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News Feature: Beyond graphene

Fueled by the surge of interest in graphene, scientists are racing to
understand other exotic 2D materials; the payoff would be some
impressive applications.
Stephen Ornes
are more like a buckled honeycomb. And
Science Writer
researchers have identified more than 40 tran-
sition metal dichalcogenides, such as molyb-
denum disulphide, that form monolayers.
These are the halcyon days of research on database. Although graphene transistors are Right now, its anyones game, as researchers
graphene, a much heralded superstrong still in the experimental stage, the material is seek to push the field in new directions that
material. Since atom-thin sheets of carbon already starting to appear in commercial elicit the kind of excitement that greeted
were first isolated in 2004, thousands of applications, from strengthening carbon com- graphene.
researchers have leapt at the chance to get posite materials to enhancing touchscreens
to know this exotic material better and figure in smartphones. Signs of Weakness
out what to do with it. Not only is graphene This quest to expand the library of 2D ma-
But graphenes potential has also inspired a
robust and relatively easy to prepare in the scramble for the next breakthrough. Re- terials is partly motivated by graphenes
laboratory, it also boasts an astonishing searchers are searching for other materialsAchilles heel. It lacks a natural bandgap
portfolio of useful properties. Electrons can that can form atomic sheets with extraordi-the energy hurdle in semiconductors that
zip through graphene many times faster than electrons must overcome before they can
nary properties, and the catalog grows every
they do through silicon. Graphene is stronger flow as a currentwhich means that it can-
year. Boron nitride, for example, forms a flat
than steel, and can absorb light at any not switch between conducting and non-
hexagonal pattern of atoms very close to gra-
wavelength. Last year, researchers published phenes honeycomb structure. Silicon and conducting states. This is an essential quality
nearly 18,000 papers on graphene, according germanium atoms can be assembled into for the transistors at the heart of every elec-
to the Thomson Reuters Web of Science similar sheetssilicene and germanenethat tronic gadget, and the main reason why
graphene will probably need some help in
many applications.
Many researchers hope that by combining
different 2D materials in stackslike a well-
filled club sandwichthey will be able to
fine-tune the materials properties, making
them useful in transistors, sensors, and a
wide range of other electronics applications.
That in turn could usher in a new age of faster,
cheaper, and more ubiquitous electronics.
We dream of the day when you go to
Starbucks and you get a cup of coffee, and
there are electronics in the coffee mug, says
Tomas Palacios, who leads the Massachusetts
Institute of TechnologyMicrosystems Tech-
nology Laboratories Center for Graphene
Devices and 2D Systems in Cambridge,
Massachusetts. Such electronics might track
temperature, the fill level, or even coffee shop
rewards points. As you drink your coffee, you
look outside your office, Palacios imagines,
through a window outfitted with invisible
electronics that moderate the amount of
incoming sunlight.
But many hurdles remain that could keep
these materials from reaching their potential,
Following on the success of graphene, various 2D materials are vying to be the next break- cautions Jari Kinaret, director of the Graphene
through. But substantial technical challenges remain. Image courtesy of Shutterstock/Shilova Flagship, the European Unions billion-Euro
Ekaterina. research effort that aims to shepherd 2D

1312813130 | PNAS | October 27, 2015 | vol. 112 | no. 43

stick to the underlying substrate, making it
difficult to transfer into a device. Indeed, re-
searchers at Argonne National Laboratory in
Illinois last year questioned previous silicene
research, claiming that the material being
studied was actually a combination of silicene
and its silver substrate, in which case the
experiments revealed little about the behavior
of isolated silicene.
Researchers are already finding ways to
deal with these problems. In February 2015,
for example, Akinwande and Alessandro
Molle at the Institute for Microelectronics
and Microsystems in Agrate Brianza, Italy,
unveiled the first silicene transistor (6). They
relied on techniques that effectively circum-
This rendering shows the electrodes (yellow) at either end of a silicene channel (in blue). The vented silicenes tendency to fall apart.
silicene was grown on a mica substrate (in gray) and capped with alumina to prevent After creating their silicene layer on silver,
degradation. Reproduced from ref. 6, with permission from Macmillan Publishers Ltd, the researchers protected it with a thin coat-
Nature Nanotechnology. ing of alumina. This process allowed them to
move the silicene sheet, still sandwiched be-
tween silver and alumina, to an insulating
materials from the laboratory into com- physicists led by Novoselov showed that silicon substrate. Then they etched away
mercial applications. Many of the materials monolayers of these two materials could be some of the silver to create a transistor that
beyond graphene are much trickier to deal sandwiched between layers of graphene to worked for a couple of minutes. We have
with than graphene, he says. create a light-emitting diode (3). In the de- hope because weve seen the first silicene
Kinaret notes that most of the work done vice, an applied voltage across the graphene
transistor, says Le Lay, who is applying the
on atomic sheets, other than graphene, has layers frees electrons to leave behind posi-
method in his own laboratory. Akinwande
been conducted on the scale of a laboratory. tively charged holes. The electrons and
and Le Lay are collaborating to try the same
Scaling up production methods to be able to holes tunnel through the hexagonal boron
trick with germanene, which Le Lays team
make enough to use in electronic devices nitride and combine in the transition metal
first isolated last year (7).
could be an insurmountable challenge. He dichalcogenide, emitting red light. In labo-
In August, a group led by physicists from
also cautions that because many of these ratory experiments, the LED monolayer
Chinas Shanghai Jiao Tong University re-
materials are unstableespecially the ones sandwich was almost as energy-efficient as
ported the first successful growth of stanene,
made from transition metalsthey quickly conventional LEDs. Unlike conventional
LEDs, however, those built from 2D di- a single layer of tin atoms (8). Stanene is
bond to the surface on which theyre grown
predicted to have a large bandgap, like other
and become difficult to separate. You may mensional materials are transparent and flex-
ible, and other researchers suggest they may materials, and may let electrons flow without
say that youre studying some material, but
emit electromagnetic waves in the wave- resistance, but the paper on the materials
actually you dont have good tools to mea-
length ranges used by telecommunications first synthesis did not confirm those be-
sure it, so you dont have a perfect grasp of
devices. Molybdenum disulphides bandgap haviors. Researchers at the Stanford Linear
what the material is, he says.
also makes it useful for molecular-scale mea- Accelerator Center National Accelerator
A Growing Family surements, including as a gas sensor (4). Laboratory in Menlo Park, California, sug-
The rush to understand atomic sheets began Other researchers think that silicene might gest the material could be used to make
in 2004 (1), when physicists Andre Geim and prove to be a better fit for the microelec- topological insulators, which allow electrons
Konstantin Novoselov at the University of tronics industry. Not only has silicon been to travel freely on their surface but not in the
Manchester, United Kingdom, announced the mainstay of computer chips for more interior (9). Right now, topological insulators
that they had isolated graphene by using an than 50 years, but also silicene itself can be are still more interesting from a pure science
astonishingly low-tech method. The physi- made with a suitable bandgap, and its elec- standpoint because they can shed light on
cists used sticky cellophane tape to peel away trons may also flow at high speeds. Several quantum electronic behaviors, but proposed
superthin layers of carbon from a graphite research groups isolated silicene in 2012, in- applications for these materials range from
pencil, and kept on peeling at the flakes until cluding physicist Guy Le Lay at the Aix- quantum computing to new ways to store
they were left with an atomic monolayer. The Marseille University in France (5), whose information.
following year, the two showed that by sim- team created the material by condensing hot And in November 2014, a team of re-
ply rubbing the surface of various crystalline silicon atoms onto a silver crystal in a vac- searchers in China, led by Xian Hui Chen
compounds they could scratch off monolayer uum chamber. and Yuanbo Zhang at Fudan University,
flakes of boron nitride, molybdenum disul- But silicene is tricky to work with. Once created a transistor using black phosopherene,
phide, and several other materials (2). you remove it from the vacuum chamber, it a few-layers-thick sheet of phosophorous
The physicists found that molybdenum degrades in a matter of minutes, says nano- atoms arranged in a puckered honeycomb
disulphide monolayers have a sizeable materials researcher Deji Akinwande at the shape (10). Akinwandes group is also working
bandgap, and hexagonal boron nitride is University of Texas, Austin. Like Kinaret, on protecting black phosphorene by coating
an insulator. In February 2015, a team of Akinwande cautions that silicene tends to it with Teflon (11).

Ornes PNAS | October 27, 2015 | vol. 112 | no. 43 | 13129

This catalog of atomic sheets is still glass and paper. He imagines a wired world, about 15 years to get to high-end products.
growing quickly. These materials have such where every object is connected to the Inter- Plastics, first developed in the mid-19th cen-
large potential, and it is clear that something net. In this Internet of Things everyday ob- tury, didnt become mainstream until the
very interesting is coming out, says Kinaret. jects would have the ability to communicate 1930s and 1940s.
But Kinaret cautions that it is difficult to with everything else. Imbued with machine For now, graphene remains the front-
pinpoint which materials or combinations intelligence, countless devices and even entire runner of all of the atomic sheets, thanks to
will lead to marketable devices. buildings could become more energy-efficient, its robust research history and its tendency to
The literature is already rife with proposed remain stable at room temperature. And it
applications that extend into almost every The new physics of these keeps delivering surprises: in February 2015,
field related to energy, heat, or electricity. materials can lead us researchers showed how graphene nano-
Some researchers propose that 2D materials ribbons can be fashioned to let electrons move
could bolster the efficiency of solar cells beyond Moores Law. more efficiently than previous studies have
when used as photosensitizers or charge Deji Akinwande predicted (14). In June, physicists in the
transporters. As good heat conductors,
and precisely tuned to the tastes and prefer- United States and South Korea reported the
atomic sheets might make efficient thermo- worlds thinnest light bulb, using light-emit-
ences of users. We want ubiquitous elec-
electric devices. And because they can quickly ting graphene as an ultrathin filament (15).
tronics, says Palacios.
shuttle charge, they might show up in high- And in September, an international team of
Such a future requires high-performing
performance batteries and conductors. Some researchers reported that, at low temperatures,
materials with low energy demands. Future
researchers have proposed novel ways to use the material becomes a superconductor when
devices must be smaller, faster, and cheaper
these materials to sequence DNA (12) or coated with lithium (16).
than anything around today. Theyll also need
detect genetic translocations (13). And although most people want to know
to be durable, flexible, maybe rollable, envi-
But it is in microelectronics where 2D how 2D materials can be used to make better
ronmentally friendly, and recyclable. Such a
materials could eventually have the biggest gizmos, physicists are increasingly interested
vision seems a far cry from the rigid tablets
impact, by offering an alternative to the in how these atomic sheets can be used to
and smart phones that dominate the market.
ubiquitous silicon chip. uncover new physics. Paring a material down
Right now, though, high-volume and cost-
Ubiquitous Electronics effective manufacturing of stable forms of to such thinness gives rise to bizarre quan-
In 1965, when integrated circuits had been these materials remains a daunting challenge. tum electronic properties. For example, 2D
around only a few years, semiconductor re- Processes that make atomic sheets on a large materials are believed to be able to shuttle
searcher Gordon Moore made a simple but scale typically introduce defects into the ma- electrons so quickly because the electrons
prescient forecast about how much computer terial that can, for example, cripple their behave as though they have no mass. Re-
power could be crammed onto a single com- electronic properties; physicists do not yet searchers are also investigating 2D materials
puter chip. The number of transistors on an understand exactly how to mitigate these for their use in spintronics, a concept that
integrated circuit would double every year, he effects. One challenge is to produce a per- would see data represented by the spins of
predicted; he later amended the prediction to fectly crystalline, very large area sheet of electrons, rather than the flow of charge.
say the number would double every two years. one- or two-layer material, says Palacios. Even though graphene was the first 2D
That idea became known as Moores Law. Theres been a lot of recent work on using material to make a splash, Palacios says hes
Moore, who went on to found chipmaker chemical vapor deposition for that process, thrilled that it wont be the only player in the
Intel, later admitted that he expected the but scaling is still a big issue. field. Graphene was first, but it doesnt have
trend to continue for only a decade. Instead, Still, graphenes rapid rise offers hope for to be the most successful. Two-dimensional
it has held true for five decades thus far. its flat cousins. Kinaret notes that graphenes materials are no longer about graphene,
Now it faces huge challenges. As chips grow trajectory from isolation to market has been theyre about a completely new family of
smaller, the transistors are packed so closely unusually quick. For comparison, he says, materials with truly unique properties, he
together they risk overheating, and smaller carbon fibers developed in the 1960s took says. We have a wide variety to play with.
transistors are increasingly expensive to man-
ufacture. Experts say that it is simply not
tenable to make ever-smaller silicon chips. 1 Novoselov KS, et al. (2004) Electric field effect in atomically thin 9 Xu Y, et al. (2013) Large-gap quantum spin Hall insulators in tin
That is where 2D materials might save the carbon films. Science 306(5696):666669. films. Phys Rev Lett 111(13):136804.
day. The new physics of these materials can 2 Novoselov KS, et al. (2005) Two-dimensional atomic crystals. Proc 10 Li L, et al. (2014) Black phosphorus field-effect transistors. Nat
Natl Acad Sci USA 102(30):1045110453. Nanotechnol 9(5):372377.
lead us beyond Moores Law, says Akin- 11 Kim J-S, et al. (2015) Toward air-stable multilayer phosphorene
3 Withers F, et al. (2015) Light-emitting diodes by band-structure
wande. More transistors lead to more pro- engineering in van der Waals heterostructures. Nat Mater 14(3):301306.
thin-films and transistors. Sci Rep 5:8989.
12 Farimani AB, Min K, Aluru NR (2014) DNA base detection using a
cessing power, and transistors made from 2D 4 Cho B, et al. (2015) Charge-transfer-based gas sensing using
single-layer MoS2. ACS Nano 8(8):79147922.
materialseven if they are stackedwill take atomic-layer MoS2. Sci Rep 5:8052.
13 Schneider GF, et al. (2010) DNA translocation through graphene
5 Vogt P, et al. (2012) Silicene: Compelling experimental evidence for
up less space and require less energy than graphenelike two-dimensional silicon. Phys Rev Lett 108(15):155501.
nanopores. Nano Lett 10(8):31633167.
14 Baringhaus J, et al. (2014) Exceptional ballistic transport in epitaxial
conventional silicon. 6 Tao L, et al. (2015) Silicene field-effect transistors operating at
graphene nanoribbons. Nature 506(7488):349354.
According to Palacios, 2D materials could room temperature. Nat Nanotechnol 10(3):227231. 15 Kim YD, et al. (2015) Bright visible light emission from graphene.
7 Dvila ME, et al. (2014) Germanene: A novel two-dimensional
help to produce electronic devices that are so Nat Nanotechnol 10(8):676681.
germanium allotrope akin to graphene and silicene. New J Phys 16:095002. 16 Ludbrook BM, et al. (2015) Evidence for superconductivity in Li-
smalland so cheapthat they are embedded 8 Zhu F, et al. (2015) Epitaxial growth of two-dimensional stanene. decorated monolayer graphene. Proc Natl Acad Sci USA 112(38):
in everything from clothing and wallpaper to Nat Mater, 10.1038/NMAT4384. 1179511799.

13130 | Ornes