Versatile Carbon Hybrid Films Composed of Vertical Carbon Nanotubes Grown On Mechanically Compliant Graphene Films

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Versatile Carbon Hybrid Films Composed of Vertical

Carbon Nanotubes Grown on Mechanically Compliant


Graphene Films
By Duck Hyun Lee, Ji Eun Kim, Tae Hee Han, Jae Won Hwang,
Seokwoo Jeon, Sung-Yool Choi, Soon Hyung Hong, Won Jong Lee,
Rodney S. Ruoff, and Sang Ouk Kim*
Substrate materials for carbon nanotube (CNT) growth have been
mostly limited to brittle and at dielectric oxide materials, such as
Al
2
O
3
and SiO
2
.
[16]
An alternative substrate would (i) be stable at
the moderately high temperatures needed for CNTgrowth, (ii) be
mechanically compliant and stretchable for transfer to the widest
array of base structures (exible polymers, nonplanar structures,
etc.), (iii) allow for the rapid and large-scale fabrication of complex
device architectures, and (iv) if an electrically conductive
substrate, would have Ohmic contacts at all junctions and
similar work functions of CNTand the substrate, for efcient use
of input electrical power. Thin lms composed of overlapping
nanoplatelets can satisfy either all four criteria or alternatively the
rst three criteria, if an electrically insulating substrate is desired.
Options, thus, include a transparent and electrically insulating
thin lm that could be fabricated from overlapping nanoclay
(vermiculite,
[7]
mica,
[8]
montmorillonite, etc.) platelets, over-
lapping hexagonal boron nitride platelets (as two examples) or,
alternatively, for an electrically conductive substrate that is
mechanically compliant, overlapping graphene-based plate-
lets.
[9,10]
We have fabricated thin large-area lms by deposition
of graphene oxide platelets from aqueous colloidal suspensions,
decorated themwith patterned catalyst particles, and grown CNTs
at exceptionally high growth rates and at temperatures that result
in the substrate being converted to an electrically conductive
graphene-based lm.
[24,9,11]
Such carbon hybrid lms have
excellent exibility and stretchability, can be readily transferred to
any substrate including nonplanar surfaces, and were found to
have Ohmic electrical contacts throughout the junctions in the
CNT/metal-catalyst/graphene-lm system. As examples,
among many possible applications, the hybrid lms were readily
integrated into a eld-emitting device and its excellent perfor-
mance is reported herein.
Graphene is a one-atom-thick, two-dimensional layer of
sp
2
-hybridized carbons that possesses excellent mechani-
cal,
[9,10,12]
electrical, and thermal transport properties.
[1320]
Monolayer graphite, thus graphene, was originally synthesized
on catalytic metal substrates by thermal chemical vapour
deposition (CVD) and is the subject of extensive work since
the 1970s in the surface-science community (also referred to as
monolayer graphite (MG), rather than graphene; see references
such as [21]). A breakthrough occurred in 2004 with several
reports on the creation of graphene on insulating substrates, one
method involving micromechanical exfoliation
[21]
to achieve thin
layers on SiO
2
-on-Si wafer pieces,
[15]
and another involving the
growth of graphene by sublimation of Si from single-crystal
SiC,
[22]
so that the transport physics could be studied without the
interference of a conductive substrate in direct contact with the
graphene.
[15]
An alternative to micromechanical exfoliation is the
chemical production of graphene,
[23,24]
such as the exfoliation of
graphite oxide by creation of a liquid dispersion, followed by
deposition onto various substrates to yield thin lms,
[24]
paper-like materials,
[9]
etc. For example, the ready dispersion
of graphene oxide platelets in water allows for rapid deposition of
highly uniform large-area lms that, at the appropriate thickness,
have good mechanical exibility,
[9]
electrical conductivity,
[23]
and
optical transparency.
[25,26]
Figure 1a illustrates our method of making the CNTgraphene
hybrid lm. An aqueous dispersion of graphite oxide (i.e.,
containing suspended, individual graphene oxide platelets) is
spin-coated onto a silicon wafer yielding a uniform lm,
composed of overlapping and stacked graphene oxide platelets,
of about 7 0.3 nm thickness, which, after thermal reduction,
has a good electroconductivity as well as mechanical exibility
and optical transparency (Supporting Information, Fig. S1).
Nanopatterned iron catalyst particles were deposited on this lm
surface by means of self-assembled block-copolymer nanoporous
templates.
[24,11,2734]
Figure 1b shows scanning electron micro-
scopy (SEM) images of the uniformly sized catalyst islands upon
the graphene lm. The electron diffraction pattern of catalyst
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[*] Prof. S. O. Kim, D. H. Lee, J. E. Kim, T. H. Han, J. W. Hwang,
Prof. S. W. Jeon, Prof. S. H. Hong, Prof. W. J. Lee
Department of Materials Science and Engineering, KAIST
Daejeon 305-701 (Republic of Korea)
E-mail: sangouk.kim@kaist.ac.kr
Dr. S. Y. Choi
Convergence Components and Materials Laboratory
Electronics and Telecommunication Research Institute (ETRI)
Daejoen 305-700 (Republic of Korea)
Prof. R. S. Ruoff
Department of Mechanical Engineering and the Texas Materials
Institute
1 University Station C2200
The University of Texas at Austin
Austin, TX 78712-0292 (USA)
DOI: 10.1002/adma.200903063
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particles obtained by transmission electron microscopy (TEM)
matches that of a face-centered cubic (fcc) iron crystal.
Following preparation of the lm with patterned iron catalyst
particles, plasma-enhanced CVD (PE-CVD) growth of patterned
CNTs was achieved at 600 8C under a ow of C
2
H
2
/H
2
/NH
3
(5 sccm/80 sccm/20 sccm) at an overall pressure of 5 Torr, based
on methods recently published.
[24,11,35]
The CNTs are doped with
nitrogen (N-doped) and are primarily metallic. During the
PE-CVD step, the underlying lm composed of overlapping/
stacked graphene oxide platelets is thermally reduced and has an
electrical conductivity of about 1800 Sm
1
. The electron
diffraction pattern of the multilayer graphene lm consists of
concentric rings and not of individual spots and, thus, indicates a
lm of overlapping and reduced graphene platelets that are
randomly oriented (Fig. 1b).
Figure 1c shows that the CNTdiameter is precisely tunable by
adjusting the catalyst particle size. As previously reported, our
nanoporous templates of self-assembled block
copolymer enables subnanometer-scale tuning
of the particle size of the catalyst, such that
highly selective growth of wall-number-selected
CNTs is possible.
[11]
The fully grown carbon
hybrid lm, with CNTs having controlled
heights ranging from 10 to 100 mm (Fig. 1d),
were left as a raw hybrid lm (S1) or inltrated
with a poly(dimethyl siloxane) (PDMS) elasto-
mer (S2). The thickness of the PDMS inltra-
tion was precisely controlled to expose the
top ends of the CNTs (Fig. S2). Both
PDMS-inltrated hybrids and raw carbon
hybrids were readily detached from the under-
lying silicon substrate by chemical etching
(Fig. 1e). Owing to their mechanical exibility,
the hybrid lms could be transferred onto
nonplanar and/or exible substrates indicating
the critical role that the graphene lm plays.
Direct growth on nonplanar substrates, for
example, could be very challenging depending
on the substrate dimensions and, thus, its
impedance match in a PE-CVD chamber and
the fact that growth of wall-number-selected
CNTs by our templating method is impossible
on many types of nonplanar substrates.
Growth of CNTs by PE-CVD or CVD at such
high temperatures as 600 8C on exible
polymer substrates would be out of the
question.
Therefore, we emphasize that the compliant
substrate comprised of overlapped and stacked
nanoplatelets that are also durable at high
temperature in the presence of a variety of
reactants such as for CVD or PE-CVD growth
is a critical aspect, as was mentioned above.
While others have emphasized the possibilities
of reduced graphene oxide thin lms on
exible polymer substrates,
[18]
we are here
emphasizing the exceptional possibilities for
new technology by using a thin graphene lm
as the substrate, which, at least with reactants
that are not strong oxidants, will be stable to at least 1000 8C if not
considerably higher.
We note that the vertical CNTs of PDMS inltrated lm can be
macroscopically patterned in a square array, where the gap
between the square CNT arrays looks transparent due to the
optical transparency of the graphene lm (Figure 1e).
In order to accomplish a successful catalytic growth of a
densely packed vertical CNT array, catalyst shaping by
thermal treatment is a crucial step.
[11,36]
This step is generally
successful if the substrate material has a low surface energy. In
addition, the catalyst particles should not be contaminated with
the substrate material during the high-temperature CNT
growth. Graphene is an outstanding substrate material for
CNT growth due to its low surface energy and high thermal
stability. Typically, CNTs grow to a length of 20 mm within 1 min
and 100 mm within 10 min on the graphene-lm substrates
(Fig. S3).
Figure 1. a) Schematic illustration of the fabrication process for carbon hybrid lms. A multilayer
graphene oxide lm is spin-coated onto a SiO
2
/Si substrate from an aqueous dispersion.
The following block-copolymer lithography creates a nanopatterned iron catalyst array on the
graphene oxide lm. Highly aligned vertical CNT arrays are grown by catalytic PE-CVD. The
underlying graphene oxide lm is reduced and becomes electrically conductive during this
high-temperature PE-CVD growth. The fabricated hybrid lm with (S1) or without (S2) PDMS
inltration is detached from the Si substrate by wet-etching the SiO
2
layer. b) SEM image of iron
catalyst particles on graphene lm. The inset image shows the electron diffraction pattern.
c) Cross-sectional SEM images of hybrid lms. d) SEM image of a square-patterned CNT array on
the graphene lm. e) Photograph of S1 and S2 oating on a water surface.
1248 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2010, 22, 12471252
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The carbon hybrid lms demonstrated superb structural
integrity during mechanical deformation of different types.
Figure 2a shows that a PDMS-inltrated lm (S2) could
be signicantly stretched and bent without damage. As for
neat PDMS lms, the PDMS-inltrated lms could be
repeatedly attached to and detached from nonplanar substrates
(Fig. S2a). Figure 2b shows the high deformability of a
raw hybrid lm transferred onto a exible poly(ethylene
terephthalate) (PET) lm. The lm remains conformally
contacted to the exible PET lm even when the PET lm
is highly deformed. The excellent mechanical compliance
allows for rapid creation of highly nonplanar structures.
Figure 2c shows a raw hybrid lm conformally coating the
edge of a thin PET lm (thickness: 130 mm). As shown in the
magnied SEM images (Fig. 2d and 2e), the CNT forest
morphology exactly follows the right-angle edge shape of the
PET lm. Figure 2Figures 2f and 2g show raw hybrid lms that
are highly bent on PETsubstrates. The hybrid lms preserve their
structural integrity and good contact with the PET lm for both
severe outward (Fig. 2f) and inward (Fig. 2g) bending. When the
substrate is released, the hybrid lm returns to their original
planar shapes.
To quantitatively evaluate the impact of
bending and stretching on the electrical
conductivity, the electrical resistances of a
graphene lm and a hybrid lm were
measured under successive bending and
stretching cycles, as was done previously for
lms composed of the CVD-grown, large-area
graphene on exible polymer substrates.
[19]
The variation in the normalized resistance for
a 7-nm-thick graphene lm on a PDMS
substrate and of a PDMS-inltrated hybrid
lm under successive bending cycles are
shown in Figure 3a and 3b. Upon bending,
the resistance of the graphene lm increases at
a radius of curvature of about 6 mm, probably
due to changes in the relative positions of the
individual platelets in the lm (Fig. 3a). In
contrast, the resistance of the PDMS-inltrated
hybrid lm begins to increase at the much
smaller radius of curvature of about 3 mm
(Fig. 3b). The maximum increase in the
normalized resistance for the PDMS-inltrated
hybrid lm (0.2%) is also much lower than
that of the graphene lm (13%). When the
samples are released from bending after a few
cycles, both the graphene lm and the
PDMS-inltrated hybrid lm fully recover
their original resistance values. After 1000
bending cycles, the resistance of the hybrid
lm increases by only about 1% (inset of
Fig. 3b), demonstrating an extremely high
structural stability. Figure 3c and 3d present
the variations in the normalized resistance
of the graphene lm (Fig. 3c) and the
PDMS-inltrated hybrid lm (Fig. 3d) under
several stretching cycles. The resistance of the
graphene lm increases when the strain
exceeds 15%, but up to a limiting strain of about 45% it fully
recovers upon release, evidently due to the sliding of the
overlapped and stacked reduced graphene oxide platelets in the
lm.
[9,37]
At 70% elongation the resistance exhibits a sharp
increase and the zero-strain value is not recovered upon release,
hence, the lm fails (it disintegrates) as can be seen by the
naked eye. Owing to the high stretchability of the supporting
graphene lm, the PDMS-inltrated hybrid can also be reversibly
stretched up to the large strain of 45% (Fig. 3d).
The electrical contact between the CNT forests and graphene
lm was measured for a PDMS-inltrated hybrid lm. Figure 4a
and 4b show the electrical characterization by means of
two-point-probe measurements and the obtained currentvoltage
(IV) curves, respectively. Because each CNT forest is a square in
the overall array, each square makes isolated contact. The IV
curves measured across the CNT forest/iron catalyst/graphene
lm (red curve in Fig. 4b) or the CNT forest/iron catalyst/
graphene lm/iron catalyst/CNT forest (green curve in Fig. 4b)
show typical Ohmic response. The N-doped CNT forest shows
Ohmic response and a work function of 4.27 0.03 eV. The
multilayer graphene lm also exhibits typical Ohmic response
(blue curve in Fig. 4b) and has a work function of 4.37 0.03 eV
Figure 2. Photographs demonstrating: a) high stretchability/exibility of S2 and b) extreme
exibility of S1 on a PET lm. c) Photograph and d,e) SEM images of a hybrid lm that encloses
the PET lm edge. High- and low- (inset) magnication SEM images of a carbon hybrid lm on a
PET lm bent outward (f) and inward (g).
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(Fig. S1d). The work function of the iron metal catalyst is known
to be 4.5 eV.
[38]
The system thus consists of Ohmic conductive
components with work functions that range from 4.2 eV to 4.5 eV.
As a consequence, all of the electric junctions are Ohmic without
any signicant barriers in resistance.
A hybrid carbon lm oating on a water surface could be
readily transferred onto a conductive substrate and integrated into
a eld emission device. We measured the room-temperature
eld-emission characteristics of hybrid lms with different CNT
wall numbers (CNT length: 40 mm for all lms). Owing to the
highly uniform CNT length and diameter as well as the
stable electric contact to the underlying device substrate
through the graphene lm the emission is highly uniform over
the entire lm area (Fig. 4c). Figure 4d presents the variation in
current density with the applied electric eld. The turn-on eld
(measured at a current density of 10 mAcm
2
) decreases as the
CNT wall number decreases (the CNT tip becomes sharper).
The typical turn-on voltage for the double-walled CNTs exhibits an
extremely low value of 0.4 0.06 Vmm
1
, which is one of
the lowest values reported for CNT-forest eld emitters
(Supporting Information, Table S1). The PDMS inltrated lm
showed an increased turn-on eld, presumably due to the limited
number of exposed CNT tips at the top surface (see the reduced
effective surface area in Table S1). The eld emission from the
highly uniformensemble of CNTtips in these hybrid lms can be
t with the FowlerNordheim equation over a broad
voltage range.
[39]
The calculated eld-enhancement factors (b)
range from 9000 to 14500 (Fig. 4e). Moreover, the emission
current showed a high reliability over one week of continuous
operation (Fig. 4f). Owing to the uniform length and diameter
and the low work function of the N-doped CNTs as well as the
good electrical contact with the underlying graphene lm, the
mechanically compliant carbon hybrid lms have excellent
eld emission.
The high temperature stability and mechanical compliance of
lms of overlapped nanoplatelets and the ready scalability to a
very large area by straightforward deposition from colloidal
suspensions (such as achieved commercially for paints, inks, etc.)
suggest that the methods used here will be broad and versatile for
fabricating not only CNT/graphene lm hybrids but for the
fabrication of a very wide array of materials on such thin and
mechanically compliant lms for transfer onto exible and/or
nonplanar substrates. This will be of great utility because
there will be innumerable examples where such materials
could not be directly prepared on the exible and/or nonplanar
substrates.
[5,40]
Figure 3. Resistance variations of: a) a graphene lmon a 50-mm-thick PDMS substrate and b) a PDMS-inltrated hybrid lm(S2) as a function of bending
radius. The insets show the results for the 1
st
, 100
th
, and 1000
th
cycle, respectively. Resistance variations of: c) a graphene lm on a 50-mm-thick PDMS and
d) a PDMS inltrated hybrid lm subjected to moderate (0 45%) and large (0 70%; inset) stretching.
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Experimental
Carbon Hybrid-Film Preparation: First, an aqueous dispersion of
graphene oxide was prepared using methods described elsewhere
[9,23]. The average diameter of graphene oxide platelets was 1.30 mm.
A lm comprised of overlapping and stacked graphene oxide platelets was
prepared by spin-coating the aqueous dispersion onto a SiO
2
(500 nm)/Si
wafer. Such spin-coated lms were typically about 7 nm thick as measured
in cross-section by SEM. Self-assembled nanoporous templates of
block-copolymer thin lm were prepared on the spin-coated lm, using
methods described elsewhere [9,24]. A lm of iron particles was deposited
onto the nanoporous block copolymer template. After complete lifting off
of the block copolymer template by sonication, a nanopatterned iron
catalyst particle array remained on the lm. Vertical CNTs were grown from
the nanopatterned catalyst array by PE-CVD. The graphene oxide lm
substrate was heated to 600 8C under a C
2
H
2
/H
2
/NH
3
stream (5 sccm/
80 sccm/20 sccm). When the substrate temperature reached 600 8C, the
chamber pressure was xed at 5 Torr and a 470 V direct current (DC)
plasma was activated. Slow streaming of acetylene gas (5 sccm for 1 min to
achieve, e.g., 20-mm-tall CNTs) resulted in vertical CNTs. During this
high-temperature CNT growth, the underlying graphene oxide lms were
reduced and, thus, rendered electroconductive.
Field-Emission Measurements: A carbon hybrid lm was transferred onto
an ITO/glass substrate and an ITO/glass anode was positioned parallel to
the top surface of the hybrid lm. The spacing between the ITO anode and
the top surface of the hybrid lm was set to 500 mm. The eld-emitting
properties were measured under a vacuum of 10
6
Torr by applying a
voltage of 0 V2000 V between the two electrodes.
Acknowledgements
This work was supported by National Research Laboratory Program
(R0A-2008-000-20057-0), the World Class University (WCU) program
(R32-2008- 000-10051-0), Basic Science Research Program (2009-0081359),
the Pioneer Research Center Program (2009-0093758), and the Korea Science
and Engineering Foundation (KOSEF) grant (R11-2008-058-03002-0) funded
by the Korean government, and KAIST EEWS (Energy, Environment, Water,
and Sustainability) Initiative (EEWS0903). R.S.R. was supported by NSFgrants
#CMMI-0802247 and #CMMI-0742065. Supporting Information is available
online from Wiley InterScience or from the author.
Received: September 9, 2009
Revised: October 13, 2009
Published online: January 13, 2010
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