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

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

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

Chem. Eur. J. 2012, 00, 0 0  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &1&
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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 detected, revealing complete removal of the catalyst layer
catalyst layer on the Si substrate by immersing it in concen- from the graphene (Figure 2 b).
trated HF (48 %), allowing the graphene to be detached and Transmission electron microscopy (TEM) examination of
flow freely in solution (Figure 1). the graphene films showed a honeycomb lattice structure
Scanning electron microscopy (SEM) investigations re- with a threefold symmetry associated with the graphene
vealed the formation of a continuous graphene film showing structure (Figure 3 a).[23] A single-area electron diffraction
some wrinkles and scrolls, which are associated with the (SAED) pattern reveals two rings corresponding to the dif-
thermal expansion coefficient difference between the Ni-cat- fractions of the < 002 > and < 101 > planes of nanocrystal-
alyst layer and the graphene formed during synthesis (Fig- line, hexagonally ordered graphitic sheets (inset in Fig-
ure 2 a).[12, 22] The corresponding energy-dispersive X-ray ure 3 a). Grazing incidence X-ray diffraction (GIXRD) of
(EDX) spectrum shows only C (graphene) besides the sig- 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
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
values (26.5 to 22.28 according to Braggs equation). This
in 48 % HF aqueous solution (a, b), which delaminated the graphene slightly larger d spacing is probably due to a lower degree of
from the substrate and resulted in a freely floating graphene sheet (c). crystallization and thus the presence of some defects in

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Synthesis, Characterization, and Properties of Low-Layer Graphene

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
Figure 3. a) High-resolution TEM image of the CVD-derived graphene formation of single-layer graphene at the measured spatial
film. Representative SAED pattern of the graphene sample is given as
inset of a. b) XRD spectrum of the transferred graphene on SiO2/Si
area (ca. 2 mm).[28] The 2D band got broader as was studied
wafer. Focused pattern between 15308 2q is given as inset of b. 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
CVD-derived graphene, which resulted in a somewhat ratio for different areas over the sample provides reliable in-
broader and therefore shifted C (200) reflection in the XRD formation with respect to the quality of large-area, transpar-
pattern. Besides X-ray diffraction, Raman spectroscopy is a ent graphene. Two randomly chosen areas are marked with
versatile and precise technique to probe the graphene quali- arrows 1 and 2 in Figure 4 b. Their distance is significantly
ty, especially the number of layers.[26, 27, 28] Thus, shape, posi- larger than the diameter of the Raman laser spot (ca. 2 mm).
tion, and relative intensities of D, G, and 2D bands allow es- As can be seen, the intensity of the D band is very low for
timating the quality of the graphene films.[29, 30, 31] The D all areas studied, indicating a highly ordered graphene struc-
band[32] (ca. 1353 cm1) is related to the breathing mode of ture as deposited. However, the sharpness of the G band
the rings of sp2-hybridized carbon and is activated by the and intensity ratio I(G)/I(D) varies between 0.21.1, indicat-
presence of defects. Thus, the intensity of the D band does ing that the number of layers is lower by a conservative esti-
not relate to the number of layers, but is affected by the mate of at least ten (Figures 4 and 4 d).[34] Such Raman line-
amount of disorder. The G band[33] (ca. 1580 cm1) relates to mapping results are thus a good experimental proof to sug-
the in-plane vibration of sp2 C atoms in single-layer gra- gest that almost single- up to a few-layer graphene was ob-
phene and is located at slightly higher wavenumbers than in tained by the employed CVD method.
graphite (Figure 4 a). The 2D band[28] (ca. 2702 cm1), which The reason for the thickness inhomogeneity within the
is the second-order zone boundary phonon signal of the D sample can be attributed to the microstructure of the Ni-cat-

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J. J. Schneider et al.

alyst layer responsible for the formation of graphene. Sub- silicon oxide (SiOx) passivation layer. This graphene sample
strates onto which Ni is deposited were thermally annealed had a uniform sheet structure without graphene nanoribbons
to form mm-sized nearly atomically flat Ni grains before the present (Figure 2). Measurements performed by using the
CVD growth process was started (see the Experimental Sec- transmission line method (TLM) showed a sheet resistance
tion).[35] The mm-sized Ni grains thus contain multiple grain of (Rsheet) of approximately 1435 W per &, a contact resist-
boundaries, which were formed during the thermal treat- ance (Rc) of about 127 W, and specific contact resistance
ment of the sample. This can be clearly detected in an (Rsc) of approximately 2.8  104 W cm2 (defined as Rsc =
atomic force microscopy (AFM) image of the annealed Ni- Rc2 w2/Rsheet, in which w is contact width of 50 mm). Transis-
catalyst film before the CVD graphene growth starts tor output characteristics for the graphene sample demon-
(Figure 5). Accordingly, the uneven and rough surface of the 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 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- Figure 6. a) Output current/voltage (I/V) characteristics and b) input I/V
responding sample. (current/voltage) characteristics of the graphene film.

Ni surface with its particulate surface morphology and the

presence of inter grain boundaries is strongly affecting the sponse of a transistor for different values of gate voltage,
graphene-film growth.[22] parallel to the gas-sensing results (see below) clearly indicat-
ed the p characteristics of graphene that upon application of
Electrical measurements on CVD graphene: Electrical char- a gate/source voltage led to a loss of drain current. The
acterization of the CVD-derived graphene was achieved by modulation can be further improved by appropriate nano-
transferring individual graphene flakes onto a 10 mm  structuring. The hysteresis behavior was also investigated
10 mm < 100 > silicon substrate coated with a 230 nm-thick for the sample. Only a small difference was measured for in-

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Synthesis, Characterization, and Properties of Low-Layer Graphene
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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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.
Figure 8. a) Transient response and b) sensor signal of CVD-graphene
2 mm). The laser power (ca. 20 mW) was attenuated on the sample in the
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. 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
Conclusion 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
We have demonstrated that single-layer to few-layer gra- transparent graphene specimen was fixed, was partially O2-plasma treat-
phene can be obtained by a direct CVD method by using Ni ed to etch some part of graphene and isolate the drain and source con-
as catalyst layer. The material can be transferred to nonspe- tacts from the bottom gate contact (Figure 9).
cific substrates by a solvent-deposition process, which al- Gas-sensor measurements on CVD-derived graphene: Gas-sensor (DC
electrical) measurements were performed to monitor the sensor response
lowed its electrical characterization as p-type electronic ma-
of graphene to CO and H2 in dry nitrogen.[47, 48] The sensing layer was de-
terial. Inhomogeneity in the number of layers of graphene
posited by immersing the alumina substrates with Pt electrodes on the
on randomly selected areas of the graphene flakes is attrib- front side and a Pt heater on the back side, as shown in Figure 10.
uted to the formation of grain-boundaries on the Ni surface Defined concentrations of H2 (200, 500, 1000, 2500, 5000, and
during thermal annealing. These have been studied by micro 10 000 ppm) and of CO (50, 100, and 250 ppm) were obtained from a PC-
Raman spectroscopy. Gas-sensor measurements upon H2 controlled gas-mixing bench, which consisted of a combination of com-
and CO exposition revealed an increase in the resistance of puter-controlled mass-flow controllers and computer-controlled valves to
the graphene films, indicating that CVD graphene is a prom- 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
ising candidate as sensitive gas sensor towards both reducing
chamber and operated. Besides RT experiments, the studies were per-
gases at higher temperatures.
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
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.

[1] A. K. Geim, K. S. Novoselov, Nat. Mater. 2007, 6, 183 191.

[2] C. Lee, X. Wei, J. W. Kysar, J. Hone, Science 2008, 321, 385 388.
[3] D. C. Elias, R. R. Nair, T. M. G. Mohiuddin, S. V. Morozov, P. Blake,
M. P. Halsall, A. C. Ferrari, D. W. Boukhvalov, M. I. Katsnelson,
A. K. Geim, K. S. Novoselov, Science 2009, 323, 610 613.
[4] I. Jung, D. A. Dikin, R. D. Piner, R. S. Ruoff, Nano Lett. 2008, 8,
4283 4287.
[5] A. Peigney, C. Laurent, E. Flahaut, R. R. Bacsa, A. Rousset,
Carbon 2001, 39, 507 514.
[6] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang,
S. V. Dubonos, I. V. Grigorieva, A. A. Firsov, Science 2004, 306,
666 669.
[7] Y. Xu, Z. Liu, X. Zhang, Y. Wang, J. Tian, Y. Huang, Y. Ma, X.
Zhang, Y. Chen, Adv. Mater. 2009, 21, 1275 1279.
[8] K. S. Kim, Y. Zhao, H. Jang, S. Y. Lee, J. M. Kim, K. S. Kim, J.-H.
Ahn, P. Kim, J.-Y. Choi, B. H. Hong, Nature 2009, 457, 706 710.
[9] C. Berger, Z. Song, X. Li, X. Wu, N. Brown, C. Naud, D. Mayou, T.
Li, J. Hass, A. N. Marchenkov, E. H. Conrad, P. N. First, W. A.
de Heer, Science 2006, 312, 1191 1196.
[10] J. Coraux, A. T. NDiaye, C. Busse, T. Michely, Nano Lett. 2008, 8,
565 570.
[11] P. W. Sutter, J.-I. Flege, E. A. Sutter, Nat. Mater. 2008, 7, 406 411.
[12] X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner, A. Velama-
kanni, I. Jung, E. Tutuc, S. K. Banerjee, L. Colombo, R. S. Ruoff,
Science 2009, 324, 1312 1314.
[13] M. Gautam, A. H. Jayatissa, Mater. Sci. Eng. C 2011, 31, 1405 1411.
[14] R. K. Joshi, H. Gomez, F. Alvi, A. Kumar, J. Phys. Chem. C 2010,
114, 6610 6613.
Figure 9. a) Four parallel TLM line structures with Ni contacts on gra- [15] F. Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake, M. I.
phene and b) resistance between contacts versus contact distance. Katsnelson, K. S. Novoselov, Nat. Mater. 2007, 6, 652 655.
[16] K. S. Subrahmanyam, S. R. C. Vivekchand, A. Govindaraj, C. N. R.
Rao, J. Mater. Chem. 2008, 18, 1517 1523.
[17] R. Arsat, M. Breedon, M. Shafiei, P. G. Spizziri, S. Gilje, R. B.
Kaner, K. Kalantar-zadeh, W. Wlodarski, Chem. Phys. Lett. 2009,
467, 344 347.
[18] L.-S. Zhang, W. D. Wang, X.-Q. Liang, W.-S. Chu, W.-G. Song, W.
Wang, Z.-Y. Wu, Nanoscale 2011, 3, 2458 2460.
[19] A. Kaniyoor, R. I. Jafri, T. Arockiadoss, S. Ramaprabhu, Nanoscale
2009, 1, 382 386.
[20] W. Wu, Z. Liu, L. A. Jauregui, Q. Yu, R. Pillai, H. Cao, J. Bao, Y. P.
Chen, S.-S. Pei, Sensors and Actuators B: Chemical 2010, 150, 296
[21] G. Singh, A. Choudhary, D. Haranath, A. G. Joshi, N. Singh, S.
Singh, R. Pasricha, Carbon 2012, 50, 385 394.
[22] S. J. Chae, F. Gnes, K. K. Kim, E. S. Kim, G. H. Han, S. M. Kim,
H.-J. Shin, S.-M. Yoon, J.-Y. Choi, M. H. Park, C. W. Yang, D.
Pribat, Y. H. Lee, Adv. Mater. 2009, 21, 2328 2333.
[23] W. Eck, A. Kller, M. Grunze, B. Vlkel, A. Glzhuser, Adv.
Mater. 2005, 17, 2583 2587.
[24] X. Wang, H. You, F. Liu, M. Li, L. Wan, S. Li, Q. Li, Y. Xu, R. Tian,
Z. Yu, D. Xiang, J. Cheng, Chem. Vap. Deposition 2009, 15, 53 56.
[25] C. H. See, A. T. Harris, Ind. Eng. Chem. Res. 2007, 46, 997 1012.
[26] Z. Ni, Y. Wang, T. Yu, Z. Shen, Nano Res. 2008, 1, 273 291.
[27] A. C. Ferrari, J. C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F.
Mauri, S. Piscanec, D. Jiang, K. S. Novoselov, S. Roth, A. K. Geim,
Phys. Rev. Lett. 2006, 97, 187401.
[28] L. G. Canado, A. Reina, J. Kong, M. S. Dresselhaus, Phys. Rev. B
2008, 77, 245408.
Figure 10. Layout of a planar alumina substrate with integrated platinum [29] L. M. Malard, M. A. Pimenta, G. Dresselhaus, M. S. Dresselhaus,
electrodes and separated heater electrodes for sensor tests. Phys. Rep. 2009, 473, 51 87.

Chem. Eur. J. 2012, 00, 0 0  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &7&
These are not the final page numbers!
J. J. Schneider et al.

[30] Y. Y. Wang, Z. H. Ni, Z. X. Shen, H. M. Wang, Y. H. Wu, Appl. [40] O. Leenaerts, B. Partoens, F. M. Peeters, Phys. Rev. B 2008, 77,
Phys. Lett. 2008, 92, 043121. 125 416.
[31] J. S. Bunch, A. M. van der Zande, S. S. Verbridge, I. W. Frank, D. M. [41] Y.-H. Zhang, Y.-B. Chen, K.-G. Zhou, C.-H. Liu, J. Zeng, H.-L.
Tanenbaum, J. M. Parpia, H. G. Craighead, P. L. McEuen, Science Zhang, Y. Peng, Nanotechnology 2009, 20, 185504.
2007, 315, 490 493. [42] Y. Zou, F. Li, Z. Zhu, M. Zhao, X. Xu, X. Su, Eur. Phys. J. B: Con-
[32] C. Thomsen, S. Reich, Phys. Rev. Lett. 2000, 85, 5214 5217. densed Matter and Complex Systems 2011, 81, 475 479.
[33] M. A. Pimenta, G. Dresselhaus, M. S. Dresselhaus, L. G. Cancado, [43] A. Z. Sadek, C. Zhang, Z. Hu, J. G. Partridge, D. G. McCulloch, W.
A. Jorio, R. Saito, Phys. Chem. Chem. Phys. 2007, 9, 1276 1290. Wlodarski, K. Kalantar-Zadeh, J. Phys. Chem. C 2009, 113, 238
[34] S. Kumar, N. McEvoy, T. Lutz, G. P. Keeley, V. Nicolosi, C. P. 242.
Murray, W. J. Blau, G. S. Duesberg, Chem. Commun. 2010, 46, [44] J. S. Arellano, L. M. Molina, A. Rubio, J. A. Alonso, J. Chem. Phys.
1422 1424. 2000, 112, 8114 8119.
[35] A. Reina, X. Jia, J. Ho, D. Nezich, H. Son, V. Bulovic, M. S. Dressel- [45] Y. Okamoto, Y. Miyamoto, J. Phys. Chem. B 2001, 105, 3470 3474.
haus, J. Kong, Nano Lett. 2008, 8, 30 35. [46] G. Ko, H. Y. Kim, J. Ahn, Y. M. Park, K. Y. Lee, J. Kim, Curr. Appl.
[36] H. Mousavi, Commun. Theor. Phys. 2011, 56, 373. Phys. 2010, 10, 1002 1004.
[47] J. Khanderi, R. C. Hoffmann, A. Gurlo, J. J. Schneider, J. Mater.
[37] H. Chang, J. D. Lee, S. M. Lee, Y. H. Lee, Appl. Phys. Lett. 2001, 79,
Chem. 2009, 19, 5039 5046.
3863 3865.
[48] T. Sahm, A. Gurlo, N. Barsan, U. Weimar, Partic. Sci. and Technol.
[38] J. Zhao, A. Buldum, J. Han, J. P. Lu, Nanotechnology 2002, 13, 195.
2006, 24, 441 452.
[39] R. K. Joshi, J. E. Weber, Q. Hu, B. Johnson, J. W. Zimmer, A.
Received: May 29, 2012
Kumar, Sensors and Actuators B: Chemical 2010, 145, 527 532.
Published online: && &&, 0000

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Synthesis, Characterization, and Properties of Low-Layer Graphene
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

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