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doi: 10.1038/nnano.2010.132
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RoII-to-roII production of 30-inch graphene fiIms
for transparent eIectrodes
Sukang Bae, Hyeongkeun Kim, Youngbin Lee, XianIang Xu, Jae-Sung Park, Yi Zheng,
Jayakumar Balakrishnan, Tian Lei, Hye Ri Kim, Young Il Song, Young-Jin Kim, Kwang S.
Kim, Barbaros zyilmaz, Jong-Hyun Ahn, Byung Hee Hong & Sumio Iijima

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A. Homogeneity analysis of a large-scale graphene film

Fig. S1. Distribution oI sheet resistances tested on the 300 pieces oI 1x1 inch
2
monolayer
graphene/PET Iilms. The inset shows the corresponding spatial distribution on a 20x15 inch
2

graphene/PET Iilm.

B. Strain analysis of graphene electrodes

Fig S2. Log-scaled R/R vs. strain plot Ior a graphene electrode used in touch screen panel
devices. The parameters and equations Irom Ref. S1 are used to calculate the strain. Note that we
can simply use F ~1 in the case oI ultrathin Iilm on a thick substrate.



S1) Z. Suo, E. Y. Ma, H. Gleskova, S. Wagner. Mechanics oI rollable and Ioldable Iilm-on-Ioil electronics. Appl.
Phvs. Lett. 74, 1177 (1999).
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C. Enlarged grain sizes of Cu foil after annealing/growth

Fig. S3. Grain size analyses oI Cu Ioils beIore and aIter annealing/growth. (A) Optical
microscope images oI Cu Ioils beIore and aIter graphene growth at 1,000C. The cracks on Ioils
usually Iormed at grain boundaries. (B) Optical images oI polished Cu Ioils beIore and aIter
annealing at 1,000C, Iollowed by brieI acid treatment. The grain boundaries are etched Iaster
than single crystalline surIaces, resulting in the Iormation line patterns on the polished Cu surIace.

D. SEM images of transferred graphene films


Fig. S4. SEM images oI 1~3-layer graphene Iilms transIerred on a PET by a roll-to-roll method. The
Iirst transIerred graphene layer shows adhesive residues, while the additional transIers look very clean.
We supposed that the adhesion Iorce between graphene and PET competes with the Iorce
between graphene and thermal release tapes, leaving some adhesive residues and deIects. In
the case oI the second/third transIer, the adhesive Iorces oI thermal release tapes look much
smaller than graphene-graphene adhesion, and thereIore, almost complete transIer can be
made Ior additional transIers.
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E. AFM analysis of graphene films














Fig. S5. A contact-mode AFM image oI the graphene Iilm transIerred on a PET Iilm. A Iew nm
high ripples are usually Iormed due to the diIIerent thermal expansion oI Cu and graphene, and
the cracks are Iormed during transIer process. The height proIile (red solid line) measured along
the dashed red line indicates the thicknesses oI mono- and bi-layers approximately.

F. TEM images of as-grown graphene films









Fig. S6. High-resolution TEM images showing the Iolded edges oI as-grown graphene Iilms with
diIIerent number oI layers.

G. Ultraviolet photoelectron spectroscopy (UPS) analysis of graphene films

Table S1. Work Iunctions (eJ) oI multiple transIerred graphene Iilms measured by UPS.
No. transIer 1 2 3 4
beIore HNO
3
doping
*
4.272 4.296 4.315 4.401
aIter HNO
3
doping 4.414 4.462 4.476 4.489
*The work Iunctions oI single-layer and bilayer graphene measured by scanning Kelvin probe microscopy
(SKPM) are 4.57 eV and 4.69 eV respectively (Ref. Y. Yu et al. Nano Lett. 9, 3430 (2009)).



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Fig. S7. UPS spectra oI HNO
3
-doped graphene Iilms with diIIerent number oI stacked layers.
The binding energy increases with the number oI stacked graphene layers.

H. XPS spectra of transferred 2-layer graphene films








Fig S8. XPS spectra oI 2-monolayer graphene Iilms transIerred on SiO
2
substrates. The black and red
lines denote the XPS spectra beIore and aIter HNO
3
doping, respectively. The higher energy C1s
peaks related to carbon-oxygen bonds are oIten observed in CVD-grown graphene samples, which is
probably due to oxygen and amorphous carbon contamination inside the growth chamber.


292 290 288 286 284 282
400
800
1200
1600
2000
C=O C-O C-C
C1s
~0.03eV
~0.11eV
2L_Before HNO
3
2L_After HNO
3


I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
)
Binding Energy (eV)
11.8 11.7 11.6 11.5 11.4 11.3
0
500
1000


I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
)
Binding energy (eV)
1 layer
2 layer
3 layer
4 layer
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I. Origin of low sheet resistance







Fig S9. Sheet resistance vs. doping with diIIerent charge carrier mobility. The sheet resistance is
calculated by 1/ 1/ne. During the etching process, the graphene can be p-doped by
etchants such as ammonium persulIate or iron chloride. These etchants are usually strong
oxidizing agents. ThereIore, the electrons can be withdrawn Irom graphene during the redox
process, which is supposed to be the reason Ior the low sheet resistance oI as-prepared graphene
Iilms. This can be evidenced by Dirac points showing up around V
g
~60 V in an ambient
condition, implying the doping density (n) is ~ 4.26 x 10
12
cm
-2
beIore HNO
3
doping (E
D
~0.265
eV). The Fermi energy level shiIt measured by UPS is ~0.130 V aIter HNO
3
doping (Fig 3d,
inset), and then the overall deduced doping level considering both etching and HNO
3
doping is
calculated to be ~9.43 x 10
12
cm
-2
(E
D
~0.395 eV).
1. Sheet resistance enhancement by various wet chemical p-dopants







Fig S10. Decrease oI sheet resistance vs. various wet doping agent. The large-area graphene can
be unintentionally p-doped by etchants such as ammonium persulIate or iron chloride, leading to
the low sheet resistance beIore additional doping. In the case oI the roll-to-roll method, the sheet
resistance aIter HNO
3
doping is decreased Irom 272 to 108 Ohm/sq (~59 decrease). We tested
various doping agent that have been used Ior carbon nanotubes (Ref. 25 in the main text), and
Iound that HNO
3
is suitable Ior practical applications.
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K. High voltage characteristics of graphene films






Fig S11. High voltage V characteristics oI a monolayer graphene Iilm transIerred on a PET by a
roll-to-roll method. The non-linear V characteristics oI the graphene Iilm on a PET substrate is
not observed between V
SD
-25~25 V. II V
SD
~ 30 V, The devices tend to breakdown beIore
reaching the saturation oI current probably due to deIormation oI PET (Tg~150C) substrates by
heat dissipated Irom the contact. In the case oI SiO
2
/Si substrates, the graphene Iilm withstands
V
SD
-50~50 V. Considering the practical operation voltages oI commercial electronic devices, V
SD

20 V, the graphene electrode is expected to be reliable Ior most oI high-voltage applications
including LCD and OLED.
L. Structures of graphene-based touch screen devices













Fig. S12. Structure and working principle oI graphene-based touch screen devices. The
protective conducting layer was not used in the actual experiment.
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