Phys. Status Solidi RRL 7, No. 10, 713–726 (2013) / DOI 10.1002/pssr.

201308010

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Part of Focus Issue on
Semiconductor Nanowires
Eds.: Chennupati Jagadish, Lutz Geelhaar, Silvija Gradecak

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Advances in semiconductor nanowire Review@RRL
growth on graphene
A. Mazid Munshi and Helge Weman*

Department of Electronics and Telecommunications, Norwegian University of Science and Technology, 7491 Trondheim, Norway

Received 6 June 2013, revised 25 July 2013, accepted 26 July 2013

Published online 6 August 2013

Keywords nanowires, graphene, hybrid systems, epitaxy, flexible devices

*
Corresponding author: e-mail helge.weman@ntnu.no, Phone: +47 73 594 409, Fax: +47 73 591 441
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and
reproduction in any medium, provided the original work is properly cited.

Here we review the recent research activities on the epitaxial
growth of semiconductor nanowires (NWs) on graphene sub-
strates. Semiconductor NWs with quasi one-dimensional
structure have become an active research field due to their
various interesting physical properties and potentials for fu-
ture electronic and optoelectronic device applications, such as
transistors, sensors, solar cells, light emitting diodes, and la-
sers. At almost the same time graphene, a two-dimensional
material made of carbon, was discovered and has gained an
ever increasing interest during the last few years owing to its
remarkable properties, including excellent electrical conduc-
tivity, optical transparency, and mechanical strength and flex-
ibility. A hybrid structure by epitaxially growing semicon-
ductor NWs on graphene could provide a new avenue for the
development of future advanced NW-based flexible elec-
tronic and optoelectronic devices. We address the challenges
for the growth of semiconductor NWs on graphene, with a
special focus on the III – V semiconductors, and highlight
some potential applications of the NW/graphene hybrid sys-
tem.

1 Introduction Semiconductor nanowires (NWs)
have received great interest for their potential applications
in various future nanoscale devices [1– 5]. Promising de-
vice performances in NW-based solar cells [6 – 14], light
emitting diodes [15], lasers [16 –20] and field effect tran-
sistors [21] have already been reported by utilizing the
unique physical properties of NWs. In addition, the small
cross-sectional area of the NWs has made it possible to
overcome the challenge of epitaxial growth on lattice mis-
matched substrates [22, 23], as well as growth of axial and
radial heterostructures in a single NW [24 –29] even with
atomically abrupt heterointerfaces [30, 31]. While promis-
ing works related to the NW-based structures and device
applications are on their high, graphene, a two-dimensional
material has emerged and developed in parallel [32– 35].
Graphene, due to its intriguing material characteristics
including high electrical [35] and thermal [36, 37] conduc-
tivities, optical transparency [38], and mechanical flexibil-
ity and strength [39], is a potential material for next-
generation transparent, foldable and stretchable device
applications [40 –43]. Therefore the longtime quest for
creating a wide variety of flexible devices [44 – 47] could
be enabled through graphene. Over the past years, there
has been a tremendous improvement on the synthesis of
high quality graphene using different techniques, such as
graphene grown on Cu [48 – 51], Ni [52 – 54], and Pt [55,
56] foils by chemical vapor deposition (CVD), and high-
temperature synthesis of epitaxial graphene on SiC sub-
strates [57 –60]. Moreover, low-cost roll-to-roll [61, 62]
and large-area [57] production of graphene with clean sub-
strate transferable ability [63 –66] have recently been suc-
cessfully demonstrated. A new class of hybrid material
systems can now be developed by growing semicon-
ductor NWs directly on graphene, replacing the expensive
single-crystalline semiconductor substrates (e.g. III –V and
II – VI substrates) normally used for the epitaxial growth.
In these hybrid systems, graphene can simultaneously act
as a flexible, transparent electrode [67] and can produce
various unconventional electronic and optoelectronic de-
vices, including sensors [68 –72], piezoelectric power
sources [73–75], flexible displays [76–78] and solar cells
[79– 81].

© 2013 The Authors. Phys. Status Solidi RRL published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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714 A. M. Munshi and H. Weman: Advances in semiconductor nanowire growth on graphene

In this review, we discuss the challenges for the epitax- been extensively studied in recent years. The understand-
ial growth of various semiconductor NWs on graphene ing of the NW growth mechanisms and the systematic tun-
substrates. Recent research activities on the growth of ing of the growth parameters have enabled the growth of
group II – VI, IV and III –V NWs on graphene, their char- NWs with precise control of their crystal structure [106,
acterization and device applications will be presented. 112 –121], position [122– 125], axial and radial het-
Recent reviews on the growth of inorganic nanostructures erostructures [27, 31, 126], as well as formation of quan-
based on other material systems on graphene can be found tum dots (QDs) within the NW [127 –130]. All these ad-
in Refs. [82, 83]. vanced epitaxial synthesis techniques can potentially be
also adapted for NWs grown on graphene substrates.
2 Semiconductor NWs on graphene layers Het- Graphene is a single-layer of carbon atoms bonded
eroepitaxial growth of semiconductor NWs on various with sp2-hybridization and arranged in a regular hexagonal
semiconductor substrates has become an interesting re- honeycomb lattice structure [131, 132]. Due to the absence
search topic for monolithic integration of two or more sem- of dangling bonds, the graphene surface is chemically inert
iconductors with diverse or complementary properties. to any foreign atoms making it challenging to grow three-
In most of the cases, the Au-assisted vapor–liquid–solid dimensional semiconductor materials on its surface by
(VLS) mechanism has been utilized for the epitaxial conventional epitaxy. One possible method to circumvent
growth of the NWs using various techniques including this problem is to use van der Waals epitaxy (vdWE) [133].
metal-organic vapor phase epitaxy (MOVPE) [84-89], Due to the different bonding mechanism in vdWE compa-
chemical vapor deposition (CVD) [90, 91], molecular red to conventional epitaxy with strong chemical bonding,
beam epitaxy (MBE) [92 –94], chemical beam epitaxy the grown materials need not to be necessarily lattice mat-
(CBE) [95, 96], laser ablation [97– 99] and so on. However, ched with the graphitic substrate and no strain induced in-
partly due to the concern of Au incorporation in the grown terfacial defects are to be expected. Due to the increasing
material, other alternatives such as self-catalyzed [100 – interest of using graphene as a substrate material for epitax-
106] and catalyst-free [107 – 111] growth techniques have ial growth, recent density functional calculations have
been employed to investigate the adsorption sites and ad-
Abdul Mazid Munshi received his M.Sc. sorption energies of different atoms and molecules on the
degree in Physics in 2007 and M.Tech. graphene surface [134, 135]. These theoretical calculations
degree in Solid State Materials in 2009, predict the plausibility of also conventional epitaxy i.e.
both from Indian Institute of Technology non-vdWE (based on a covalent or ionic binding mecha-
Delhi, India. He is currently working to- nism) for growing different materials on graphitic surfaces.
wards his Ph.D. degree in Prof. Helge Based on this, in the following, we discuss different atomic
Weman’s group at Norwegian University arrangements of the semiconductor atoms on graphene for
of Science and Technology, Norway.
a successful non-vdWE growth to take place.
Some of his areas of research interests include semiconductor
The possible adsorption sites for the semiconductor at-
nanostructures, graphene, epitaxial growth, structural and op-
tical characterizations, and photovoltaics. oms on graphene can be identified as 1) above the center of
the hexagonal carbon rings (H-site), 2) above the bridge
Helge Weman is a full professor in nano- between the carbon atoms (B-site), and 3) above the top of
electronics in the Department of Electron- a carbon atom (T-site) as indicated in the inset of Fig. 1(a).
ics and Telecommunications at the Nor- Already from the pioneering work done by Hiruma et al., it
wegian University of Science and Tech- is known that semiconductor NWs mostly grow along the
nology (NTNU) in Trondheim, Norway. [111] direction in the case of a cubic semiconductor and
He received his Ph.D. in Semiconductor along the [0001] direction in the case of a hexagonal one
Physics in 1988 from Linköping Univer- [85, 136]. Therefore, in the (111) plane of the cubic semi-
sity, Sweden. During his career he has conductor (and (0001) for the hexagonal semiconductor),
since then held various positions at UCSB the atoms have a hexagonal symmetry as the carbon atoms
(USA), NTT Optoelectronics Lab (Japan), EPFL (Switzer-
in graphene. In a recent work by Munshi et al., it was
land), and IBM Res. Lab (Switzerland). Since 2005, Weman is
leading a research group at NTNU on III – V semiconductor shown that depending on the preferential adsorption sites
nanowires and graphene for use in solar cells and various and the type of semiconductor atoms, different lattice
photonic applications. During 2010 – 2013 he is the director of mismatch of the semiconductor with graphene will result
a Nordic consortium (NANORDSUN) on nanowire based so- in different atomic arrangements [137]. Figure 1(a)– (d) il-
lar cells. Weman has authored more than 100 refereed journal lustrate such arrangements when the atoms are adsorbed on
papers, some 200+ conference papers and is the inventor of six both H- and B-sites (Fig. 1(a), (b), (d)), and on either H-
patent applications. Since 2010 he is a member of the Norwe- or B-sites (Fig. 1(c)). The adsorption energies for most of
gian Academy of Technological Sciences (NTVA). In June the semiconductor atoms are lower on the T-sites and
2012 he co-founded the company CrayoNano AS, where he is hence excluded from the discussion here [135]. The lattice
currently the Chief Technology Officer and member of the constants, calculated for the four different atomic arrange-
Board. ments in Fig. 1(a) –(d), are plotted together with the band-

© 2013 The Authors. Phys. Status Solidi RRL published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pss-rapid.com

Phys. Status Solidi RRL 7, No. 10 (2013)
Figure 1 (a – d) Relative orientation and arrangement when semi-
conductor atoms are adsorbed on (a, b, d) H- and B-sites, and
(c) H- or B-sites. (e) Generic model describing the semiconductor
bandgaps vs. lattice constants together with lattice constants for
the lattice-matched atom arrangements on graphene shown in
(a) (black vertical line), (b) (green vertical lines), (c) (blue verti-
cal line) and (d) (red vertical line). Dashed and solid lines corre-
spond to the hexagonal (ahex) and cubic (acub = ahex × 2) crystal
phases of these lattices, respectively. The square (䊏) and the
hexagon (¥) represent the cubic and the hexagonal phases, re-
spectively. Reprinted with permission from Ref. [137], Copyright
(2012), American Chemical Society.
gap vs. lattice constant diagram for some conventional se-
miconductors in Fig. 1(e). Therefore, Fig. 1(e) represents
an overview of the lattice mismatch conditions to achieve
non-vdWE growth in the (111) ((0001)) direction for cubic
(hexagonal) semiconductors on graphene. It should be not-
ed that the maximum lattice mismatch obtained here is
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within the lattice mismatch for which successful heteroepi-
taxial growth of semiconductor NWs has been achieved
(e.g. InAs NWs on Si).
2.1 Group II–VI compound semiconductors
Among II –VI compound semiconductors, so far the epi-
taxial growth of ZnO NWs on graphene has been success-
fully demonstrated. ZnO being a wide bandgap oxide se-
miconductor is suitable for various device applications
such as light emitting diodes [138 –142], lasers [16, 143,
144], piezoelectric nanogenerators [145 –147], sensors
[148 –151] as well as solar cells [152– 154]. Therefore, a
hybrid structure between ZnO NWs and graphene would
be interesting for designing a device where both of their
unique properties can be exploited. Pioneering work has
been done by Gyu-Chul Yi’s group on the growth of ZnO
NWs on graphene [82]. They demonstrated the growth of
vertically aligned ZnO NWs on few-layer-graphene by ca-
talyst-free MOVPE using diethylzinc (DEZn) and oxygen
as reactants [155]. Before the NW growth, graphene sheets
were transferred onto SiO2/Si substrates using a mechani-
cal exfoliation technique. The NWs grew vertically ori-
ented on the graphene layers, whereas they grew tilted with
random orientation on the SiO2/Si surface as can be seen in
the scanning electron microscopy (SEM) image in Fig. 2(a).
In addition to the NWs, nanowalls were also formed at the
step edges due to the increased nucleation and crystal
growth process. The morphology and density of the NWs
were also found to be dependent on the growth temperature.
With increasing growth temperature, the nanostructures
became longer and needle-like because of the increased
surface diffusion of the adatoms, and their density reduced
due to a reduction in the nucleation rate.
Recently, the growth of ZnO NWs on graphene layers
was also successfully demonstrated using a hydrothermal
process, as depicted in Fig. 2(b) [156]. The growth of ZnO
NWs took place on the graphene covered surface, and no
growth on SiO2 surface. The hydrothermal process being a
Figure 2 (a) SEM image of ZnO NWs grown on the graphene/
SiO2/Si substrate using catalyst-free MOVPE. Reprinted with
permission from Ref. [155], Copyright (2009), American Institute
of Physics. (b) SEM image of ZnO NWs grown on the gra-
phene/SiO2/Si substrate using a hydrothermal method. Inset
shows magnified view of the NWs grown on graphene layers.
Reprinted with permission from Ref. [156], Copyright (2011), In-
stitute of Physics.
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716 A. M. Munshi and H. Weman: Advances in semiconductor nanowire growth on graphene
Figure 3 SEM images of ZnO (a) NWs, (b) NW/nanowall hybrid, and (c) nanowall structures grown by CVD. Reprinted with permis-
sion from Ref. [157], Copyright (2011), American Chemical Society.
low-temperature synthesis technique may thus be useful
for fabricating NWs on graphene deposited on plastic sub-
strates. Later, Kumar et al. used catalyst-assisted CVD to
grow ZnO NWs and nanowalls on graphene layers [157].
They showed that by controlling the Au layer thickness
(used as the catalyst) the morphology of the ZnO na-
nostructure could be changed from NWs to nanowalls,
through an intermediate stage where the NWs and nano-
walls coexist and are interconnected. Figure 3(a)– (c) de-
pict the growth of ZnO nanostructures for Au layer thick-
nesses of 0.5 nm, 1 nm, and 2 nm, respectively, showing
the formation of NWs, intermediate structures and nano-
walls. In a previous report by Ng et al., a similar depen-
dence of the Au film thickness on the morphology of ZnO
nanostructures grown on highly oriented pyrolytic graphite
(HOPG) was observed [158]. However, in none of these
reports was the nature of the epitaxy discussed. In the case
of a vdWE binding mechanism for these growths no lattice
matching conditions would be required. However, using
the atomic model described in Fig. 1, a non-vdWE with the
H- and B-site configuration depicted in Fig. 1(a) is also
possible. This atomic arrangement results in an almost
coherent lattice-matching condition (mismatch ~0.26%) for
ZnO with graphene and this could be a key reason for
achieving such high yield of vertical NWs on graphene.
2.2 Group IV semiconductors The most important
semiconductor in electronics as well as in solar cells today
is silicon. A hybrid system between Si and graphene would
open up opportunities to fabricate new types of Si-based
functional devices [159, 160]. Growth of Si NWs has re-
cently been demonstrated on graphene by metal-assisted
VLS mechanism using atmospheric pressure CVD [161].
CVD grown graphene on Cu foil was transferred onto a
SiO2 covered Si substrate using chemical exfoliation me-
thod. The Si NWs were grown on the graphene/SiO2/Si
substrate using Au as a catalyst. After growth, the
NW/graphene hybrid structure was transferred onto an ar-
bitrary substrate. However, the Si NWs were randomly
oriented with no preferred growth direction, indicating the
absence of an epitaxial relationship with the underlying
graphene layers. The lack of epitaxial relation between the
Si NWs and graphene could be attributed to the transfer
© 2013 The Authors. Phys. Status Solidi RRL published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
process. The atomic arrangement of Fig. 1(b) would result
in a lattice mismatch of Si with graphene (~3.9%) showing
that non-vdWE growth is likely to be successful for Si
NWs if the graphene substrate preparation and the Si NW
nucleation and growth conditions are properly optimized.
In fact, epitaxial growth of Si nanoislands on graphene
sheet was demonstrated by Lee at al. using a vapor trans-
port technique [162], however in this case the epitaxial na-
ture was attributed to vdWE. Interestingly, the Si nanois-
lands were found to produce a small bandgap opening in
graphene. Therefore future fundamental studies on how the
properties of graphene are modified due to the epitaxial
growth of NWs will become interesting topics for future
studies and very important in order to optimize these hy-
brids systems for various device applications.
2.3 Group III– V compound semiconductors
III– V semiconductors are very useful for various optoelec-
tronic applications including photovoltaics [163], as well
as for high-power and high-speed electronics [164]. How-
ever, the high cost of III –V semiconductor substrates and
the difficulty in achieving hetero-epitaxial growth with
high quality on cheaper substrates like Si still hinder their
full potential in applications. Alternatives, such as epitaxial
lift-off, and peel-and-stamp techniques to transfer the
grown structures from their original substrates to an ar-
bitrary target substrate have been successfully demonstra-
ted. Such techniques would not only allow reusing the ex-
pensive III –V substrates but also create the possibility for
fabricating flexible, low-cost electronic and optoelectronic
devices [165– 167]. Another alternative would be to grow
these semiconductor materials directly on a flexible and
cheap substrate such as graphene, which could then also
act as a transparent electrode [168] in optoelectronic de-
vice applications [169 –173]. Therefore, the rationale for
synthesizing III– V NWs on graphene in a controllable way
has to be studied extensively in order to use the III– V
NW/graphene hybrid systems for various functional device
applications.
GaAs being one of the most important III– V semicon-
ductors, we first discuss studies made on the growth of
GaAs NWs on graphitic substrates. Recently, the Ga self-
catalyzed VLS technique was successfully utilized to syn-
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Figure 4 (a) SEM image of GaAs NWs grown on a graphite substrate by self-catalyzed MBE at 610 °C for 10 min. (b, c) GaAs NWs
grown on graphite and epitaxial graphene synthesized on SiC, respectively, using a two-temperature growth strategy where the NWs
were nucleated at 540 °C for 10 s and the growth was continued at 610 °C for 5 min. Insets show magnified view confirming the uni-
form hexagonal cross-sectional shape of the GaAs NWs. Scale bars in the insets are 100 nm. Reprinted with permission from Ref.
[137], Copyright (2012), American Chemical Society.

thesize the GaAs NWs on different graphitic substrates us-
ing molecular beam epitaxy (MBE) [137]. In this study,
prior to the growth, a Ga pre-deposition step for 20 s was
applied to form liquid Ga droplets which facilitate the NW
growth. The NW growth was initiated by opening the As
flux. The temperature of the Ga effusion cell was pre-set to
yield a nominal planar GaAs growth rate of 2 Å/s, and the
valve position of the As cracker cell was adjusted to yield
the required fluxes. Figure 4(a) shows such GaAs NWs
grown for 10 min with an As flux 6 × 10–6 Torr at a sub-
strate temperature 610 °C. As can be seen, the NWs are
vertically aligned with the substrate and have uniform hex-
agonal cross-sectional shape, indicating that the growth is
epitaxial. Although, NWs with good morphology were ob-
tained, the average density of the NWs across the entire
sample was low. The low density of NWs was attributed to
the reduced nucleation rate at high temperature. To increa-
se the NW density, two series of growth experiments were
performed the 1st series by varying the growth temperature
and the 2nd series by varying the As flux. It was found that
the NW density was improved by using a low growth tem-
perature (540 °C) with an As flux 3 × 10–6 Torr. However,
due to the low growth temperature the diffusion length of
Ga adatoms reduced and formed two-dimensional parasitic
crystals which eventually covered the entire graphitic sur-
face for longer growth durations. Based on this observation,
a two-temperature growth strategy was adapted where the
NW nucleation process was induced at a low temperature
for a short duration (10 s) and the NW growth was contin-
ued (5 min) at higher temperature. Figure 4(b) represents a
SEM image of the GaAs NWs grown using the two-
temperature growth strategy. Figure 4(c) depicts the GaAs
NWs grown with the same condition as for Fig. 4(b) but
grown on few-layer epitaxial graphene synthesized on a
SiC substrate. Similar results were also obtained when the
growth was carried out on exfoliated graphene on SiO2/Si
substrates. The results obtained here on the GaAs NW
growth on different graphitic substrates ensure the ro-
bustness and reproducibility of the adapted method, and
confirm the epitaxial relationship of the NWs with the sub-
strates.
In a separate report by Tateno et al., the growth of dif-
ferent III– V semiconductor NWs was demonstrated on
graphitic substrates using Au-assisted MOVPE [174]. Here,
GaP NWs were grown on both graphene/SiC and HOPG
substrates, whereas GaAs and InP NWs were grown on
HOPG substrate. It was observed that in addition to the
vertically oriented NWs, tilted and surface grown NWs
were also formed. The NW growth was also performed on
Si(111) substrates for comparison. In all cases, however,
the yield of vertical NWs was found to be low, indicating a
need for further optimization of the growth conditions. Nu-
cleation at step edges was argued to be a necessary condi-
tion to produce vertically aligned NWs. Earlier, Mohseni
et al. employed Au-assisted MBE to grow GaAs NWs on
carbon nanotube composite films [175]. However, the
NWs were randomly oriented and did not grow epitaxially
from the carbon nanotube which seems to be due to that
the NW nucleation took place at parasitic GaAs crystals
and not directly on the carbon nanotubes.
Epitaxial growth of InAs NWs on graphitic substrates
has also been reported recently. Hong et al. used catalyst-
free MOVPE to grow the InAs NWs [176, 177]. They
employed two different substrate preparation methods:
1) pristine graphitic substrates and 2) O2 plasma treated
graphitic substrates. Both InAs NWs and nanoislands for-
med on both types of substrates. It was observed that the
O2 plasma treated graphitic substrates could produce a hig-
her density of NWs and a lower density of islands when
the treatment time was well optimized. At longer O2 plas-
ma treatment times the NW density reduced and the island
density increased. Figure 5(a) and (b) show such InAs
NWs grown on an O2 plasma treated graphitic substrate. It
can be seen that the NWs are vertically aligned and both
NWs and islands have the same hexagonal in-plane orien-
tation suggesting an epitaxial growth mechanism, which
was attributed to vdWE. Later, the epitaxial growth of
InAs NWs on pristine graphitic substrates was also suc-

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718 A. M. Munshi and H. Weman: Advances in semiconductor nanowire growth on graphene
Figure 5 (a, b) Tilted- and top-view SEM images of InAs NWs
grown on a graphitic substrate using catalyst-free MOVPE, re-
spectively. Reprinted with permission from Ref. [176], Copyright
(2011), American Chemical Society. (c) Tilted-view SEM image
of InAs NWs grown on a graphic substrate using catalyst-free
MBE. Reprinted with permission from Ref. [137], Copyright
(2012), American Chemical Society. (d) Tilted-view SEM image
of InGaAs NWs grown on graphene layers using catalyst-free
MOVPE. Reprinted with permission from Ref. [178], Copyright
(2013), American Chemical Society.
cessfully demonstrated by Munshi et al. using catalyst-free
MBE as depicted in Fig. 5(c) [137]. In addition to the bi-
nary III – V semiconductors, the growth of a ternary In-
GaAs NWs on graphene layers was recently demonstrated
by Mohseni et al. using catalyst-free MOVPE as shown in
Fig. 5(d) [178]. The general observation from Fig. 5 is that
Figure 6 (a) Cross-sectional TEM image of a self-catalyzed GaAs NW grown on epitaxial graphene layers synthesized on a SiC sub-
strate. Reprinted with permission from Ref. [137], Copyright (2012), American Chemical Society. (b, c) Cross-sectional TEM image
of a catalyst-free InAs NW grown on a graphite substrate. Reprinted with permission from Ref. [176], Copyright (2011), American
Chemical Society.
© 2013 The Authors. Phys. Status Solidi RRL published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
the catalyst-free InAs (and InGaAs) NWs have an asym-
metric NW cross-section and higher NW density as com-
pared to the self-catalyzed GaAs NWs in Fig. 4. The
asymmetric cross-section could be attributed to the cata-
lyst-free growth mode for the InAs and InGaAs NWs,
whereas the higher InAs NW density to the nearly coherent
lattice matching condition with graphene (cf. Fig. 1(e)).
The epitaxial relationship of the grown NWs was fur-
ther confirmed by investigating the GaAs and InAs
NW/graphene interfaces using cross-sectional transmission
electron microscopy (TEM) (Fig. 6) [137, 176]. The gra-
phene layer underneath the GaAs NW was found to be flat
in Fig. 6(a). The GaAs NWs mainly have a cubic crystal
structure (zinc blende) and grow in the [111]B direction
with side-facets. In contrast to the GaAs NW/graphene in-
terface, the InAs NW/graphite interface shows the pre-
sence of 1 – 2 monolayer ledges of graphitic layers
(Fig. 6(b, c)). On the other hand, the InAs island/graphite
interface was found to be rough. In the former case, it was
concluded that the 1 – 2 monolayer ledges (using a short O2
plasma treatment) act as preferential nucleation sites for
the InAs NWs whereas the rough graphitic surface (using a
long O2 plasma treatment) for the InAs islands. Although
there are several challenges for growing vertically aligned
III– V NWs on graphene with high yield, the above men-
tioned results are already very interesting and will proba-
bly encourage many new studies in order to optimize the
process as well as explorations of other III – V materials.
2.4 Nature of the semiconductor/graphene epi-
taxial binding As has been described above, the epitaxial
nature of the grown semiconductor NWs on graphene and
graphene-like substrates have been debated to be vdWE or
non-vdWE in the literature. Since the absence of dangling
bonds at the surface of a substrate is a pre-requisite for
vdWE, the growth of NWs on graphene has mostly been
ascribed to vdWE [176, 178, 179] and it is only recently
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Phys. Status Solidi RRL 7, No. 10 (2013) 719

that a non-vdWE involving covalent/ionic bonds has been replacement of indium tin oxide (ITO) as a transparent
suggested [134, 135, 137, 174, 180]. These types of electrode has already been reported for organic solar cells
chemical bonds are likely to be originated from the prefer- [182, 183]. In these reports graphene has been deposited
ential adsorption sites of the semiconductor atoms or due onto a pre-existing structure. However if semiconductor
to the presence of defect related dangling bonds on gra- NW solar cells are grown on graphene it can act as a sub-
phene. Therefore in the case of non-vdWE, a lattice- strate as well as a transparent, conducting electrode. Such
matching condition would be preferred for the epitaxial idea has recently been attempted by Park et al. who have
growth. Due to the presence of these chemical bonds, the fabricated a ZnO NW/graphene hybrid solar cell [179].
latter type of epitaxy would result in a mechanically stron- Figure 7(a) illustrates the scheme used for making this
ger adhesion between the grown NWs and graphene. In
fact, ultrasonication treatment and bending experiments
performed on ZnO [180] and GaAs [137] NWs, respective-
ly, qualitatively indicated such mechanical stability. A
quantitative measure of the bonding type and bonding
strength will require further detailed studies of the
NW/graphene hybrid system in the future.

3 Nanowire material quality The quality of the

grown semiconductor nanowires has to be considered for
any successful device applications. Contamination from
the graphitic substrates, especially carbon, during the high
temperature growth might raise a concern on the material
quality. In order to address this issue, the grown NWs have
been characterized. Optical characterization of ZnO NWs
grown on the graphitic substrates by catalyst-free MOVPE
showed no evidence of any carbon related defect peak,
indicating no carbon contamination [155]. Similarly, pho-
todetectors made of single GaAs NWs grown by self-
catalyzed MBE showed a high photoresponsivity compa-
rable to that when the NWs were grown on a GaAs sub-
strate, again suggesting a high purity material [137]. These
results demonstrate that high quality materials can be
grown on the graphitic substrates. However, a graphene
substrate if “not clean” could be a potential source of con-
tamination of the grown materials particularly in the case
of an ultra-clean system like MBE. For example, the chem-
ical exfoliation process of CVD grown graphene usually
uses polymethyl methacrylate (PMMA) for support which
leaves residues on the transferred graphene and may not
only degrade the quality of the materials grown on it but
also could affect the intrinsic properties of graphene [181].
The exfoliation of graphene without using PMMA usually
results in a wrinkled rather than a smooth graphene surface,
affecting the vertical alignment of the grown NWs. There-
fore, a clean graphene transfer technique should be adapted
in order to ensure a good NW morphology and high mate-
rial quality.

4 Nanowire/graphene hybrid applications The

NW/graphene hybrid system has the potential to be utilized
in a number of functional electronic and optoelectronic de-
vice applications. Here we outline some of the reported po-
tential applications.
4.1 Solar cells Due to the high electrical conductivity
and optical transparency, graphene is an ideal candidate as
an electrode material in solar cells. Using graphene as a
Figure 7 (a) Schematic illustration of a ZnO NW/graphene hy-
brid solar cell. (b) Flat-band energy diagram for the structure in
(a). (c, d) Comparison of current density–voltage characteristics
of a NW/graphene hybrid-PbS QD and a NW/graphene hybrid-
P3HT solar cell device, respectively, with different polymer inter-
layers. Reprinted with permission from Ref. [179], Copyright
(2013), American Chemical Society.

www.pss-rapid.com © 2013 The Authors. Phys. Status Solidi RRL published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 rrl
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720 A. M. Munshi and H. Weman: Advances in semiconductor nanowire growth on graphene
NW/graphene hybrid structure. Arrays of ZnO NWs were
grown on graphene by a hydrothermal method after treat-
ing it with two different conducting polymers, poly(3,4-
ethylenedioxythiophene)-block-poly(ethylene glycol)
(PEDOT :PEG) and poly(thiophene-3-[2-(2-methoxy-
ethoxy)-ethoxy]-2,5-diyl) (Plexcore OC RG-1200) to in-
crease the NW yield. PbS QDs and poly(3-hexylthiophene)
(P3HT) were used as a hole-transporting donor materials,
whereas the ZnO NWs acts as an electron transporting
channel to the graphene cathode. The flat-band energy dia-
gram of the device is depicted in Fig. 7(b). Figure 7(c) and
(d) illustrate the comparison of the solar cell device per-
formances using a standard ITO electrode and a graphene
electrode. Results show that the power conversion effi-
ciencies for the graphene-based devices approach those of
the ITO-based devices, demonstrating the promising appli-
cation of graphene as a combined substrate and transparent
electrode in a solar cell device.
4.2 Light emitting diodes Light emitting diodes us-
ing semiconductor NWs in foldable and stretchable forms
would add new functionalities in next generation displays
and solid state lighting [184]. One way of fabricating such
devices is to grow the semiconductor NWs, although non-
epitaxially, on conventional plastic substrates using low
temperature techniques [185]. However, the high tempera-
ture required for the epitaxial growth of the semiconduc-
tors NWs using MOVPE or MBE techniques makes plastic
substrates unsuitable. Other viable route could instead be
to use graphene as the substrate due to its inertness and
stability with temperature. Lee et al. grew ZnO/GaN core-
shell NWs on a graphene/SiO2/Si substrate using CVD
[186]. After making the metal top contact, SiO2 was etched
by chemical etching, and the core–shell NWs with gra-
phene were transferred onto a Cu-coated polyethylene
terephthalate (Cu/PET) substrate. Figure 8 depicts the per-
formance of the device for different degrees of bending
of the Cu/PET substrate. By comparing the light emission
from the device (Fig. 8(a)), electroluminescence (EL)
(Fig. 8(b)), and electrical characteristics (Fig. 8(c)) for
bending radii: ∞, 5.5 mm and 3.9 mm, it was observed that
the device performance does not change significantly. This
results show that light emitting diodes based on a NW/
graphene hybrid can be reliable and sustainable to me-
chanical strain and suitable for flexible display applications.
4.3 Other applications Other device applications
based on the NW/graphene hybrid system have also been
successfully demonstrated. Choi et al. have fabricated a
fully rollable and transparent piezoelectric nanogenerator
based on a ZnO NW/graphene hybrid architecture where
graphene has been used both as the top and bottom elec-
trode [187]. The excellent device characteristics under dif-
ferent rolling and bending conditions demonstrate the sta-
bility and reliability of the hybrid device. Yi et al. have
demonstrated a flexible gas sensor made of vertically
aligned ZnO NWs on graphene [188]. This device show
© 2013 The Authors. Phys. Status Solidi RRL published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 8 (a) Light emission from a flexible ZnO NW/graphene
based light emitting diode at bending radii ∞, 5.5 mm and 3.9 mm.
(b, c) EL spectra and current–voltage characteristics of the device
at different bending radii. Reprinted with permission from Ref.
[186], Copyright (2011), WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim.
stable mechanical and electrical characteristics with high
sensitivity under multiple bending and releasing cycles.
Therefore NW/graphene based hybrid structures are prom-
ising candidates for various rollable and stretchable de-
vices.
5 Conclusions and outlook In conclusion, the
semiconductor NW/graphene hybrid system holds great
potential for a future generation of flexible and stretchable
electronic and optoelectronic devices. Recent advances on
the growth of NWs on graphene, the device fabrication of
the hybrid structure and their device performance are al-
ready intriguing. However, there are several challenges
both on growth aspects and on the device fabrication which
have to become understood and overcome. The inertness of
the two-dimensional graphene surface makes the growth of
the NWs much more difficult and challenging as compared
to when they are grown on other three-dimensional semi-
conductor substrates, e.g. Si. Therefore, proper strategies
have to be developed to modify the graphene surface
which favor the nucleation and can enhance the vertical
yield of the NWs with desired density. Moreover, a posi-
tion controlled growth using a proper mask, like what has
been achieved on various semiconductor substrates, would
be desired for a better understanding of the growth mecha-
nisms, control of the NW morphology and a better tuning
of other physical parameters. Due to the rapid improve-
ments in wafer-scale and roll-to-roll production of CVD
graphene, the semiconductor device cost could soon drasti-
cally reduce if graphene is used to replace the semiconduc-
tor substrate for the epitaxial growth. Once a controlled
NW growth and device fabrication have been achieved,
new types of functional devices may become realized
based on the NW/graphene hybrid structure.
www.pss-rapid.com

Phys. Status Solidi RRL 7, No. 10 (2013)
Acknowledgements We would like to thank our col-
leagues at NTNU, D. L. Dheeraj, V. T. Fauske, D. C. Kim,
A. T. J. van Helvoort, and B. O. Fimland for their support. We
acknowledge the financial support from NTNU and the Research
Council of Norway.
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