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Two-dimensional crystals-based heterostructures: materials with tailored properties

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2012 Phys. Scr. 2012 014006
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IOP PUBLISHING

PHYSICA SCRIPTA

Phys. Scr. T146 (2012) 014006 (6pp)

doi:10.1088/0031-8949/2012/T146/014006

Two-dimensional crystals-based
heterostructures: materials with
tailored properties
K S Novoselov1 and A H Castro Neto2,3
1

School of Physics and Astronomy, University of Manchester, Oxford Road, Manchester M13 9PL, UK
Graphene Research Centre, National University of Singapore, 2 Science Drive 3, Singapore 117542,
Singapore
3
Department of Physics Boston University 590 Commonwealth Avenue Boston, MA 02215, USA
2

E-mail: [email protected]

Received 3 May 2011

Accepted for publication 8 June 2011
Published 31 January 2012
Online at stacks.iop.org/PhysScr/T146/014006
Abstract
Graphene is just one example of a large class of two-dimensional crystals. These crystals can
either be extracted from layered three-dimensional materials or grown artificially by several
different methods. Furthermore, they present physical properties that are unique because of the
low dimensionality and their special crystal structure. They have potential for semiconducting
behavior, magnetism, superconductivity, and even more complex many-body phenomena.
Two-dimensional crystals can also be assembled in three-dimensional heterostructures that do
not exist in nature and have tailored properties, opening an entirely new chapter in condensed
matter research.
PACS numbers: 81.05.ue, 73.22.Pr, 72.80.Vp, 61.48.Gh
(Some figures may appear in colour only in the online journal)

of three strategies: creation of various 2D materials by

micro-mechanical exfoliation and/or growth; modification of
electronic, structural, optical and chemical properties of such
materials by strain engineering, chemical functionalization
or other means; and development of novel 3D materials by
controlled multi-stacking of such 2D platforms. The number
of different structures that one can obtain based on these
strategies is practically unlimited and their physical properties
are hard to predict a priori. Nevertheless, by understanding
the properties of the 2D components, one should be able to
create materials that have interesting structural, electronic,
optical, mechanical and other properties.
Moreover, these strategies also open doors for a
multitude of applications, since it becomes possible to create
artificial materials which would combine several unique
properties that will allow their use in novel multi-tasking
(mechanical, optical and electronic) applications, as, for
instance, smart composites and coatings for flexible
electronic and photovoltaics or photonic devices for integrated
optoelectronic circuits. One can identify already several
key areas where this kind of approach can have a strong

1. Introduction
Technological progress is determined, to a great extent, by
the developments in materials science. The most surprising
breakthroughs are attained when a new type of material,
with unusual dimensionality and complexity, is created. Some
of the most famous examples are the conducting polymers,
heavy-fermion magnets, high temperature superconducting
cuprates, carbon nanotubes, graphene, topological insulators,
iron superconductors, just to name a few. One of the
ultimate goals of modern materials science is to develop
novel complex architectures and structures with tailored and
emergent properties. These properties are not necessarily easy
to predict due to the structural and electronic complexity
involved. Hence, beyond new technologies, new materials
create new challenges in condensed matter research.
The current progress in two-dimensional (2D) crystal
isolation [1] and growth [2] can lead to a new paradigm
of complex materials on demand by first identifying and
constructing the key building blocks and then combining
them into complex architectures. This approach consists
0031-8949/12/014006+06$33.00

2012 The Royal Swedish Academy of Sciences

Printed in the UK

Phys. Scr. T146 (2012) 014006

K S Novoselov and A H Castro Neto

Figure 2. Transfer of chemical vapor deposition (CVD) grown 2D

crystals. (a), (b) 2D crystals are grown by CVD on a surface of a
metal. (c) A sacrificial layer is deposited on top of the 2D crystal.
(d) The metal is etched away, leaving 2D crystal stuck on the
sacrificial layer. (e) The sacrificial layer, together with the 2D
crystal is transferred onto the substrate of choice. (f) The sacrificial
layer is removed.

Figure 1. Micromechanical exfoliation of 2D crystals. (a) Adhesive

tape is pressed against a 2D crystal so that the top few layers are
attached to the tape (b). (c) The tape with crystals of layered
material is pressed against a surface of choice. (d) Upon peeling off,
the bottom layer is left on the substrate.

conducting electrodes [9] to high speed electronics [10]. The

major reason why it took only five years for the transition
from the laboratory bench-top to industrial production is
because graphene offers really unique properties of which
the most striking is the 2D nature [11]. Many applications,
already in place, have been waiting for a material like
this for years. Hence, when graphene became available, a
whole community of scientists and technologists reacted
immediately. There have been significant efforts to improve
the existing processes and procedures and develop novel
methods of graphene production, as well as investigate other
2D materials which might be similarly successful in the
future. One emerging example is boron-nitride (BN), which
is sometimes called insulating graphite and it might be
in use everywhere where graphenes high conductivity is
a disadvantage (ultra-thin, high quality, insulating layers
for nano-electronics, non-conductive, ultra-strong, composite
materials). However, there is a huge class of 2D materials,
including exotic types such as MoS2 , NbSe2 , Bi2 Te3 , that
can be either isolated by micro-mechanical or chemical
exfoliation or epitaxial growth (figure 3).
The capability of growing different families of 2D
crystals artificially will enhance tremendously the library
of materials that one can obtain and will also allow the
exploration of the unusual physics that occurs in 2D. Unlike
the case of 1D materials, such as conducting polymers
(such as polyacetylene) and carbon nanotubes, where phase
space strongly constraints electronelectron interactions,
and ordinary 3D solids, where interactions are essentially
suppressed, 2D crystals are characterized by strong quantum
fluctuations and an enhanced phase space for interactions,
making the physics in this dimensionality very special.

impact: (i) smart ultra-strong nano-composite materials;

(ii) electro-mechanical devices for ultra-fast electronics;
(iii) materials with predetermined band-gap and work
functions for next generation photovoltaic (solar-cells)
applications; (iv) atomically thin film transistors for photonic
applications.
The real advantage of this approach is that one is
able to create materials that can perform several functions
(mechanical, electronic, and optical) simultaneously. Such
materials (let alone devices based on them) are not available
yet. However, as the functionality of modern portable
electronic equipment grows exponentially, we already see
a huge demand for such multi-functional, multi-task,
materials.

2. 2D crystals
Since graphene was isolated for the first time [3] several
ways of synthesizing this material have been introduced. This
includes mechanical exfoliation (see figure 1) [1, 3] epitaxial
growing on the surface of silicon carbide [4], epitaxial
growth on metal surfaces [5], chemical exfoliation [6], etc.
Depending on the particular application, one or another
method can/should be used. There are also a number of ways
to modify the properties of graphene obtained by various
methods. The most common ones are the introduction of
mechanical strain (of various configurations) and chemical
modification. The latter also leads to the production of other
2D materials. Simply using graphene as a scaffolding, one can
attach various chemical species to it and end up with a new 2D
atomic crystal.
In general, all the methods of graphene production known
to us could be also applied to the production of other
2D crystals. Thus, mechanical exfoliation of other layered
materials has already been demonstrated [1] as well as
epitaxial growth on the surface of a metal [7] or chemical
exfoliation [8] (figure 2). This gives us huge opportunities
in terms of a variety of different properties covered by those
materials.
It seems clear that graphene is going to play an important
role in a series of technological applications, from transparent

3. 2D-based, 3D materials
Composite materials are omnipresent in technology and many
existing applications rely on light, conductive (or insulating),
and strong composites. The performance of such materials is,
however, fundamentally limited by the interaction between the
filler and the matrix. Hence, out of a great number of possible
combinations, only a few really work. Moreover, having a
2

Phys. Scr. T146 (2012) 014006

K S Novoselov and A H Castro Neto

Figure 4. Hypothetical example of a 2D-crystals based

heterostructure.

graphene surface, for instance, it was shown that hydrophobic

graphene can be turned hydrophilic by hydrogenation [13]),
but also adding additional functionalities, such as the ability
to monitor stress distributions, the control of optical gaps, and
electrical conductivity. One can apply a similar strategy to
other 2D materials to produce high-performance composites
with a wide range of functionalities and physical behavior
(figure 4).
Micro-mechanical cleavage and artificial growth can be
used to obtain other 2D materials (graphene, BN, MoS2 ,
Bi2 Te3 , etc) to be used as fillers in composite materials.
Using materials other than graphene allows one to expand
the complexity of such composites. One can make them
optically active in various parts of the optical spectra
by using chemically modified graphene or materials with
various band-gaps. By creating semiconductormetal and/or
semiconductingsemimetal interfaces, either in the form of
dispersed heterojunctions or layered junctions, efficient light
collection and charge transfer across the interface can be
achievedgiving rise to the photovoltaic effect. Previous
work has explored, for instance, electrostatically stacked
TiO2 -graphene layers [14], where functional segregation
of exciton generation and charge transport can be separated.
It has also been shown that graphenes Raman spectrum
is extremely sensitive to applied strain and that strain transfer
between the matrix and graphene is very efficient [15].
This property can be used to create composite materials
where accumulated stress could be monitored by contactless,
non-invasive, optical methods. Such techniques can be of
crucial importance in certain areas of engineering where
catastrophic material failure is a major issue and where

Figure 3. Exfoliating other 2D crystals: BN (top panel), MoS2

(middle panel) and NbSe2 (bottom panel).

complex structure, such materials are subject to unpredictable

failure. It has been recently demonstrated that graphene can
improve mechanical, chemical and electrical properties of
composite materials dramatically. Graphene is the strongest
material known to us [12], but also it is truly 2D (so it
cannot be cleaved further and has the ultimate aspect ratio).
Moreover, one can produce graphene of suitable dimensions
and in large quantities very cheaply. Thus, one can improve
the quality of such composite materials by fine-tuning the
interaction with the matrix (via controlled chemistry on
3

Phys. Scr. T146 (2012) 014006

K S Novoselov and A H Castro Neto

with different properties, into a 3D matrix, one is able to

modify the final electronic properties.
A completely new field of exploration is the study of
multi-stacked materials under strain. Given that the elastic
properties of the 2D layers can be rather different because
of the atomic bonding (say, graphene in comparison to
BN), the final elastic properties of the 3D super-structure
can be engineered as well. The electronic properties of
such engineered 3D structures will also be affected by
strain leading to new possibilities in terms of electronic
functionalities. Even in the simplest case of stackingbilayer
graphenethe electronic structure depends crucially on the
stacking order. A small uniaxial strain or a minute shift
between the layers would immediately lead to strong changes
in the electronic structure.
By arranging different 2D materials into stacks it should
be possible to achieve new, composite, materials with novel
electronic, mechanical and optical properties. The typical
mechanisms for the modification of the electronic bands in
such stacks are based on changing the symmetry of the
structure and opening gaps in the electronic spectrum.

Figure 5. Introducing local strain in graphene by an atomic force

microscopy cantilever.

permanent monitoring of the performance of a material is

crucial (such as avionics, electrical grids, medicine, etc).

4. Strain engineering or straintronics

5. Optically active materials

One of the pillars of solid state physics is that the band

structure of 3D materials is set by their geometry and
chemistry. Although this concept is the force behind modern
electronics and technology, it also has its limitations: it
is very difficult to modify and manipulate (to create a
new functionality one has to create a new crystal); the
structure might not be stable (for instance, one can have
electron migration) or can be strongly modified by external,
environmental, conditions (such as radiation damage); the
same chemistry that is used to achieve the desired electronic
structure (for instance, by doping) might cause detrimental
effects on other parameters (such as the decrease of the
mobility due to scattering by dopants). In contrast, 2D
materials open a new avenue for control of electronic
properties. It has been demonstrated that the electronic
structure of 2D materials can be considerably modified by
strain, shear and bending [16]. Moreover, one gets much better
control of those parameters in 2D as compared to 3D systems
(for instance, graphene can be stretched up to 20% without
structural failure) (figure 5).
Uniaxial and biaxial strain, applied along different
crystallographic directions, can reversibly tune graphene from
metallic to insulating [17, 18] or significantly change the
band structure. Furthermore, usually the two valleys are
affected differently by strain, which gives us a mechanism
to differentiate between the valleys and effectively leads to
valleytronics. Just as spin can be used for spintronics where
the electron spin is manipulated by external magnetic fields,
valleytronics uses the orbital degree of freedom (the valley
index) as a new quantum number that can be manipulated
externally. Band structure is also strongly influenced by
stacking. A well-known example is graphite, depending
on the stacking order (Bernal versus rhombohedral versus
hexagonal versus turbostratic) its electronic properties can be
rather different [19]. Furthermore, intercalation of layers of
different atoms can completely change the electronic states.
For instance, graphite intercalated with alkali metals becomes
superconducting [20]. By introducing different 2D materials,

It has been demonstrated that, due to the long mean-free

path and high Fermi velocity, graphene can serve as an
excellent light-to-current converter with quantum efficiency
reaching close to 100% [21]. Its use for solar-cell applications
is however limited, due to the low absorption of graphene
(hence, the total efficiency is low) and difficulties with
creation of pn junctions (necessary for electronholes
separation) in 2D materials. Nevertheless, the efficiency of
these devices can be greatly enhanced by exploring different
geometries, for instance the vertical geometry, where the
electronhole pair is separated between two neighboring
layers (figure 6).
The strategy would be to separate electron and hole pairs
into the neighboring layers of multi-layer structures. This can
be achieved either by applying an external electric field or by
selective doping of the two layers (one n-type, another p-type).
Selective doping can be implemented either during growth by
substitutional doping or by doping with adatoms. It has been
shown that strain generates scalar potential [22], which leads
to the formation of local pn junctions. It is possible to use
this concept to create an array of pn junctions. One can use
stacks of various 2D crystals (either the same materials with
different doping or completely different materials) to form
multi-layers. One can also use layers of insulating material
(such as BN) to separate the conductive layers for more
efficient electronhole separation (to create weak tunneling
barriers).
It has been demonstrated that graphene absorbs only
2.3% of light in the wide range of visible spectra [23].
This number is even lower for chemically modified
graphene and for some other 2D materials. Combined
with the excellent conductivity properties, these materials
are extremely promising for transparent conductive coating
applications. One can use local chemical modification
to define conductive and non-conductive areas to create
atomically thin film transistors.
4

Phys. Scr. T146 (2012) 014006

K S Novoselov and A H Castro Neto

of these 2D crystals can have different physical properties we

can imagine creating a library of 2D crystals and using those
to make new 3D artificial structures with unique properties.
The outcome of such a scheme would be a large portfolio
of new materials with different functionalities. In this way,
we could develop a materials-on-demand strategy for novel
complex architectures and structures with precisely tailored
properties for emerging technological applications.
The most important lesson from the graphene story is
probably this one: there is a universe of 2D crystals out there
just waiting to be studied. Each one of them has its own beauty
and purpose. Paraphrasing Isaac Newton we can say that we
are still in the infancy of a broad field and diverting ourselves
with graphene, a material that looks more interesting than
ordinary, whilst a great field of 2D crystals lays undiscovered
before us.

References
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Morozov S V and Geim A K 2005 Two dimensional atomic
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Dubonos S V, Grigorieva I V and Firsov A A 2004 Electric
field effect in atomically thin carbon films Science
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Figure 6. Optically active material. Two graphene layers are

separated by several layers of BN, which serve as a tunneling
barrier. One of the graphene layers is in close proximity to a layer
of NbSe2 , and gets doped due to the difference between the
work-functions of NbSe2 and graphene. Such doping creates a
built-in electric field between the two graphene layers. Such a field
separates an electronhole pair which is created by an incoming
photon, resulting in photocurrent.

Another large application for 2D materials is coating.

The high quality of 2D crystals one can obtain make them
perfect gas barriers. Even a single layer of graphene is
impermeable for most gases [24]. Furthermore, such a coating
can be created by CVD growth directly on an arbitrary shaped
surfaceacting as a protective barrier. Another promising
application in coating technology is in transparent conductive
films. Two types of approaches can be used to create
transparent conductive coating: chemical exfoliation and
epitaxial growth of graphene and other conductive materials.
Uniaxial strain breaks the symmetry of the lattice and
produces rotation of the planes of polarization. This effect is
enhanced in an applied magnetic field. Application of strain
allows the production of tunable polarizers in a broad band
of optical frequencies. One can use chemical modification
to define conductive and non-conductive areas for atomically
thin film transistors.

6. Conclusions
We have learned in the last few years that 2D crystals
can be obtained by several methods such as exfoliation,
molecular bean epitaxy and chemical vapor deposition. We
also know that the physical and chemical properties of these
2D crystals can be modified by chemical or molecular doping,
by application of strain, shear or pressure, and by intercalation
with different types of atoms and molecules. We can now
create a new class of 2D artificial materials that do not exist in
nature and whose properties we can control and explore.
It is not hard to imagine that we can take all these 2D
crystals and pile them into 3D structures. Given that each one
5

Phys. Scr. T146 (2012) 014006

K S Novoselov and A H Castro Neto

[18] Levy N, Burke S A, Meaker K L, Panlasigui M, Zettl A,

Guinea F, Castro Neto A H and Crommie M F 2010
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