probe microscope, Yun et al. demonstrated that raphy,148,149 nanoimprint lithography,150 or m-contact printing151,152
nonvolatile electric polarization can be reproducibly induced and is used to pattern desired nanostructures. Besides, focused ion
manipulated on single crystal BaTiO3 nanowires.140 The ferro- beam technique153,154 or chemical etching in conjunction with
electricity is retained in nanowires as thin as 0.8 nm, which can be suitable masks can also be used to carve out nanowires from an
attributed to surface adsorbates such as OH and carboxylates.141 oxide film. In addition, Suzuki et al. invented a unique combination
Multiferroic materials show simultaneous ferroelectric and of atomic force microscopy lithography and Mo lift-off technique
magnetic orders, promising novel applications.142 Among them, to create oxide nanowires with dimensions down to 100 nm.155
BiFeO3 (BFO) has received the most attention, due to its high The lithography process has the advantage of excellent
ferroelectric Curie temperature (1103 K) and the AFM Neel controls over position and shape of the nanowires, and making
temperature (647 K). Periodic ferroelectric domains143 and contacts and multilayers always involve lithography. However,
electrical control of AFM domains144 have been realized in top-down fabrication often entails expensive equipment and
BFO. Different from the AFM order in bulk BFO, weak complicated processing. Furthermore, most of the oxide mate-
ferromagnetism and superparamagentic behaviour at low rials need high deposition temperature, and the typical electron
temperature were observed in polycrystalline nanowires, indi- beam and photo resists are incompatible with this requirement.
cating significant size effects on the magnetic order of The bottom-up synthesis mainly refers to the self-assembly of
BFO.145,146 Synthesis of single crystalline BFO nanowires has nanowires without involving any lithography. It has advantages
not been reported yet, which is also the status for many other in terms of mass production and cost-effectiveness. In addition,
complex oxides. Ground breaking efforts are needed to realize the bottom-up nanowires are single crystalline and free from
high quality nanowires of complex perovskite oxides with defects such as edge roughness, which is a major challenge in
controlled composition and morphology. A promising lithographically patterned nanowires. So far there has been few
approach towards well ordered complex oxide nanostructures is work on using self-assembled nanowires in spintronic devices,
to combine lithography and epitaxial thin film growth,147 which and a series of baby steps need to be taken, such as rational
will hopefully facilitate future studies. nanoscale synthesis, controlled positioning of nanowires, making
multilayer structure, and creating good electrical contacts.
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In some cases, combining top-down and bottom-up techniques et al.180 grew in-plane nanowire stacks of Py, Cu and Co using
have more advantages.156,157 Lithographically patterned resists interference lithography and ion milling. Core–shell nanowires
can be used as masks and then directed growth of oxide nano- were also demonstrated recently, which act as integrated spin
wires is achieved by spin coating of sol–gel precursors. Recently, valves (Fig. 6).181 The fully functional devices contain a chemical-
there have been a few reports on creating oxide nanowires by vapor-deposited Ni core nanowire which was surrounded by
using laser interference techniques.158–160 In this process a peri- sequential shell layers of CoO(10 nm)–Co(5 nm)–Cu(5 nm)–
odic interference pattern can be generated by using a laser source Co(5 nm) deposited by sputtering, and a MR effect of 9% was
and prisms with different numerical apertures, creating regular reported in this structure.
arrays of oxide nanowires. While nanowire based spin valves with transition metals have
Guided synthesis and assembly have been demonstrated in been extensively exploited, similar devices with oxide ferromag-
nanowire-based devices. Dai showed that the locations of carbon nets have been rarely reported. Recently, Gaucher et al.182
nanotubes can be controlled by using lithographically patterned successfully fabricated La2/3Sr1/3MnO3 nanowires with the
catalytic nanoparticles, and their growth directions can be smallest width of 65 nm by combining electron beam lithography
determined by van der Waals self-assembly forces and applied and ion beam etching. They showed that the electronic transport
electric fields.161 The electrical-field-controlled alignment of properties of these oxide nanowires are comparable to those of
nanowires was also demonstrated for semiconductor nano- unpatterned films. Goto et al. demonstrated GMR effect in
wires,162,163 and Langmuir–Blodgett (LB) technique was used for (Fe,Mn)3O4 nanowires with constrictions, which serve as lateral
similar purposes.164 In addition, structures of crossed nanowires, spin valves with pinned domain walls.183
suitable for memory devices and logic circuits, have also been Oxide nanowires are very promising to serve as building blocks
realized by using a combination of top-down and bottom-up in lateral spin valves or MTJs. One possible scheme starts with
approaches.165,166 Such fabrication techniques should be feasible bottom-up synthesized FM oxide nanowire, and a small portion
for making spintronic devices with oxide nanowires. of the nanowire can be converted into nonmagnetic by using
techniques like selective Ar+ ion milling, resulting in FM-NM-
FM lateral devices. Such nanowire-based spintronic devices are
3.2 Spin valve and magnetic tunnel junctions
attractive, but the central modified region must be thin enough to
Spin valve may be the most influential spintronic device which retain the spin coherent transport. Recently, Dai et al. theoreti-
has already found applications in magnetic data storage cally showed that by selective partial hydrogenation of C-doped
industry. Its basic working principle is the GMR effect,1,2 where ZnO nanowires, it is possible to create a nanowire-based MTJ
the resistance of a FM/NM/FM multilayer depends on the (Fig. 7).66 Electronic phase separation in manganites may be
relative alignment between the two FM layers; In general, an exploited to realize such lateral nanowire-based devices.
antiparallel alignment gives rise to larger resistance than the
parallel alignment. Most GMR research focuses on transition
metals, but spin valves have also been realized in oxides, in 3.3 Magnetic domain walls and spin transfer torque in oxide
particular FM manganites.167,168 nanowires
A related concept is the magnetic tunnel junction (MTJ)169,170 A magnetic domain wall separates two oppositely polarized
which also has vast applications in nonvolatile magnetic memory magnetic regions, and a number of data storage schemes based
devices. The basic difference between spin valve and MTJ lies in
the middle spacer layer, which needs to be insulating for MTJ,
whereas for spin valve, this layer is conducting. A number of
efforts have been devoted to create oxide based MTJ devices so
far, especially due to the 100% spin polarization in several FM
oxides, such as La1xSrxMnO3 (LSMO) with x 0.33, CrO2 and
Fe3O4. Lu et al.171 and Sun et al.172 first fabricated all-oxide MTJ
device with LSMO and SrTiO3 as FM and insulating layer,
respectively. Subsequently, a record tunneling magnetoresistance
(TMR) ratio of 1850% was reported in 2003 by Bowen et al.173
Despite these promising results, a major issue for the oxide based
MTJ devices is that the working temperature is often lower than
the room temperature, generally ascribed to the degraded
interfaces.174,175
Nanowire-based spin-valve devices were first realized in
metallic systems. Piraux et al.176 and Blondel et al.177 reported on
such devices based on NiFe/Cu and Co/Cu by using electro-
deposition in nanoporous polymer templates. In 2000, Evans
et al.178 synthesized multilayered (Co–Ni–Cu/Cu) nanowire spin Fig. 6 Schematic of a core–shell nanowire-based spin valve device. The
valves in anodic aluminum oxide (AAO) membranes which CoO shell biases the Co reference layer, and Cu acts as the nonmagnetic
showed very large GMR effect (55% at room temperature and spacer. The inset shows the scanning electron microscopy (SEM) image
115% at 77 K). Among other works, Dubois et al. used permalloy of such a device. Copyright 2010 IEEE Magnetic Society, reproduced
(Py) and Cu stacked in a vertical template,179 whereas Casta~ no from ref. 181 with permission.
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Fig. 7 (a) Atomic configuration of a TMR device made of a partially

hydrogenated C-doped ZnO nanowire. Two electrodes are semi-infinite
partially hydrogenated C-doped ZnO wires. The center region contains Fig. 8 Magnetic domain pattern in 500 nm diameter LSMO islands on
one unit cell of unhydrogenated wire and one unit cell of each electrode. (001) oriented STO substrates with (a) square, (b) diamond, and (c)
(b) Theoretical calculation of the spin resolved total density of states of circular shapes. The lower panel to each image shows the effect of
partially hydrogenated electrodes, showing a conversion from semi- distortions of the island shape. Copyright 2006 American Chemical
conducting to metallic characteristics. Copyright 2011 American Institute Society, reproduced from ref. 148 with permission.
of Physics, reproduced from ref. 66 with permission.
and Zou et al.197 have performed pioneering experiments to

on domain walls in magnetic nanowires have been create well defined magnetic domain walls in CrO2 nanowires
proposed.184,185 In the race-track memory, each magnetic domain using Ar+ ion milling and selective area growth techniques. These
wall represents a data bit.184 During the write operation, the works suggest that it is possible to pin magnetic domain walls at
domain wall is moved by external magnetic field or spin transfer the notched areas and inject them controllably along the CrO2
torque.186–188 To read a bit, GMR or TMR type devices are used nanowires by using a nucleation pad and an external magnetic
to detect the stray field from the domain wall. To utilize such field.
a scheme, it is critical to controllably create domain walls. In spite of challenges in controlling magnetic domain walls in
Magnetic nanowires with an artificial pinning center, such as oxide nanowires, several groups have reported current induced
notches,184 bent conduits,189 and narrow rings190 can serve this domain wall motion in oxide materials such as La0.7Sr0.3MnO3,
purpose. Extensive research works have been performed to La0.67Ba0.33MnO3d, CrO2, and Fe3O4. By using focused ion
realize such memory devices using transition ferromagnetic beam (FIB) milling, Ruotolo et al.198 and Cespedes et al.199
metals such as Py, Co, and Ni. patterned La0.7Sr0.3MnO3 into nanowires containing notches as
In manganites, various types of domain patterns such as the domain wall pinning centers. The MR measurements confirm
stripes,191 bubbles,192 and checker-boards193 have been reported. the current induced domain wall depinning with a critical current
Wu et al. observed perpendicular stripe magnetic domains in density of 1011 A m2 (Fig. 9). Liu et al.200 reported current
LSMO nano dots.194 Recently, Takamura et al. reported flower- dependent low field MR effect in La0.67Sr0.33MnO3 nanowires
shaped, flux closure domain and vortex structures in patterned with constrictions and ascribed this effect to the spin polarized
manganites created by Ar+ ion milling (Fig. 8).148 Mathews et al. bias current. In a similar constricted La0.67Ba0.33MnO3d nano-
reported successful fabrication of LSMO nanowires on NdGaO3 wire, Pallecchi et al. observed magnetic field and DC bias current
substrate by using interference lithography.159 It was demon- dependent asymmetric resistance hysteresis, which was also
strated that not only the shape anisotropy but also the substrate connected to the effect spin transfer torque.201 Surprisingly, the
induced anisotropy play important roles in determining the threshold current was found to be in the range of 107–108 A m2,
magnetic easy axis in these manganite nanostructures. much smaller than the typical current needed for moving domain
Controlled manipulation of domain walls in manganite walls in metals (1011 A m2).202 A number of possibilities, such as
nanostructures, which is essential for domain wall based memory stronger spin torque due to half metallicity, Joule heating assis-
devices, has not been thoroughly investigated. A few successes in tance and spin wave excitation may contribute to such a drastic
this context came by using CrO2. K€ onig et al.,195 Biehler et al.196 reduction in the threshold current.
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devices can be much more stable. Finally, as the domain

configuration in oxide materials depend sensitively on the strain
state,206,207 strain may provide an extra handle to control and
manipulate the domain walls.
3.4 Oxide nanowire based spin-field-effect transistor

(spin-FET)
Since the invention of the spin valve, a number of novel device
concepts have been proposed, including spin-field-effect tran-
sistor (spin-FET)208 and spin-LED.209,210 Datta and Das first
proposed the concept of spin-FET, where instead of the charge
degree of freedom, the spin state of the electron is used as the

information carrier. It consists of similar structure to the typical
metal-oxide-semiconductor FET device, except that the drain
and source contacts are half-metallic ferromagnets which are

magnetized in the channel current direction. The spin of the
channel electrons and hence the resistance of the device, can be
manipulated by pure Rashba type211 or Dresselhaus type spin–
orbit coupling212 or a delicate mixture of them,213,214 with the
assistance of an external gate voltage.
Two very important issues in designing spin-FET are the
leakage current in the off-state and the spin relaxation in the
channel. In this context, nanowires are suitable candidates as
the channel (Fig. 10). 1D or quasi-1D nanowires may help
suppress the leakage current as a result of their small cross
section. Typically, semiconductor channels have mainly two
Fig. 9 Schematic of the fabrication process of a LSMO notched nano- types of spin relaxation mechanisms, i.e., the D’yakonov–Perel
wire: (a) Ar+ ion milling of 5 mm wide tracks, (b) FIB milling of 3 mm long, mode215 and the Elliott–Yafet mode.216 In ‘‘narrow’’ nanowire-
500 nm wide bridges, (c) FIB milling of nanoconstrictions at the bridge based channels these relaxation mechanisms are expected to be
borders, and (d) SEM image of a patterned nanoconstriction. (e) Resis- suppressed and new diffusion modes may emerge during the
tance change due to the current-induced DW displacement for a device propagation of spins.217–219
with 50 nm constriction. The arrows indicate the direction of the In general, the operation of spin-FET relies on the controlla-
sweeping current. Copyright 2007 American Institute of Physics, repro-
bility over channel electron spins through the spin–orbit inter-
duced from ref. 198 with permission.
action. Therefore, in order to realize oxide nanowire based spin-
FET, one need to choose materials with a long spin de-phasing
length (L4) and strong spin–orbit coupling. Indium tin oxide
Apart from the manganite nanowires, current-induced domain
(ITO) nanowires could be a promising candidate in this regard.
wall motion has also been experimentally reported in constricted
Recently Hsu et al. showed that L4 in ITO nanowires can be as
Fe3O4203 and CrO2196 nanowires with threshold current densities
large as 520 nm at low temperatures.220 Furthermore, it was
of 1013 A m2 and 1010 A m2, respectively. However, none of
shown that by modifying the level of disorder in these nanowires,
these experiments showed direct evidence of current-induced
the strength of spin–orbit coupling can be adjusted.
domain wall motion by using imaging techniques such as
Apart from serving as channel materials, half-metallic oxides
magnetic force microscopy. Overall, more efforts from the
are promising candidate as the source and drain materials in
community are needed to shed light on the pinning and removal
a spin-FET. Due to the 100% spin-polarization and the possi-
of domain walls in oxide nanowires, which is essential for future
bility of controlling the magnetization by an external field,
device applications.
LSMO, CrO2 and Fe3O4 can be incorporated as sources of
In this research area of domain wall manipulation, oxide
nanowires are very promising to present breakthroughs. The
threshold current density needed for getting enough spin torque
to move a domain wall in typical transition metals is very high
(1010 A m2). To overcome this challenge, it can be advanta-
geous to use half metallic oxides, such as LSMO, Fe3O4 and
CrO2. Furthermore, a typical drawback of metals is their strong
tendency for oxidation, which demands the incorporation of
a protective capping layer in the device configuration. However, Fig. 10 Schematic of the proposed Datta–Das spin-FET208 (OFF state)
due to the spin flipping at the capping layer, the spin-torque- with a nanowire channel. By tuning the spin–orbit interaction strength,
assisted domain wall motion and the magnetization switching the electron spin can be modulated and the device can be switched
process often become complicated.204,205 Oxide-based spintronic between the ON and OFF states.
View Online
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Cite this: Nanoscale, 2012, 4, 1529

1. Introduction There exists the grand material challenge: so far there is no

Yufeng Tian received his bach- Saidur R. Bakaul received his

theory and computation (Fig. 1). It is recognized that nanoscale

responsible for the negative MR at high fields (Fig. 3).86

combining with FM electrodes, we can envisage nanowire-based

2.2 Mixed-valence manganites

evidence to confirm such spin-dependent band structures have

properties were studied. Ferromagnetism of magnetite nanowires

temperature is around 120 K.120 In a magnetic tunnel junction

Fig. 7 (a) Atomic configuration of a TMR device made of a partially

and Zou et al.197 have performed pioneering experiments to

devices can be much more stable. Finally, as the domain

3.4 Oxide nanowire based spin-field-effect transistor

degree of freedom, the spin state of the electron is used as the

and source contacts are half-metallic ferromagnets which are

2002, 420, 57–61.

based spintronic devices, considerable challenges remain to be 2010, 2, 1984–1998.

Matter Mater. Phys., 2007, 75, 144428. 1814.

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