Polarized Light Boosts Valleytronics: News & Views

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488 NATURE NANOTECHNOLOGY | VOL 7 | AUGUST 2012 | www.nature.

com/naturenanotechnology
news & views
nanoparticles into the incinerator by
spraying them either onto the waste in
the furnace or over the space above the
furnace. Cerium was quantifed in the
combustion exhaust gas (known as the
fue gas), ash, water and solid combustion
residues. Te Swiss team found that
crystalline cerium dioxide nanoparticles
seemed unchanged afer incineration of
the wastes and were seen to bind loosely
to the surface of the solid combustion
residues. Electron microscopy suggested
that no discharge of nanoparticles occurred
through the clean, fltered fue gas.
Tese results are consistent with the
expectation that cerium dioxide will be
stable at the incinerator temperature of
1,200C, as the melting temperature of
cerium dioxide is approximately 2,400C.
Furthermore, the proportionately
high surface area of nanoparticles and
intermolecular forces between individual
particles typically results in agglomerates
of micrometre-sized clusters that can
be fltered by many fue gas treatment
technologies
4
. Although the results were
predictable to some extent for these cerium
dioxide particles under the conditions
described by Stark and co-workers, such
studies are critical to understanding the
ultimate fate of and risk due to engineered
nanoparticles, and we encourage the
exploration of a wider range of conditions
using nanoparticles with diferent
thermalstabilities.
However, for risk management
purposes, attention should also be given to
unintentionally produced nanomaterials
(known as incidental nanoparticles), which
can form from incomplete combustion
processes or condensation of materials
afer the fltration process. Based on
exposure volume, the risks presented by
incidental nanomaterials, which have been
produced for millennia, may outweigh
those due to engineered nanomaterials
(Fig.1). For example, soot (also known as
black carbon), which is formed from the
incomplete combustion of hydrocarbon
fuels, infuences the global heat budget
5,6
,
air quality
5,7
and public health
7,8
. Te global
formation of black carbon from incidental
and natural sources currently dwarfs the
production of their engineered counterpart,
carbon nanotubes. Tis means that the risk
due to ultrafne particles of black carbon
should outweigh that of carbon nanotubes,
unless nanotubes present some exceptional
toxicities relative to black carbon.
Te contribution from inorganic
nanoparticles is similarly complex. For
example, metal nanoparticles and non-
nanoparticulate metals present in wastes
may volatilize in the incinerator and
re-form as nanoparticles afer fltration
of the fue gas. Indeed, engineered
nanoparticles are ofen synthesized using
vapour deposition techniques that are
similar to the condensation processes in
fue gas, and fy ash from coal combustion
has been shown to contain nanoparticles
of iron, aluminium, silicon oxides and
fullerene-like carbon nanoparticles
9,10
. It is
therefore important to track the source of
nanoparticles from incinerators, whether
incidental or engineered. To assess the
relative risks, it will be necessary to defne
the toxicities and release rates for incidental
and engineered nanoparticles alike.
However, current analytical methods still
cannot discern incidental from engineered
nanoparticles, and this area deserves
urgentattention.
Te work by Stark and co-workers is
one step towards demystifying the fate of
nanoparticles in incineration that must be
followed by work to understand the role of
incineration in transforming engineered
nanoparticles, generating nanoscale
phases throughout the process, and fnally,
understanding the relative importance of
diverse sources of nanoparticles to human
health and the environment.
Mark R.Wiesner and Desiree L.Plata are at
Duke University, 121 Hudson Hall, Durham,
North Carolina 27708, USA.
e-mail: [email protected]
References
1. Kiser, M. etal. Environ. Sci. Technol. 43, 67576763 (2009).
2. Gottschalk, F. & Nowack, B.J.Environ. Monitor.
13, 11451155 (2011).
3. Walser, T. etal. Nature Nanotech. 7, 520524 (2012).
4. Buonanno, G. etal. J.Air Waste Manage. Assoc. 62, 103111 (2012).
5. Goldberg, E.D. Black Carbon in the Environment: Properties and
Distribution (Wiley, 1985).
6. Kaufman, Y.J. & Fraser, R.S. Science 277, 16361639 (1997).
7. National Research Council Medical and Biological Efects of
Environmental Pollutants (National Academy of Sciences, 1976).
8. Oberdrster, G., Stone, V. & Donaldson, K. Nanotoxicology
1, 225 (2007).
9. Chen, Y. etal. Environ. Sci. Technol. 39, 11441151 (2005).
10. Hower, J.C. etal. Environ. Sci. Technol. 42, 84718477 (2008).
M
odern electronic devices
manipulate information by keeping
track of the fow of electric charge.
It is also possible to make spintronic
devices that work by controlling the spin
angular momentum of electrons. Now,
writing in Nature Nanotechnology and
Nature Communications, three independent
groups
1,2,3
report that they have
demonstrated a new way of controlling
a less-familiar property of the electron:
its valley quantum number. Tese results
could help move valleytronic devices,
which were frst proposed fve years ago
4,5
, a
step closer toreality.
Electrons travel through a crystal
as waves, which are described by a
momentum (which is a continuous
variable) and a spin (which is a discrete
index). It is possible for a crystal to have
two or more crystal axes that difer in their
orientation, but are otherwise identical:
such axes can support electron waves that
are also identical apart from their direction
(or, more precisely, their momentum), so
an additional discrete index known as the
valley quantum number is needed to fully
describe these waves. Te term valley is a
reference to the fact that the diferent axes
support electrons with diferent momenta,
which appear as a valley in a plot of energy
versus momentum.
As in spintronics, there are two main
challenges facing researchers trying to
make valleytronic devices. Te frst is
restricting electrons to one quantum
number, which for valleytronics means
localizing them to one momentum valley.
Tis is also referred to as achieving valley
CONDENSED-MATTER PHYSICS
Polarized light boosts valleytronics
Electrons can be conned to individual momentum valleys in the electronic structure of molybdenum disulphide by
shining circularly polarized light onto single layers of this two-dimensional material.
Kamran Behnia
2012 Macmillan Publishers Limited. All rights reserved
NATURE NANOTECHNOLOGY | VOL 7 | AUGUST 2012 | www.nature.com/naturenanotechnology 489
news & views
polarization. Te second challenge is
to detect the resulting valley-polarized
current. Although spin can be polarized
using ferromagnetic contacts, creating
valley polarization is rather less
straightforward. Prior to the latest work,
Mansour Shayegan and co-workers at
Princeton University used uniaxial stress to
valley-polarize aluminium arsenide
6
, and
the present author and co-workers have
used a rotating magnetic feld to modulate
the contribution of diferent valleys to the
conductivity of bulk bismuth
7
. Neither
technique, however, represents a dynamic
and complete valley polarization of the
kind necessary for devices.
Xiaodong Cui and co-workers at the
University of Hong Kong, SUSTC in
Shenzhen and Oak Ridge
1
, Tony Heinz
and co-workers at Columbia University
and Case Western Reserve University
2
,
and Enge Wang, Ji Feng and co-workers at
Peking University, the Chinese Academy
of Sciences and the University of Texas at
Austin
3
, demonstrated valley polarization
in single layers of molybdenum disulphide
(MoS
2
) (ref.8). Studied in bulk form
for several decades, MoS
2
was cleaved
to produce single-layer samples for the
frst time by Heinz and co-workers in
2010
9
. Like graphene, which is a single
layer of carbon atoms, monolayer MoS
2

has a hexagonal honeycomb lattice, but
unlike graphene, its crystal structure
lacks an inversion centre (Fig.1). Tis
lack of an inversion centre means
that electrons travelling in opposite
directionsencounterdiferent energetic
environments.
When combined with the strong spin
orbit coupling and the large direct bandgap
that are found in monolayer MoS
2
two
features not found in graphene the
missing inversion centre allows complete
valley polarization to be achieved by
simply shining circularly polarized light
on the sample. Incoming photons with a
given circular polarization will only excite
electrons with a particular spin. And
because spinorbit coupling links spin and
momentum, the momentum of an electron
that has been excited is determined by its
spin. Monolayer MoS
2
has two momentum
valleys, and right-hand circularly polarized
light (which is said to have positive helicity)
results in one of these valleys being
populated, whereas lef-hand circularly
polarized light (negative helicity) results
in the other valley being populated. Te
absence of inversion symmetry is the
ultimate source of chirality in this context.
Because electrons with opposite momenta
difer in their energy spectrum, they do
not respond in the same way to incoming
polarized light.
Te three groups illuminated single
layers of MoS
2
with right- or lef-hand
circularly polarized light, and measured the
degree of valley polarization through the
helicity of the resulting photoluminescence.
Te Cui and Heinz groups also studied
bilayer MoS
2
: this material has an inversion
centre, so it should not be possible to
establish a valley polarization in it. Both
groups confrm that there is no valley
polarization in bilayer MoS
2
, which
is compelling evidence for the valley
polarization mechanism described above.
Tese experiments represent a
milestone for valleytronics, and suggest
new directions of research for work on
single layers of MoS
2
and other transition
metal dichalcogenides. Monolayer MoS
2

is an insulator with a large bandgap, but
mobile charge carriers may be introduced
by chemical doping, applying an electric
feld or shining a light on the material.
Te transport properties of such a metallic
system are expected to be very intriguing.
For example, theorists have predicted
10
that
the intimate coupling between spin and
valley degrees of freedom in these materials
should host a combination of valley and
spin Hall efects.
Kamran Behnia is in the Ecole Suprieure
de Physique et de Chimie Industrielles,
75005Paris,France.
e-mail: [email protected]
References
1. Zeng, H., Dai, J., Yao, W., Xiao, D. & Cui, X. Nature Nanotech.
7, 490493 (2012).
2. Mak, K.F., He, K., Shan, J. & Heinz, T.F. Nature Nanotech.
7, 494498 (2012).
3. Cao, T. etal. Nature Commun.
http://dx.doi.org/10.1038/ncomms1882 (2012).
4. Rycerz, A., Tworzydlo, J. & Beenakker, C.W.J. Nature Phys.
3, 172175 (2007).
5. Xiao, D., Yao, W. & Niu, Q. Phys. Rev. Lett. 99, 236809 (2007).
6. Bishop, N.C. etal. Phys. Rev. Lett. 98, 266404 (2007).
7. Zhu, Z., Collaudin, A., Fauqu, B., Kang, W. & Behnia, K. Nature
Phys. 8, 8994 (2012).
8. Wilson, J.A. & Yofe, A.D. Adv. Phys. 18, 193335 (1969).
9. Mak, K.F., Lee, C., Hone, J., Shan, J. & Heinz, T.F. Phys. Rev. Lett.
105, 136805 (2010).
10. Xiao, D., Liu, G-B., Feng, W., Xu, X. & Yao, W. Phys. Rev. Lett.
108, 196802 (2012).
Published online: 1 July 2012

a b
C Mo
S
Figure 1 | The atoms in single layers of molybdenum disulphide (MoS
2
) and graphene are arranged hexagonally, but there are important diferences between
the two materials. a, Graphene is said to have an inversion centre because any vector (short black arrow) from the centre of the hexagon (green circle) to one
of the carbon atoms can be inverted (grey dashed line) and still point to another carbon atom. b, The unit cell for MoS
2
is shown top left. MoS
2
does not have an
inversion centre because the S atoms (blue circles) do not lie in the same plane as the Mo atoms (red circles): when a vector from the centre of the hexagon to,
say, a S atom (short black arrow; top right), is inverted it will point to a vacant site. This lack of an inversion centre means that circularly polarized light can be
used to establish a valley polarization which is one of the prerequisites for making a valleytronic device in a single layer of MoS
2
.

2012 Macmillan Publishers Limited. All rights reserved

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