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Tailoring Electrical Transport Across Grain

Boundaries in Polycrystalline Graphene
ARTICLE in SCIENCE JUNE 2012
Impact Factor: 33.61 DOI: 10.1126/science.1218948 Source: PubMed

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10 AUTHORS, INCLUDING:
Fereshte Ghahari

Carlos Ruiz-Vargas

Columbia University

Cornell University

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Acknowledgments: The authors are grateful to Samsung

Advanced Institute of Technology colleague X. Li for TEM
analysis assistance and the Nano Fabrication group for process

assistance. We are also grateful to S.-H. Lee and S. Seo for

useful discussions.

Supplementary Materials
www.sciencemag.org/cgi/content/full/science.1220527/DC1
Materials and Methods

Tailoring Electrical Transport

Across Grain Boundaries in
Polycrystalline Graphene
Adam W. Tsen,1 Lola Brown,2 Mark P. Levendorf,2 Fereshte Ghahari,3 Pinshane Y. Huang,1
Robin W. Havener,1 Carlos S. Ruiz-Vargas,1 David A. Muller,1,4 Philip Kim,3 Jiwoong Park2,4*
Graphene produced by chemical vapor deposition (CVD) is polycrystalline, and scattering of
charge carriers at grain boundaries (GBs) could degrade its performance relative to exfoliated,
single-crystal graphene. However, the electrical properties of GBs have so far been addressed
indirectly without simultaneous knowledge of their locations and structures. We present
electrical measurements on individual GBs in CVD graphene first imaged by transmission electron
microscopy. Unexpectedly, the electrical conductance improves by one order of magnitude for
GBs with better interdomain connectivity. Our study suggests that polycrystalline graphene with
good stitching may allow for uniformly high electrical performance rivaling that of exfoliated
samples, which we demonstrate using optimized growth conditions and device geometry.
ost three-dimensional electronic materials produced in macroscopic quantities are not homogeneous but incorporate
numerous classes of dislocations and defects that
degrade electrical performance (1). Although largescale graphene films produced by chemical vapor
deposition (CVD) (2, 3) might be expected to be
nearly defect free, recent transmission electron
microscopy (TEM) studies (4, 5) have shown that
these films are polycrystalline. Electrical transport between single-crystal domains could be affected by scattering at the grain boundary (GB),
as has been shown theoretically (69). Although
TEM has provided a fast and accurate means to
identify and image the structure of GBs in CVD
graphene, the electrical impact of GBs has so far
been studied only indirectly in experiments. Previous work by Huang et al. detects no measurable electrical resistance from GBs within
instrument limits (4), and ensemble measurements
done by various groups find very weak correlation between the average domain size of the
graphene film and overall device mobility (4, 10).
In contrast, Yu et al. and Jauregui et al. inferred
the presence of GBs from the shape of partially
grown graphene islands and extracted a finite GB
resistance from their measurements (11, 12). The
ambiguity in these findings arose from a lack of
knowledge of the precise domain morphology

1
Department of Applied Physics, Cornell University, Ithaca, NY
14853, USA. 2Department of Chemistry and Chemical Biology,
Cornell University, Ithaca, NY 14853, USA. 3Department of
Physics, Columbia University, New York, NY 10027, USA. 4Kavli
Institute at Cornell for Nanoscale Science, Cornell University,
Ithaca, NY 14853, USA.

*To whom correspondence should be addressed. E-mail:

jpark@cornell.edu

Supplementary Text
Figs. S1 to S10
References

for the graphene measured. To this end, we have

devised an experimental scheme to first image
(using TEM) and then electrically address individual domains and GBs in polycrystalline
graphene. Such a capability is crucial, because
graphene domain structures generated during synthesis form nontrivial patterns that are strongly
dependent on growth conditions and difficult to
predict a priori.

14 February 2012; accepted 4 April 2012

10.1126/science.1220527

In Fig. 1A, we show false-color dark-field

TEM (DF-TEM) images of graphene films grown
under three different conditions [see supplementary materials (13)] taken in a manner similar to
Huang et al. (4). Each colored region corresponds
to a separate graphene crystalline domain with
distinct lattice orientation. The image is generated
by using an aperture in the back-focal plane of
the microscope to collect electrons diffracted from
only a narrow range of angles by the graphene
lattice. In general, different graphene domains
produce a diffraction pattern rotated with respect
to one another, so each domain can be imaged
separately, colorized, and then combined.
In growth A, graphene was synthesized under high reactant flow rates, which produced fast
growth and also small average domain size D
1 mm. Graphene from growth B was synthesized
in a diluted methane environment, whereas growth
C was further enclosed in copper foil, after Li
et al. (14), resulting in slower growths. The
latter films were terminated after only partial
surface coverage to highlight their growth
structures. In subsequent microscopy and
electrical measurements, however, we used continuous films, for which growth B yielded D
10 mm and growth C, D 50 mm. The overall
shapes of partially grown graphene islands in
growth B were polygons, whereas growth C generally formed flowered islands (fig. S1). Despite

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29. L. Liao et al., Nature 467, 305 (2010).

30. Y.-M. Lin et al., IEEE Electron Device Lett. 32, 1343 (2011).

Fig. 1. (A) Composite false-color DF-TEM images of CVD graphene produced using three different
growth conditionsA, B, and Cyielding average domain size D of 1, 10, and 50 mm, respectively,
in continuous films. (B) (Left) Schematic of specially fabricated TEM chip compatible with electronbeam lithography and electrical measurements. (Top right) SEM image of top-gated, graphene Hall
bar device. (Bottom right) Overlaid SEM and DF-TEM images showing device crossing a single GB of
two domains from growth C. Scale bars, 1 mm.

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these differences, DF-TEM shows that even a

single graphene island can contain several distinct
domains, revealing the complexities of graphene
growth inherent in even seemingly simple growth
structures.
To study the impact of individual GBs on
electronic properties, electrical measurements and
TEM imaging need to be done in conjunction.
However, complicated sample preparation processes and constraints arising from chip geometry
make TEM studies currently incompatible with
other experimental schemes, such as nanofabrication. Here, we describe a method to electrically
address a material with nanometer resolution
after TEM characterization. In Fig. 1B (left), we
show a schematic of a specially fabricated TEM
chip (see supplementary materials and fig. S2)
that is 2.33 mm wide on each side, 200 mm thick,
and fits standard TEM holders. In the center is a
fully suspended, silicon nitride (SiN) TEM window (80 by 80 mm, 20 nm thickness) with metalized alignment marks. On the periphery are large
electrical leads and contacts patterned by optical
lithography. After graphene was transferred and
imaged, we selected an area of interest and used
electron-beam lithography to pattern a field-effect
transistor device with four-terminal geometry.
Raman spectra taken after our TEM imaging suggests that our graphene was not damaged during
this process (fig. S3). In three separate lithography steps, we (i) defined electrodes, (ii) patterned
the graphene, and (iii) defined a top gate. A completed structure is shown in the scanning electron

microscopy (SEM) image on the top right of Fig.

1B. By combining TEM and standard fabrication
methods, we electrically addressed individual domains and GBs in CVD graphene with 50-nm
accuracy. In the bottom right, we show an SEM
image of a representative device (before defining
the top gate) overlaid with a false-color DF-TEM
image of the underlying graphene, consisting of a
single GB between two large domains. The areas
with faded colors represent graphene that was
subsequently etched away, leaving behind only
the high-contrast pattern in the center.
We first performed room-temperature transport measurements on a GB from growth A (D
1 mm). In the upper inset of Fig. 2A, we show the
composite image of a particular device consisting
of an individual GB. In the top panel, we plot
four-terminal sheet resistance R versus gate
voltage for the left (L) and right (R) domains, as
well as that across the GB (L-R), measured simultaneously for the same gate voltage sweep. The
single-domain measurements showed field-effect
behavior that was typical for graphene with a
Dirac point at VDirac 7 V. More strikingly, the
two showed nearly identical values for the entire gated range. The cross-domain measurement
showed similar qualitative behavior with a comparable Dirac position. However, L-R exhibited
an increased resistance, particularly at gate biases
near VDirac, that we attributed to additional scattering caused by the GB. Also, L-R seemed to
scale from single-domain resistivity (r) by a constant factor of 1.4 for all gate values, as shown by

the dashed curve. Finally, by subtracting the averaged L and R values from L-R, we can extract the
resistivity per micrometer length of the GB itself,
rGB, which we plot in the bottom panel as a
function of gate voltage. rGB exhibited a similar
gate-tunable behavior as r: It is 4 k-mm at
VDirac and decreased with doping, reaching a saturated value of 0.5 k-mm in the p-type regime.
The results of our measurement can be interpreted to describe the presence of a GB as
simply an extension of the conductance channel
defined by an effective length l = rGB/r. When
a device of dimensions L and W crossed a GB,
resistance increased from the intrinsic, monocrystalline resistance R = r(L/W) to R = r(L/W) +
rGB/W = r(L+l)/W. Hence, the channel length
effectively increased by l, and both the electrical
conductance and the carrier mobility were reduced by a factor R/R = 1+l/L. Because R/R
closely followed a fixed scaling with gate voltage
in our measurements, l was approximately constant and independent of carrier density (fig. S4).
This effect, as diagrammed in the lower inset of
Fig. 2A, is a key finding of this report. In particular, the introduction and determination of l (representing GB connectivity), along with average
domain size D, will allow tailoring of overall
electrical transport in devices of all length scales.
For this particular device, we extracted a value
of l 200 nm.
Different electrical behavior was observed for
analogous measurements at a GB from growth C
(D 50 mm), which we show in Fig. 2B. Here, L

Fig. 2. (A) (Top) Four-terminal

sheet resistance R of device crossing a single GB from growth A
(SEM/DF-TEM shown in inset; scale
bar, 1 mm) measured in left (L),
right (R), and across (L-R) domains
as a function of gate bias. L-R scales
L by a factor of 1.4. (Bottom) Extracted gate-dependent GB resistivity rGB. GB acts to increase
channel length by l 200 nm at
all gate biases. (B) Corresponding
measurement of more resistive
GB from growth C device (scale
bar, 1 mm). L-R scales L by 3.2; l =
1.8 mm. (C) l and rGB (at VDirac
and p-type doping) across 11
single-GB devices from growths A
and C. Overall, GBs from growth C
are an order of magnitude more
resistive. (D) (Top and middle)
Higher resolution DF-TEM images
of GBs from suspended growth A
and C samples show better stitching from growth A. (Bottom) DF-TEM
of overlapped GB often observed in
growth C. The diffraction spots and
relative aperture positions used to
form the images are shown as insets. Scale bars, 100 nm. (E) Electrical
measurements of device consisting
of GB overlapped by 325 nm show improved GB conductance. l 250 nm.

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and R also showed similar gate dependences, but

L-R was considerably greater at all gate values,
signifying increased scattering at the GB. In fact,
we extracted a gate-dependent GB resistivity
(5 to 40 k-mm) that was overall an order of
magnitude greater than that measured for growth
A. Nevertheless, R/R 3.2 was again roughly
constant with gate bias, from which we determined l = 1.8 mm for this GB, or twice as long as
the device channel itself.
We fabricated 11 graphene devices with a
single GB and performed similar measurements
(five devices from growth A and six from C). In
Fig. 2C, we plot their GB resistivities measured
both at VDirac and with p-type doping. Although
we observed a range of different values, GBs
from growth C were an order of magnitude more
resistive overall. We also plot the corresponding
gate independent l values: The mean for growth
A samples was 110 nm, and it was 880 nm for C.
In contrast, we observe no strong correlation between r and different growth conditions (fig. S5).
The poorer conductance of GBs from growth
C can be explained by careful investigation of
their GB structure. Although graphene in growth
A exhibited much greater polycrystallinity, it
yielded highly uniform coverage of the underlying copper surface. However, for growth C,
we often observed many areas between islands
with small gaps and overlaps, suggesting a re-

Fig. 3. (A) GB conductance as a function of carrier

density from data in Fig. 2, A and B. Growth C data
are fit to a model of defect scattering from midgap
states. (B) Temperature dependence of inter- (L-R)
and intra- (R) domain resistance from growth A
device shows that rGB is insensitive to temperature.

duced tendency for different domains to stitch

(fig. S6). To study the morphology of individual
GBs with higher resolution, we suspended separate graphene samples from the same growths
on top of perforated SiN chips to examine with
DF-TEM. We found distinct classes of GB behavior from growths A and C.
In Fig. 2D (top left), we show a DF-TEM
image of a GB between two colored domains
from growth A, with their respective diffraction
spots circled in the inset. On the right, we take an
image of the entire region by selecting both spots
simultaneously and see a relatively featureless
boundary region, which is further highlighted by
the flat intensity profile taken across the boundary along the marked line. Recently, Huang et al.
have imaged a particular GB of this type with
angstrom resolution and demonstrated that it can
form an atomically sharp junction locally at the
nanometer scale (4). In contrast, domains from
growth C showed a markedly different behavior,
as seen in the middle panel. Here, two domains
have physically connected, as can be seen in the
bright-field image in the inset, and showed no
slack at the boundary despite being suspended.
However, selecting the diffraction spots for both
domain orientations simultaneously revealed a
dark strip 30 nm wide where the domains join.
This result implies that this extended boundary
region had a structure different from that of the
crystals on either side, suggesting that the domains
were joined together either by graphitic material
at another orientation or by amorphous material,
although atomic resolution imaging would be
needed to confirm this directly. The presence of grain
boundaries with greater crystalline discontinuity
for growth C appeared to be a general trend (fig.
S7). Additionally, we have observed growth C
domains to connect via an overlapping region.
An example is shown in the bottom panel of Fig.
2D. Again, the overlap was seen most clearly
by selecting diffraction spots from both domains
simultaneously, because the double-layered re-

gion appeared twice as intense in the dark-field

image. Here, one domain extended 65 nm on top
of the other, although overlaps as large as 1 mm
were observed for longer growths. Similar behavior has also been observed by Robertson et al.
using atomically resolved TEM imaging (15).
We therefore conclude that the electrical properties of GBs in CVD graphene are not universal
but are, rather, keenly sensitive to growth conditions and reflect the quality of the connection
between domains. In particular, the high-reactivity
environment from growth A that yielded a faster
growth rate could also contribute to better interdomain stitching.
We have also fabricated a device across two
domains from growth C that have overlapped at
their boundary, which we show in Fig. 2E. Here,
the domains overlapped by 325 nm. Instead of an
increased cross-domain resistivity, we observed
a conductance that was enhanced by a factor of
1.45, which implies an effective negative l
250 nm. We also plotted the square conductance
from the overlapped graphene exclusively by removing contributions from the L and R domains,
and we saw that it was an order of magnitude
greater than single-layered graphene. This result
suggests that the scattering properties in doublelayered graphene are improved from single-layer,
so reliable synthesis of grain boundaries with
large overlap, if possible, would be an exciting
advance. At the same time, we would also expect
this effect to be sensitive to the length of overlap,
because a narrow overlap could still potentially
hinder interdomain transport.
To better understand the origin of GB resistance for our devices with nonoverlapping domains, we plotted in Fig. 3A the GB conductivity
sGB = 1/rGB as a function of carrier density n = C
|VG VDirac|/e for the two devices shown in Fig.
2, A and B, where C is the gate capacitance per
unit area. The GB from growth A was overall
an order of magnitude more conductive, as discussed previously. At low carrier concentrations

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Fig. 4. (A) Model of device resistance as a function of device size for growths A and C, using empirically
determined l and D. Smaller devices with 1 GB from growth C are very resistive, while growth A devices with
the statistically expected number of GBs show uniform high performance over a large range of sizes. (B) (Left)
Grayscale SEM image (scale bar, 10 mm) of 5 by 5 mm growth Atype graphene device fabricated on SiO2/Si
and representative color DF-TEM image (scale bar, 1 mm) of domain structure. Transport characteristics
demonstrate performance on par with exfoliated graphene. (Right) Histograms for field-effect mobility and
p-type sheet resistance of 28 similarly fabricated devices show excellent electrical behavior overall.

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off occurs for the above two criteria. In the limit

where device size L = W << D, graphene consisting of a single domain will clearly have the
best individual performance, as device resistance
is R = r. However, devices that cross a GB will
have R = r(1+l/L), which could pose a hindrance if l is large, such as in growth C. In the
opposite limit, where L >> D, the devices see R =
r(1+nl/L), where n is the number of GBs
crossed. However, we expect n L/D, so all
devices will see a uniform R r(1+l/D), which
also may not severely degrade performance if l is
small, such as in growth A. The plot in Fig. 4A
captures what is described here quantitatively.
Here, we calculated normalized device resistance
R/r as a function of device size L up to 15 mm
for graphene from the two electrically characterized growths A (D 1 mm) and C (D 50 mm).
The curve in black shows the result of growth C
crossing one GB using the empirically obtained
lC = 880 nm. Normalized resistance is very large
at small L and decreases asymptotically to 1, the
intrinsic limit without GBs. The curve in blue
shows the result of growth A as the device crosses
the expected number of GBs n = L/D 1 (the
error bars indicate a Tn standard deviation from
this number, rounded to the nearest integer). Here,
resistance is 1 at small L and slowly increases, as
calculated by lA = 110 nm. The two curves cross
at L 9 mm. However, even above this length, the
growth A sample will not severely degrade in
performance as resistance eventually saturates to
only 10% (l/D) larger than the intrinsic limit for
monocrystalline graphene. Similarly, device mobility will approach 90% (1 l/D) of that of a
single crystal. Of equal importance, such devices
show uniform performance over a large range of
lengths with less likelihood of failure for an individual device.
This analysis suggests that well-stitched GBs
are not the dominant scattering mechanism to
affect large-scale device transport (22) and points
to an exciting potential for the high electrical performance of polycrystalline graphene. Although
the synthesis of growth C could, in principle, be
further optimized to achieve large domains together with better GB connectivity, it seems that
we can already achieve most of the performance
capability of single-crystal graphene in large-scale,
polycrystalline devices using our current growth
conditions (growth A), despite limited domain size.
We have now demonstrated the performance
potential of such samples experimentally, as shown
in Fig. 4B. We have fabricated a set of ultra-clean
graphene devices on oxidized silicon wafers
(5 by 5 mm, with 100-nm SiO2 top gates) using
growth Atype synthesis from a semiconductorgrade CVD system that is thoroughly helium
leak-checked and conventional lithography without the additional imaging steps of TEM. For a
particular high-performance device, we achieved
a field-effect mobility of 25,000 cm2/Vs and sheet
resistance of 1 kilohm at a relatively low carrier
density (~3 1011 cm2) (Fig. 4B, bottom left), on
par with that of supported, exfoliated graphene

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(16). The use of boron nitride as a gate dielectric

could perhaps be used to further improve device
performance (23, 24). On the right, we plotted
statistics across 28 similarly fabricated devices
and saw that almost all devices had field-effect
mobilities above 10,000 cm2/Vs and resistances
below 2 kilohm. Thus, GBs in chemically grown,
polycrystalline graphene can be optimized to
have a minimal electrical impact on the overall
transport properties of the device, in accordance
with our model and findings above. We note that
our experimental techniques presented here are
not limited to the study of graphene but pave the
way for electrical studies of other newly reported
nanomaterials, such as layered, two-dimensional
inorganic compounds and their hybrids (25), together with the imaging power of TEM.
References and Notes
1. D. B. Holt, B. G. Yacobi, Extended Defects in
Semiconductors: Electronic Properties, Device Effects
and Structures (Cambridge University Press, Cambridge;
New York, 2007).
2. X. Li et al., Science 324, 1312 (2009).
3. S. Bae et al., Nat. Nanotechnol. 5, 574 (2010).
4. P. Y. Huang et al., Nature 469, 389 (2011).
5. K. Kim et al., ACS Nano 5, 2142 (2011).
6. O. V. Yazyev, S. G. Louie, Nat. Mater. 9, 806 (2010).
7. O. V. Yazyev, S. G. Louie, Phys. Rev. B 81, 195420 (2010).
8. A. Mesaros, S. Papanikolaou, C. F. J. Flipse, D. Sadri,
J. Zaanen, Phys. Rev. B 82, 205119 (2010).
9. N. M. R. Peres, F. Guinea, A. H. Castro Neto, Phys. Rev. B
73, 125411 (2006).
10. X. Li et al., Nano Lett. 10, 4328 (2010).
11. Q. Yu et al., Nat. Mater. 10, 443 (2011).
12. L. A. Jauregui, H. Cao, W. Wu, Q. Yu, Y. P. Chen,
Solid State Commun. 151, 1100 (2011).
13. Materials and methods are available as supplementary
materials on Science Online.
14. X. Li et al., J. Am. Chem. Soc. 133, 2816 (2011).
15. A. W. Robertson et al., ACS Nano 5, 6610 (2011).
16. Y. W. Tan et al., Phys. Rev. Lett. 99, 246803 (2007).
17. N. H. Shon, T. Ando, J. Phys. Soc. Jpn. 67, 2421 (1998).
18. S. Adam, E. H. Hwang, V. M. Galitski, S. Das Sarma,
Proc. Natl. Acad. Sci. U.S.A. 104, 18392 (2007).
19. T. Stauber, N. M. R. Peres, F. Guinea, Phys. Rev. B 76,
205423 (2007).
20. J.-H. Chen, W. G. Cullen, C. Jang, M. S. Fuhrer,
E. D. Williams, Phys. Rev. Lett. 102, 236805 (2009).
21. Y. W. Tan, Y. Zhang, H. L. Stormer, P. Kim, Eur. Phys. J.
Spec. Top. 148, 15 (2007).
22. G.-X. Ni et al., ACS Nano 6, 1158 (2012).
23. C. R. Dean et al., Nat. Nanotechnol. 5, 722 (2010).
24. W. Gannett et al., Appl. Phys. Lett. 98, 242105 (2011).
25. J. N. Coleman et al., Science 331, 568 (2011).
Acknowledgments: The authors thank B. Ilic and P. L. McEuen
for helpful discussions. This work was mainly supported by
Air Force Office of Scientific Research grants (FA9550-09-1-0691
and FA9550-10-1-0410) and the NSF through the Cornell
Center for Materials Research (NSF DMR-1120296). L.B. was
partially supported by a Fullbright scholarship; P.Y.H.
was supported by an NSF Graduate Research Fellowship
(DGE-0707428); R.W.H. was supported by an NSF Graduate
Research Fellowship; and C.S.R.-V. was partially supported
by Consejo Nacional de Ciencia y Tecnologa Mexico. Sample
fabrication was performed at the Cornell NanoScale Science
and Technology Facility.

Supplementary Materials
www.sciencemag.org/cgi/content/full/336/6085/1143/DC1
Materials and Methods
Figs. S1 to S7
References (26, 27)
10 January 2012; accepted 13 April 2012
10.1126/science.1218948

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near the neutrality point, both values saturated

to a minimum as a result of the residual density
induced by charge inhomogeneities (16). Away
from their minima, sGB increased slightly sublinearly with n. The increase of GB conductance
with doping indicates long-range scattering, because weak point disorder is insensitive to carrier
density (17). Currently, both charge-impurity disorder (18) and strong disorder giving rise to midgap states (19) are expected to yield conductivity
that is roughly linear with carrier density, so it is
difficult to untangle these effects a priori. However, the latter predicts increasingly sublinear
behavior as the size of the disorder is increased. If
we assume that strong disorder dominates the GB
resistance in the limit of large rGB as from growth
C, we can model sGB = (2e2/ph)(n/Ld)ln2(pn R),
where Ld is the linear density of defects at the GB
and R is the radius of the defect potential. Fitting
our data for growth C to this expression away
from the conductivity minimum, we obtained
Ld = 2.0 T 0.1 107 cm1, R 2 nm. By comparison, R here was an order of magnitude greater
than that modeled from ion-induced single-atom
vacancies reported previously (20).
Although defect scattering from GBs was
sensitive to carrier density, we expected it to be
completely insensitive to the effects of temperature. In Fig. 3B, we show the intradomain (R)
and cross-domain (L-R) resistivities for another
device (growth A), taken simultaneously as a
function of temperature from 5 K to 250 K at
p-type doping. We see similar weak temperature
dependence for both measurements, which may
be the result of impurities in the graphene or on
the substrate for this particular sample (21). L-R,
however, always appears a fixed value larger
throughout, from which we extract a relatively
constant GB resistivity of 1 k-mm for the entire
temperature range, consistent with our picture of
defect-dominated transport.
The results of our TEM and transport measurements on individual GBs in CVD graphene
show that the conductance of GBs was highly
correlated with their structure. Our data also suggest that it is necessary to control GB connectivity as well as domain size in order to maximize
the overall electrical transport properties in polycrystalline graphene. For this, it is essential to
develop a systematic understanding of the combined electrical effect of l (representing GB connectivity) and D (domain size) under various
graphene growth conditions and device geometries. Below, we present a simple model based
on these two empirically derived parameters that
can be used to optimize electrical performance in
graphene devices at all length scales.
There are two necessary criteria to uphold in
order to successfully integrate CVD graphene
into electronic applications. Not only is it important to maximize the performance of individual
graphene devices, but achieving uniform performance across many devices is also highly desirable. Because GBs introduce inhomogeneity in
the graphene film on the length scale D, a trade-

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Supplementary Materials for

Tailoring Electrical Transport Across Grain Boundaries
in Polycrystalline Graphene
Adam W. Tsen, Lola Brown, Mark P. Levendorf, Fereshte Ghahari, Pinshane Y. Huang,
Robin W. Havener, Carlos S. Ruiz-Vargas, David A. Muller, Philip Kim, Jiwoong Park*
*To whom correspondence should be addressed. E-mail: jpark@cornell.edu
Published 1 June 2012, Science 336, 1143 (2012)
DOI: 10.1126/science.1218948

This PDF file includes:

Materials and Methods
Figs. S1 to S7
References

Materials and Methods

Synthesis of graphene with various domain size D:

All graphene is grown on 25 m thick copper foil in a custom hot-wall quartz tube
furnace at 2 Torr pressure using the process reported by Li et al. (2).
Growth A (D 1 m): Copper substrates were heated to the reaction temperature of 1000
C in a hydrogen environment (H2: 100 sccm). After annealing for one hour, methane
(CH4: 6 sccm) was introduced. Following a 10 minute growth stage, the chamber was
slowly cooled to room temperature.
Growth B (D 10 m): Copper is heated to 1050 C in a hydrogen environment (H2:300
sccm) and annealed for 30 minutes. Methane (CH4: 0.8 sccm) is introduced for 30
minutes for partial growth (Fig. S1, top) and 90 minutes for complete coverage. The
furnace is subsequently cooled.
Growth C (D 50 m): After Li et al. (14), a closed "pocket" made of copper foil was
heated between 980-1000 C in a hydrogen environment (H2: 60-120 sccm) and annealed
up to 3 hours. Methane (CH4: 1 sccm) is introduced for 90 minutes for partial growth
(Fig. S1, bottom) and 3 hours for complete coverage, after which the furnace is cooled.
Fabrication of transmission electron microscopy chip compatible with electrical
measurements:
Here, we describe the fabrication of transmission electron microscopy (TEM) chips that
are compatible with electron-beam lithography and electrical measurements. A completed
chip is shown in figure S2 (A). It is 2.33 mm wide on each side, 200 m thick, and fits
standard holders. In the center is a fully suspended, silicon nitride (SiN) TEM window
(80x80 m, 20 nm thickness) with metalized alignment marks. On the periphery are large
electrical leads and contacts. The chips are fabricated on the wafer scale using optical
lithography and cleaved individually at the end. A schematic of the process flow is shown
in figure S2 (B). First, we grow 50 nm of low stress SiN on 200 m thick silicon (Si)
<100> wafers. In two separate lithography steps we pattern and metalize alignment marks
and electrical leads close to the TEM window (20 nm Cr/Au) as well as contact pads on
the chip periphery (150 nm Cr/Au). Next, we pattern and etch large SiN windows on the
backside of the chip using reactive ion etching (RIE) to allow for KOH etching of the Si
substrate underlying the TEM window. After transferring graphene, the SiN TEM
window is further thinned from the back to 20 nm with RIE.

Growth B

Growth C

Fig. S1
Top: optical image of polygon graphene islands from growth B transferred onto SiO2/Si.
Bottom: optical image of flowered graphene islands from growth C on copper foil. Scale
bars: 10 m.

2.33 mm

Si <100>, 200 m

CVD SiN, 50 nm

2.33 mm

Metallize leads/alignment marks, 20 nm

Metallize contacts, 150 nm

RIE etch SiN backside

50 m

KOH etch Si

TEM Window (SiN, ~20 nm)

Transfer graphene

RIE etch SiN, ~20 nm

Fig. S2
(A) Optical images of completed TEM chip compatible with e-beam lithography and
electrical measurements. (B) Schematic outlining fabrication procedure: 1) Grow 50 nm
of SiN on 200 m thickness Si wafer. 2) Metallize electrical contacts and leads. 3) RIE
etch SiN windows on backside for 4) KOH etch of Si. After transferring graphene, 5) thin
SiN TEM window to 20 nm from backside with RIE.

Fig. S3
Micro-Raman spectrum (inset) of graphene taken after dark-field TEM imaging (main
panel). Small D peak shows minimal radiation damage in contrast with (26) and (27).
Raman location is indicated by circle. Scale bar: 1 m.

10

|| (nm)

10

10

growth A GB
growth C GB
overlapped GB

10

10

10

10

11

10

12

10

n (cm-2)
Fig. S4
Effective length || as function of hole density n = C |VG -VDirac|/e for devices shown in
Fig. 2A, B, E. changes only within a factor of 2 as n is tuned by three orders of
magnitude.

100

Growth A

Growth C

R (k)

L
R

10

Device
Fig. S5
Intra-domain sheet resistance (L, R) measured at the Dirac point for all TEM-resolved
devices. No strong differences are seen between growths A and C.

Growth A

Growth C

Fig. S6
Scanning electron micrographs of growths A (top) and C (bottom) on copper foil. Growth
A completely covers copper surface, but growth C shows many areas with gaps and
overlaps (denoted by red arrows), suggesting reduced tendency for inter-domain merging.
Zoom-in image of area between islands shows dark line and small holes on boundary
(denoted by black arrows).

Growth A

Growth C

Fig. S7
Dark-field TEM images of individual grain boundaries from growths A (left) and C
(right) suspended on holes. Diffraction spots and apertures used to form images are
shown in insets. Domains from growth A almost always make seamless connections
when selecting both spots simultaneously, although dark spots (denoted by black arrows)
indicate imperfect stitching occasionally. Boundaries from growth C (denoted by gold
arrows) are always visible with varying amounts of discontinuity.

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