FULL PAPER

DOI: 10.1002/chem.201201880

Synthesis, Characterization, Electronic and Gas-Sensing Properties towards

H2 and CO of Transparent, Large-Area, Low-Layer Graphene

Emine Kayhan,[a] Ravi Mohan Prasad,[b] Alexander Gurlo,[b] Oktay Yilmazoglu,[c]

Jrg Engstler,[a] Emanuel Ionescu,[b] Songhak Yoon,[d] Anke Weidenkaff,[d] and
Jrg J. Schneider*[a]
Dedicated to Professor Dr. Dieter Fenske on the occasion of his 70th birthday

Abstract: Low-layered, transparent
graphene is accessible by a chemical
vapor deposition (CVD) technique on
a Ni-catalyst layer, which is deposited
on a < 100 > silicon substrate. The
number of graphene layers on the sub-
strate is controlled by the grain boun-
daries in the Ni-catalyst layer and can
be studied by micro Raman analysis.
Electrical studies showed a sheet resist-
ance (Rsheet) of approximately
1435 W per &, a contact resistance (Rc)
of about 127 W, and a specific contact
resistance (Rsc) of approximately 2.8 
104 W cm2 for the CVD graphene sam-
ples. Transistor output characteristics
for the graphene sample demonstrated
linear current/voltage behavior. A cur-
Keywords: chemical vapor deposi-
tion electrical properties
graphene Raman spectroscopy
sensors
rent versus voltage (IdsVds) plot clearly
indicates a p-conducting characteristic
of the synthesized graphene. Gas-
sensor measurements revealed a high
sensor activity of the low-layer gra-
phene material towards H2 and CO. At
300 8C, a sensor response of approxi-
mately 29 towards low H2 concentra-
tions (1 vol %) was observed, which is
by a factor of four higher than recently
reported.

Introduction at a time. Several methods of formation of graphene, includ-

Graphene has attracted intense scientific interest due to its
exceptional electrical,[1] mechanical[2] and chemical[3] proper-
ties over the last couple of years. This strictly two-dimen-
sional (2D) material has potential applications in transis-
tors,[2] flexible electronics,[3] and as gas-sensor material.[4] Es-
pecially for the last application, its theoretical high surface
area of approximately 2600 m2 g1[5] might allow altering its
electrical conductivity to the ultimate limit of one molecule
[a] E. Kayhan, Dr. J. Engstler, Prof. Dr. J. J. Schneider
Technische Universitt Darmstadt
Eduard-Zintl-Institut, Fachbereich Chemie
Fachgebiet Anorganische Chemie
Petersenstrasse 18, 64287 Darmstadt (Germany)
Fax: (+ 49) 6151-163470
E-mail: joerg.schneider@ac.chemie.tu-darmstadt.de
[b] R. M. Prasad, Dr. A. Gurlo, Dr. E. Ionescu
Technische Universitt Darmstadt
Fachbereich Material- und Geowissenschaften
Petersenstrasse 22, 64287 Darmstadt (Germany)
[c] Dr. O. Yilmazoglu
Technische Universitt Darmstadt
Fachgebiet fr Hochfrequenzelektronik
64283 Darmstadt (Germany)
[d] S. Yoon, Prof. Dr. A. Weidenkaff
EMPA, Solid State Chemistry and Catalysis
8600 Dbendorf (Switzerland)
ing micromechanical cleavage,[6] chemical exfoliation,[7] and
epitaxial growth by chemical vapor deposition (CVD),[8]
have been utilized to fabricate high-quality, large-area
mono-layer graphene on various substrates. The highest
quality graphene in terms of its monolayered defect-free
structure is obtained by mechanical cleavage of highly ori-
ented pyrolytic graphite (HOPG)[6] and by decomposition of
SiC.[9] However, both methods have drawbacks in scalability.
Other methods, such as the combined chemical exfoliation
and reduction technique, which allow scalability on the one
hand, suffer of aggregation caused by strong pp stacking
and van der Waals aggregation of individual graphene
sheets on the other hand and thus have the problem of get-
ting few-layer graphene. However, when using high-quality
metallic substrates, such as Ir,[10] Ru,[11] Ni,[8] or Cu[12] in a
CVD process and employing a strict control of synthesis
temperature and control of the cooling rate and substrate
quality, the graphene layer aggregation can be avoided, and
formation of graphene with controllable thicknesses down
to a monolayer is possible.
Due to its low resistance and high integration capability
in electronics, high impedance circuits necessary for metal-
oxide gas sensors are not required for graphene-based gas-
sensing devices.[13] Therefore, studies on functionalized gra-
phene and bare graphene have revealed that graphene-
based materials are promising candidates as gas sensors.[1321]
Of these, it is important to analyze bare graphene to study
the influence of adsorbant gases on the graphene surface

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without interference of a catalytically active metal or metal-
oxide interface.
Herein, we report the Ni-catalyzed CVD synthesis of few-
layer graphene, the spatial characterization of the few-lay-
ered transparent graphene by micro Raman spectroscopy, its
electrical characterization showing p-semiconductor behav-
ior, as well as studies on the gas-sensing properties towards
low concentrations of CO and H2.

Results and Discussion

Synthesis and characterization of low-layer graphene: A

methane-based CVD growth process operating at 950 8C
and obtained large-scale high-quality crystalline single-to-
few-layer graphene films by using a Ni-catalyst layer as thin
film on a SiO2/Si substrate.[8] The quality of the deposited
Ni-catalyst layer mainly determines the crystalline quality of
the obtained graphene film, which can be monitored by spa-
tially resolved micro Raman investigations. The overall syn-
thesis process leading routinely to the formation of approxi-
mately 1  1 cm2 transparent graphene films is shown in
Scheme 1 (for details, see the Experimental Section).

Figure 2. a) SEM image of a graphene film detached from the substrate/

catalyst layer. b) EDX spectrum of the corresponding area depicted in a.
Scheme 1. Fabrication steps for CV graphene (scheme based on
Ref. [24]).

nals of the substrate (Si and O). No signals of Ni could be

The as-formed graphene layer can be detached from the
catalyst layer on the Si substrate by immersing it in concen-
trated HF (48 %), allowing the graphene to be detached and
flow freely in solution (Figure 1).
Scanning electron microscopy (SEM) investigations re-
vealed the formation of a continuous graphene film showing
some wrinkles and scrolls, which are associated with the
thermal expansion coefficient difference between the Ni-cat-
alyst layer and the graphene formed during synthesis (Fig-
ure 2 a).[12, 22] The corresponding energy-dispersive X-ray
(EDX) spectrum shows only C (graphene) besides the sig-
Figure 1. Photographs showing the transfer process for a centimeter-scale
graphene film grown on a Ni/SiO2/Si substrate. SiO2 and Ni were etched
in 48 % HF aqueous solution (a, b), which delaminated the graphene
from the substrate and resulted in a freely floating graphene sheet (c).
detected, revealing complete removal of the catalyst layer
from the graphene (Figure 2 b).
Transmission electron microscopy (TEM) examination of
the graphene films showed a honeycomb lattice structure
with a threefold symmetry associated with the graphene
structure (Figure 3 a).[23] A single-area electron diffraction
(SAED) pattern reveals two rings corresponding to the dif-
fractions of the < 002 > and < 101 > planes of nanocrystal-
line, hexagonally ordered graphitic sheets (inset in Fig-
ure 3 a). Grazing incidence X-ray diffraction (GIXRD) of
such a sample showed a characteristic weak and broad peak
at approximately 22.28, which can be indexed to the < 200 >
reflection, the most prominent signal for the graphitic struc-
ture (Figure 3 b).[24, 25, 14]
TEM and XRD results for the graphene film gave the
same interlayer spacing between graphene sheets, corre-
sponding to the < 002 > (0.399 nm is calculated from XRD
and TEM). The interlayer distance d of graphene is larger
than that of graphite (0.335 nm), which in turn explains the
shift of the < 002 > peak of graphite towards lower 2q
values (26.5 to 22.28 according to Braggs equation). This
slightly larger d spacing is probably due to a lower degree of
crystallization and thus the presence of some defects in

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Synthesis, Characterization, and Properties of Low-Layer Graphene
Figure 3. a) High-resolution TEM image of the CVD-derived graphene
film. Representative SAED pattern of the graphene sample is given as
inset of a. b) XRD spectrum of the transferred graphene on SiO2/Si
wafer. Focused pattern between 15308 2q is given as inset of b.
CVD-derived graphene, which resulted in a somewhat
broader and therefore shifted C (200) reflection in the XRD
pattern. Besides X-ray diffraction, Raman spectroscopy is a
versatile and precise technique to probe the graphene quali-
ty, especially the number of layers.[26, 27, 28] Thus, shape, posi-
tion, and relative intensities of D, G, and 2D bands allow es-
timating the quality of the graphene films.[29, 30, 31] The D
band[32] (ca. 1353 cm1) is related to the breathing mode of
the rings of sp2-hybridized carbon and is activated by the
presence of defects. Thus, the intensity of the D band does
not relate to the number of layers, but is affected by the
amount of disorder. The G band[33] (ca. 1580 cm1) relates to
the in-plane vibration of sp2 C atoms in single-layer gra-
phene and is located at slightly higher wavenumbers than in
graphite (Figure 4 a). The 2D band[28] (ca. 2702 cm1), which
is the second-order zone boundary phonon signal of the D
Chem. Eur. J. 2012, 00, 0 0  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Figure 4. a) Raman spectra for a CVD-derived graphene film. b) Optical
image of graphene transferred on SiO2/Si wafer. c), d) Raman-line map-
pings of the areas depicted with arrows 1 and 2 in b, respectively. Spectra
17 are from area 1 (see arrow) and 813 are from area 2 (see arrow).
band usually appears as a sharp and one-signal peak in
single-layer graphene, with a full width at half maximum (G)
of around 30 cm1.[28] The intensity ratio I(G)/I(2D) allows
furthermore to estimate of the numbers of layers in gra-
phene-based materials. It is therefore most often used to dis-
criminate single-layer from multi-layer graphene or graphite.
A detailed micro Raman analysis on the prepared graphene
sample was performed (Figure 4). For our CVD-derived gra-
phene specimens G of the 2D band were 30 cm1 indicating
formation of single-layer graphene at the measured spatial
area (ca. 2 mm).[28] The 2D band got broader as was studied
at some randomly chosen sample areas indicating few-layer
graphene. The ratio I(G)/I(2D) decreased, whereas the
number of layers increased. Thus, the determination of this
ratio for different areas over the sample provides reliable in-
formation with respect to the quality of large-area, transpar-
ent graphene. Two randomly chosen areas are marked with
arrows 1 and 2 in Figure 4 b. Their distance is significantly
larger than the diameter of the Raman laser spot (ca. 2 mm).
As can be seen, the intensity of the D band is very low for
all areas studied, indicating a highly ordered graphene struc-
ture as deposited. However, the sharpness of the G band
and intensity ratio I(G)/I(D) varies between 0.21.1, indicat-
ing that the number of layers is lower by a conservative esti-
mate of at least ten (Figures 4 and 4 d).[34] Such Raman line-
mapping results are thus a good experimental proof to sug-
gest that almost single- up to a few-layer graphene was ob-
tained by the employed CVD method.
The reason for the thickness inhomogeneity within the
sample can be attributed to the microstructure of the Ni-cat-
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alyst layer responsible for the formation of graphene. Sub-
strates onto which Ni is deposited were thermally annealed
to form mm-sized nearly atomically flat Ni grains before the
CVD growth process was started (see the Experimental Sec-
tion).[35] The mm-sized Ni grains thus contain multiple grain
boundaries, which were formed during the thermal treat-
ment of the sample. This can be clearly detected in an
atomic force microscopy (AFM) image of the annealed Ni-
catalyst film before the CVD graphene growth starts
(Figure 5). Accordingly, the uneven and rough surface of the
Figure 5. a) Optical-microscopy image of the thermally annealed, Ni-cata-
lyst layer (e-beam deposited) on SiO2/Si wafer. b) AFM image of the cor-
responding sample.
Ni surface with its particulate surface morphology and the
presence of inter grain boundaries is strongly affecting the
graphene-film growth.[22]
Electrical measurements on CVD graphene: Electrical char-
acterization of the CVD-derived graphene was achieved by
transferring individual graphene flakes onto a 10 mm 
10 mm < 100 > silicon substrate coated with a 230 nm-thick
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J. J. Schneider et al.
silicon oxide (SiOx) passivation layer. This graphene sample
had a uniform sheet structure without graphene nanoribbons
present (Figure 2). Measurements performed by using the
transmission line method (TLM) showed a sheet resistance
of (Rsheet) of approximately 1435 W per &, a contact resist-
ance (Rc) of about 127 W, and specific contact resistance
(Rsc) of approximately 2.8  104 W cm2 (defined as Rsc =
Rc2 w2/Rsheet, in which w is contact width of 50 mm). Transis-
tor output characteristics for the graphene sample demon-
strated a linear current/voltage behavior with some gate
modulation [Ids(@Vgs = 15 V)/Ids(@Vgs = 15 V) = 1.5:1.25]
(Figure 6 a). A current versus voltage (IdsVds) plot, the re-
Figure 6. a) Output current/voltage (I/V) characteristics and b) input I/V
(current/voltage) characteristics of the graphene film.
sponse of a transistor for different values of gate voltage,
parallel to the gas-sensing results (see below) clearly indicat-
ed the p characteristics of graphene that upon application of
a gate/source voltage led to a loss of drain current. The
modulation can be further improved by appropriate nano-
structuring. The hysteresis behavior was also investigated
for the sample. Only a small difference was measured for in-
Chem. Eur. J. 0000, 00, 0 0
Synthesis, Characterization, and Properties of Low-Layer Graphene
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creased gate voltage (Vgs from 20 to 20 V) compared with
decreased gate voltages (Vgs from 20 to 20 V; Figure 6 b).

Sensoric studies of CVD-derived graphene towards H2 and

CO: The large surface area with unique electronic proper-
ties makes graphene an interesting candidate for gas-sensor
applications.[15] The conductivity of graphene (that arises
from delocalized p electrons) is directly altered by the
probe molecules adsorbed at the graphene surface.[36] Be-
cause graphene is a strictly 2D material and exposes nearly
its complete surface area to the gas atmosphere, the effect
of adsorbing-gas molecules on the conductivity is rather
large. Besides reports of gas-sensing properties of bare gra-
phene towards H2 and CO detection,[14, 16, 15, 17, 18, 13] studies of
graphene gas sensors functionalized by metal and metal
oxides, such as Pt,[19] Pd,[20] and ZnO,[21] have been reported.
Studies of bare graphenegas interactions are important, be-
cause they allow examining the adsorbant/graphene influ-
ence without additional interference of the metal particle/
graphene interface. The graphene specimen used for the
sensoric measurements was a continuous film. As shown in
the AFM image of the specimen, the graphene film consists
of micrometer-sized areas, which are separated from each
other by grains, however, the whole film specimen is contin-
uous. Thin-layered graphene was exposed to CO or H2 at
different concentrations and its gas-sensing activity was
studied by monitoring the resistance change. Exposure of re-
ducing gases, such as CO and H2 on a CVD-derived gra-
phene surface resulted in an increase of the resistance of the
graphene film. This confirms p-type conductivity of the
transferred CVD-derived graphene as was found in the elec-
trical characterization studies (see above). As was reported
previously, chemically derived graphene (by exfoliation/re-
duction route) might give some contradictory results upon Figure 7. a) Transient response and b) sensor signal of CVD-graphene
exposure to different types of e donors. This can be attribut- film to CO (steps of a, b, and c; 50, 100, and 250 ppm, respectively) at
ed to an incomplete chemical reduction of graphene oxide 300 8C.
to graphene, if it is obtained by the exfoliation/reduction
route.[17] However, this effect can be ruled out on CVD-de-
rived graphene studied herein. The gas-sensing response of showed by DFT computations, the adsorption of H2 onto
CVD graphene is similar to that of CNTs[37, 38] and diamond graphene is very weak with binding energies of < 0.1 eV and
surfaces.[39] At room temperature, no resistance change of adsorbate-surface separations between 5.075.50 .[44, 45] Al-
our CVD-derived graphene was observed, if it is exposed to ready at a low amount of adsorbed hydrogen, the graphene
CO (Figure 7 a). DFT studies of CO adsorption on gra- surface was saturated, leading to the same resistance change
phene[4042] suggest small binding energies (0.0080.02 eV), even with increasing hydrogen concentrations (Figure 8 a).
large adsorbate-surface distances (d; 3.702.80 ), and small In addition, due to the limited desorption at room tempera-
adsorption-energy values for CO (Ea ; 0.12 to 0.05 eV). ture, the base-line resistance slightly increased upon hydro-
These findings indicate that CO undergoes a physical ad- gen exposure. Similar behavior was observed required an
sorption on graphene due to rather weak van der Waals in- annealing at 150 8C in vacuum to recover the initial gra-
teractions between the graphene surface and CO. However, phene surface free of adsorbates.[15, 13, 46] At 300 8C, a much
a very small Mulliken charge transfer (0.01 j e j) from gra- higher sensor signal (ca. 29) to a lower H2 concentration
phene to CO suggests that an electrostatic interaction be- (1 vol %) was observed than that reported recently on
tween the graphene and CO does exist.[41, 42] CVD-derived graphene (ca. 7 for 3.35 vol % H2 at
Exposure of graphene towards H2 gas at room tempera- 200 8C.[13])
ture induced a slight increase in the resistance; the latter did
not show a concentration dependency. This behavior can be
explained by the very weak interaction of H2 with graphene
under ambient conditions (Figure 8 a).[20, 43] Again, as was

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Figure 8. a) Transient response and b) sensor signal of CVD-graphene
film to H2 (steps of a, b, c, d, and e; 200, 500, 1000, 5000, and 10 000 ppm,
respectively) at room temperature and 300 8C.
Conclusion
We have demonstrated that single-layer to few-layer gra-
phene can be obtained by a direct CVD method by using Ni
as catalyst layer. The material can be transferred to nonspe-
cific substrates by a solvent-deposition process, which al-
lowed its electrical characterization as p-type electronic ma-
terial. Inhomogeneity in the number of layers of graphene
on randomly selected areas of the graphene flakes is attrib-
uted to the formation of grain-boundaries on the Ni surface
during thermal annealing. These have been studied by micro
Raman spectroscopy. Gas-sensor measurements upon H2
and CO exposition revealed an increase in the resistance of
the graphene films, indicating that CVD graphene is a prom-
ising candidate as sensitive gas sensor towards both reducing
gases at higher temperatures.
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J. J. Schneider et al.
Experimental Section
Synthesis of CVD-derived graphene: Graphene was synthesized by a
CVD method by using Ni-film-deposited silicon wafer as a substrate. Ni
metal (200500 nm) was deposited by electron-beam evaporation on a
SiO2 (600 nm)/Si wafer with < 100 > crystal orientation (p-type, light-
boron doped (from Silicon Materials, Si-Mat)). Substrate (12 cm2) was
placed into the CVD chamber and heated to 950 8C under a flow of
argon (600 sccm) and hydrogen (500 sccm). Substrates were further
heated at that temperature under Ar and H2 flow for 20 min to generate
mm-sized atomically flat Ni grains. It is claimed that the CVD growth of
graphene on atomically flat Ni grains is similar to the growth of graphene
on the surface of a single-crystal substrate in this way.[35] Accordingly, to
get high quality of graphene films, thermal annealing of NiSiO2/Si sub-
strates was conducted. The graphene growth was carried out at 950 8C by
using H2 (5001000 sccm) and CH4 (25 sccm) for 10 min. After the
growth step, CVD chamber was purged with Ar (700 sccm) for 10 min to
flush the remained CH4, and the sample was cooled to RT under flow of
Ar (200 sccm). To etch the underlying Ni layer of graphene, HF (48 %)
was used. When graphene film floated over the solution, the solution was
diluted and finally exchanged multiple times with distilled water, and
then graphene was transferred onto the desired substrate for further
analyses. Similarly, a Cu-coated lacey grid was immersed into the solution
to transfer graphene flakes onto the grid for TEM investigation.
Experimental characterization techniques:
Microscopy: Electron microscopic characterization was performed by
SEM (Philips XL 30 FEG), TEM (FEI Titan 80300@300 keV), AFM
(CP II, Veeco Instruments), and GIXRD (PANalytical XPert PRO 2q
scan with CuKa radiation).
Raman spectroscopy: Micro Raman spectra (ten scans, each lasting 3 s)
were recorded in back-scattering mode with a Horiba LabRam HR 800
micro Raman spectrometer (Horiba Jobin Yvon, Bensheim, Germany)
equipped with an air-cooled Ar + ion laser (emission line l = 514.5 nm).
The excitation line has its own interference filter (to filter out the plasma
emission) and a Raman notch filter (for laser-light rejection). The meas-
urements were performed with a spectrometer grating of 1800 g mm1
and a confocal microscope (long-working-distance objective, magnifica-
tion  50; numerical aperture (NA) 0.5; focused laser-spot diameter ca.
2 mm). The laser power (ca. 20 mW) was attenuated on the sample in the
range of 2 mW20 mW by using neutral density (ND) filters. Spectral res-
olution at the conditions was about 1 cm1 and the spatial resolution was
about 1 mm.
Electrical characterization of CVD-derived graphene: The bottom side of
a n-doped-Si wafer was fixed to a metal electrode using a conducting
silver paste to form a backside gate contact. The top side onto which the
transparent graphene specimen was fixed, was partially O2-plasma treat-
ed to etch some part of graphene and isolate the drain and source con-
tacts from the bottom gate contact (Figure 9).
Gas-sensor measurements on CVD-derived graphene: Gas-sensor (DC
electrical) measurements were performed to monitor the sensor response
of graphene to CO and H2 in dry nitrogen.[47, 48] The sensing layer was de-
posited by immersing the alumina substrates with Pt electrodes on the
front side and a Pt heater on the back side, as shown in Figure 10.
Defined concentrations of H2 (200, 500, 1000, 2500, 5000, and
10 000 ppm) and of CO (50, 100, and 250 ppm) were obtained from a PC-
controlled gas-mixing bench, which consisted of a combination of com-
puter-controlled mass-flow controllers and computer-controlled valves to
mix the certified N2 and H2/N2 and CO/N2 test-gas samples. Graphene
samples were transferred to an alumina substrate in a Teflon-based test
chamber and operated. Besides RT experiments, the studies were per-
formed at 300 8C. The sensor signal is given as the resistance ratio; S =
100 %  (RH2R0)/R0 for H2 and 100 %  (RCOR0)/R0 for CO, in which
RH2, RCO, and R0 denote the sensors resistances in the presence H2, CO
and in the absence of H2 and CO, respectively.
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Synthesis, Characterization, and Properties of Low-Layer Graphene
Figure 9. a) Four parallel TLM line structures with Ni contacts on gra-
phene and b) resistance between contacts versus contact distance.
Figure 10. Layout of a planar alumina substrate with integrated platinum
electrodes and separated heater electrodes for sensor tests.
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FULL PAPER
Acknowledgements
TEM measurements were performed at the Ernst-Ruska-Zentrum fr
Elektronenmikroskopie (ER-C), Jlich, Germany, under the cooperative
research program ERC-TUD 01. We thank Dr. Lothar Houben at ER-C
for technical assistance with the measurements.
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Published online: && &&, 0000
Chem. Eur. J. 0000, 00, 0 0
Synthesis, Characterization, and Properties of Low-Layer Graphene
FULL PAPER
Graphene sensor: Low-layered gra- Chemical Vapor Deposition
phene is accessible by chemical vapor
deposition followed by detachment E. Kayhan, R. M. Prasad, A. Gurlo,
from the substrate by an acid etch. O. Yilmazoglu, J. Engstler, E. Ionescu,
Graphene can be transferred onto vari- S. Yoon, A. Weidenkaff,
ous substrates allowing studies of its J. J. Schneider* . . . . . . . . . . . . . . . &&&&&&&&
chemical sensor activity towards H2
and CO. The picture shows a Synthesis, Characterization, Electronic
1 cm1  1 cm1 graphene piece after and Gas-Sensing Properties towards
detaching from the substrate. TEM H2 and CO of Transparent, Large-
depicts a high degree of order in gra- Area, Low-Layer Graphene
phene and gas-sensing results show a
high sensitivity towards H2 gas (see
figure).

Chem. Eur. J. 2012, 00, 0 0  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org &9&
These are not the final page numbers!