ARTICLE

Surface Doping and Band Gap

Tunability in Hydrogenated Graphene
Bernard R. Matis,† James S. Burgess,† Felipe A. Bulat,‡ Adam L. Friedman,§ Brian H. Houston,^ and
Jeffrey W. Baldwin^,*
†
NRC Postdoctoral Associate, Naval Research Laboratory, Washington, D.C. 20375, United States, ‡Sotera Defense Solutions Inc., Crofton, Maryland 21114,
United States, §Naval Research Laboratory, Code 6361, Washington, D.C. 20375, United States, and ^Naval Research Laboratory, Code 7130, Washington,
D.C. 20375, United States

G
raphene lacks a band gap in its elec-
tronic spectrum; thus graphene's ABSTRACT
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electronically as in conventional semicon-

ductor materials.1
3 The absence of a band
gap is one of the biggest hurdles that must
be overcome before graphene can be used
as an electronic material for use in logic
operations and one that has sparked an
intense research effort to this effect. Chemi-
cal functionalization of graphene4
6 is a
promising method for tuning the material's
unique band structure7,8 and majority car-
rier type for future electronic and optical
We report the first observation of the n-type nature of hydrogenated graphene on SiO2 and
applications.9
12
demonstrate the conversion of the majority carrier type from electrons to holes using surface
Graphane, a recently discovered completely
hydrogenated derivative of graphene,4 is a doping. Density functional calculations indicate that the carrier type reversal is directly related
stable two-dimensional structure in which to the magnitude of the hydrogenated graphene's work function relative to the substrate,
the sp2 C
C double bonds are hybridized to which decreases when adsorbates such as water are present. Additionally, we show by
sp3 C
C single bonds by the addition of temperature-dependent electronic transport measurements that hydrogenating graphene
hydrogen to the carbon lattice. Unlike gra-
induces a band gap and that in the moderate temperature regime [220
375 K], the band gap
phene, which is a zero band gap semimetal,
has a maximum value at the charge neutrality point, is tunable with an electric field effect,
hydrogenated exfoliated and CVD-grown gra-
phene has been shown to exhibit a strong and is higher for higher hydrogen coverage. The ability to control the majority charge carrier in
temperature dependence (ΔR/ΔT < 0) char- hydrogenated graphene, in addition to opening a band gap, suggests potential for chemically
acteristic of semiconducting materials.4,13 modified graphene p
n junctions.
Theoretically, the band gap of hydrogenated
graphene has been shown to depend upon KEYWORDS: graphene . hydrogenated graphene . transport . band gap .
majority charge carrier
the amount of H coverage on each side of
the graphene film as well as the distribu-
tion and ordering of H atoms on the film,
reaching values as high as 5.4 eV.9,14 Several gap, which is tunable by varying the H/C
recent experimental studies have shown that ratio as well.15 In spite of these significant
hydrogenated graphene has a band gap. achievements, many open questions still
Haberer et al. have used angle-resolved remain.
photoemission spectroscopy (ARPES) to The extent to which the band gap can be
measure a band gap in quasi-free-standing tuned electrically has not been investigated, * Address correspondence to
jeff[email protected].
hydrogenated graphene on Au, where the and little is known about the precise role of
size of the gap is tuned by varying the surface adsorbates on the majority carrier Received for review September 7, 2011
H/C ratio.10 Additionally, Balog et al. using type. Here we show that hydrogenated and accepted December 21, 2011.
ARPES have shown that hydrogen adsorbed graphene on SiO2 is an n-type material
Published online December 21, 2011
onto the Moire superlattice positions of and electrically demonstrate the ability to 10.1021/nn2034555
graphene grown on an Ir(111) sub- tune the band gap opening. We report on
strate also induces an appreciable band the ability to convert the majority carrier C 2011 American Chemical Society

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 ARTICLE
type from electrons to holes using surface adsorbates
such as water, which according to our density-func-
tional theory (DFT) model is a consequence of shifting
of the material's work function relative to the sub-
strate's work function upon hydrogenation and subse-
quent adsorption/desorption of atmospheric water.
Furthermore, we demonstrate that in the temperature
regime 220
375 K the band gap has a maximum value
at the charge neutrality point (CNP), is tunable with an
electric field effect, and is increases with the H/C
ratio. This is the first report, to our knowledge, of
the n-type nature of hydrogenated graphene on a
SiO2 substrate as well as the first demonstration of the
complete reversibility of the majority carrier type with
surface doping. The temperature-dependent resistiv- Figure 1. Shift of the CNP and maximum resistivity (Fmax)
ity of hydrogenated graphene shows semiconducting with surface doping. (a) Optical image of a typical graphene
device and electrical schematic. (b) F at 296 K as a function
behavior and is well described by the variable-range of Vg for graphene sample G-X1 (black trace) and three
hopping model. We show that in our devices a band separate levels of hydrogenation (red, green, and blue
gap of up to 50 meV emerges at the CNP and that the traces) with water adsorbates (W). The solid curves are
Lorentzian fits to the data. The dashed line is a guide to
size of the gap can be tuned by varying Vg and/or the the eye. Purple trace: F versus Vg at 296 K for the D/G of 2.94
hydrogen coverage. after heating to 375 K (HG-X1). The shift of the CNP to
negative Vg demonstrates the conversion of the majority
RESULTS AND DISCUSSION carrier type from p to n. (c) F versus Vg at 295 K for graphene
sample G-Hb (black trace) and two separate levels of
Figure 1a is an optical micrograph of a typical hydrogenation (red and blue curves) without water adsor-
graphene device (G-Sq) and electrical schematic used bates. (d) Relative work functions of the graphene (G)
(center), SiO2 surface (S), hydrogenated graphene (HG)
in our experiments. A Van der Pauw cross (referred to (top), and hydrogenated graphene with water adsorbates
here as device X1) with arm dimensions of 500 and (HGþW) (bottom).
200 nm (length and width, respectively) was character-
ized before (G-X1) and after hydrogenation (HG-X1). about 12% of its initial value. The shift of the CNP to nega-
Figure 1b shows F versus Vg at 295 K for HG-X1þW tive Vg indicates that, without the presence of water on the
(þW for “with adsorbed water”) and illustrates both the surface, the hydrogenated graphene film has changed
increase in F and the shift in the CNP away from the from p-type to n-type. Raman spectra collected after
pristine graphene state with increasing levels of hydro- heating show that no measurable change occurs in the
genation, comparable to previously reported hydro- D/G ratio due to heating to 375 K, and we conclude that
genated graphene studies.4,16 The data shown in the change in hydrogen content after heating is negligible.
Figure 1b (with the exception of the purple trace) were Figure 1c shows F versus Vg for device HG-Hb after
intentionally taken as quickly as possible with each having left the hydrogenated sample under vacuum
experiment commencing within 10 min of initiation of for at least 24 h before any electrical measurements
chamber evacuation (Po > 1.0  10
4 Torr), thus not were carried out. Consistent with the slow removal of
allowing for complete removal of physisorbed water. adsorbed water in a vacuum, the CNP is seen to shift to
Ambipolar behavior is observed even for our highest negative Vg values even without heating. The data in
D/G ratios, though F at the CNP is seen to increase by a Figure 1c mirrors the symmetry seen about the gra-
factor of 11, and the CNP has shifted to the right nearly phene CNP in Figure 1b for hydrogenated graphene
30 V. The shift of the CNP to the right, indicating a with adsorbed water and definitively shows that with-
larger fraction of p-type carriers, is attributed to atmo- out water adsorbed to the film's surface, the hydro-
spheric water adsorbed to the hydrogenated graphene genated graphene material is increasingly n-type for
surface. Such behavior indicates that the hydroge- increasing levels of hydrogenation.
nated graphene is doped with holes, while water is It is surprising that although the hydrogenated film
adsorbed to the surface, and that the dopant level can displays n-type behavior, the incorporation of water;
be varied with different degrees of hydrogenation and/ a known electron donor;physisorbed on the surface
or surface water concentrations. results in a p-type material. Our DFT model indicates
To remove the adsorbed water, the sample was that this behavior is due to changes in the materials
heated while continuously maintaining a vacuum work function (WF). While graphene's WF is very close
(P < 1.0  10
6 Torr). The purple trace in Figure 1b to that of the substrate (thermal oxide on silicon),
shows F versus Vg at 295 K after the device was heated evidenced by its CNP being close to 0 Vg, the WF of
to 375 K. Here, the CNP has shifted to negative Vg, a the hydrogenated material is higher, leading to an
nearly 50 V shift, while Fmax was seen to change by only electron enrichment of the film that accounts for our

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 ARTICLE
Figure 2. Electrical properties of n-doped hydrogenated graphene. (a) Raman spectra of the graphene device (square device)
in (b)
(d) before (G-Sq) and after hydrogenation (HG-Sq). The spectra have been normalized to the G-mode intensity. (b) F as a
function of Vg at 296 K for G-Sq before heating to 375 K (black trace) and after heating (red trace). The solid curves are
Lorentzian fits to the data. Inset: temperature dependence of graphene demonstrates characteristic semimetallic properties.
(c) F versus Vg from 50 to 375 K for the hydrogenated device HG-Sq with a D/G ratio of 3.9. Data were taken after pumping the
chamber for 17 h. Note that the CNP is located at negative Vg, indicating an n-type material. The solid lines are Lorentzian fits
to the data. The graphene (black trace) was measured at 295 K. (d) F versus T for several different gate voltages. The solid lines
are fits to the VRH theory. Inset: Characteristic exponents To, extracted from a fit to the VRH theory, versus Vg. The black trace is
a Lorentzian fit to the data.

observations (n-type). Furthermore, we observe that as implemented in the Gaussian 09 software suite.19 To
our model predicts that the physisorption of water leads account for the effect of the positively charged substrate,
to a significant lowering of the WF well below that of we included an electric field in the direction perpen-
graphene (and thus that of the substrate), Figure 1d. dicular to the molecular plane. The relative changes
A film WF lower than that of the substrate's results in an on the WF were estimated by using the approximation
electron depletion (electrons moving from the film to WF =
(eHOMO þ eLUMO)/2. The WF for coronene is
the substrate), resulting in a p-type material. The estimated to be 3.74 eV, and although this is about 0.9
different type of majority carriers is thus accounted eV lower than the experimental value for graphene, we
for by the WFs of the different materials relative to the are interested in its changes due to hydrogenation and
substrate, and such a striking change in majority carrier subsequent water adsorption. The hydrogenated coro-
should be observed only in substrates whose WF is nene displays a WF ∼0.1 eV higher than that of coronene,
close to that of graphene. while the absorption of water results in a lowering relative
The WF of graphene has been measured17 and is to coronene of ∼0.15 to 0.20 eV, consistent with the
almost identical to that of graphite, ∼4.6 eV, very close discussion above. We emphasize the importance of
to the reported value for a > 100 nm thermal oxide layer accounting for the substrate effect through an electric
on n-type silicon,18 which explains why our exfoliated field, as when no field is present, the WFs for the hydro-
graphene on a SiO2 substrate always displays a CNP genated graphene material with and without water are
close to 0 Vg. As stated above, we performed DFT both approximately ∼0.06 eV lower than that of coronene.
calculations to assess the effect of hydrogenation We further study the electronic properties of the
and subsequent water adsorption on the WF of gra- hydrogenated graphene with several additional de-
phene. For these purposes, we use a cluster model vices including a square geometry (referred to here as
consisting of a coronene molecule using a triple-ζ device G-Sq) shown in Figure 1a and a cross geometry
Gaussian basis [6-311G(d,p)] and the wB97XD functional with arm dimensions of 1.25 μm by 500 nm (length and

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 ARTICLE
Figure 3. Electrical properties of p-type hydrogenated graphene before conversion to n-type. (a) Raman spectra of the
graphene device (cross device) in (b) before (G-X2) and after hydrogenation (HG-X2). The spectra have been normalized to the
G-mode intensity. (b) F versus Vg from 220 to 375 K for the hydrogenated device HG-X2 with a D/G ratio of 2.1. Data were taken
after pumping the chamber for 17 h. Note that the CNP is to the left of the pristine graphene CNP, but to the right of 0 Vg. It is
possible that this is due to unintentional doping of the initial graphene (CNP located at ∼30 V). The solid lines are Lorentzian
fits to the data. The graphene (black trace) was measured at 295 K.

Figure 4. Band gap opening in hydrogenated graphene. (a)
ln(1/F) versus 1/2KBT for the high-temperature data in Figure 2d.
The band gap for a homogeneous semiconductor is the slope of the curve. (b) Band gap Δε versus Vg
VCNP for four different
levels of hydrogenation. D/G ratio of 3.9: HG-Sq. D/G ratio of 2.1: HG-X2. D/G ratios of 1.24 and 2.7: HG-Hb. Solid curves are
Lorentzian fits to the data. Inset: Maximum band gap versus D/G ratio, proves that a larger H/C ratio corresponds to a larger
band gap at the CNP.

width, respectively, and referred to as device G-X2), The samples were heated to 375 K though no
which all demonstrate the same effect. The black traces appreciable change was observed in the location of
in Figures 2c and 3b illustrate F versus Vg for the the CNP. Thus we conclude that the majority of the
graphene found at 295 K. The graphene was heated water on the surface was desorbed during the ex-
to 375 K, and the CNP was determined to remain fixed tended time in vacuum. Together with the small
in Vg at 295 K with no appreciable change in the Fmax changes in D/G ratios before and after the measure-
value, as seen in Figure 2b. The graphene 295 K ments and heating cycles, these observations indicate
mobility μh (p-type, hole conduction) for the G-Sq that the shift in carrier type is exclusively due to
device was measured at 0 Vg and found to be physisorption/desorption of water on the surface and
8300 cm2/(V s), while the 295 K temperature carrier not through a chemical reaction. Reversibility of the
density nh was found to be 9.4  1011 cm
2. carrier type upon exposure of the film to atmospheric
The two samples were hydrogenated to D/G ratios of water further confirms this hypothesis, as the CNP was
3.9 (HG-Sq) and 2.1 (HG-X2) and were evacuated in the seen to shift back to the right after exposing the HG-Sq
cryostat for 17 h before any electrical measurements sample to deionized water and subsequently measur-
were carried out. The CNP for both hydrogenated ing F versus Vg.
samples shifted ∼20 V to the left in Vg from the We investigated F versus T in the 50 to 375 K range
CNP of the pristine graphene even without heating, for the two different D/G ratios and at various Vg.
as can be seen in Figure 2c (HG-Sq) and Figure 3b Figures 2c and 3b show that F for each hydrogenated
(HG-X2). After the CNP had shifted the mobility device changes sharply about the CNP with decreasing
and carrier density were measured for the HG-Sq T, but that this change is not as severe when Vg is swept
sample at 0 Vg (n-type, μe = 307 cm2/V, ne = 7.4  further away from the CNP. This semi-insulating behav-
1011 cm
2). ior fits well to the two-dimensional variable range

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 ARTICLE
hopping (VRH) theory described by eq 3, which is ratios of the two materials are approximately equiva-
demonstrated in Figure 2d for the device with a D/G lent at 50 K, with the hydrogenated graphene on/off
ratio of 3.9 (HG-Sq). The inset in Figure 2d plots the ratio increasing further with decreasing temperature.
characteristic exponents To, found from the fit to the The fact that the on/off ratio for hydrogenated gra-
VRH theory, as a function of Vg, and is well fitted by a phene is still low at room temperature could be the
Lorentzian model. The values for Fo found from the result of the creation of a small band gap (∼50 meV)
VRH fit had a mean value of 5982 Ω/sqr and deviated and/or transport channels that are manifested within
from this value by no more than 20%. the band gap.
DFT calculations have been carried out within the
F ¼ Fo eð T Þ
To 1=3
(3) plane-wave pseudopotential approximation20,21 and
indicate that for free-standing films (graphene, partially
Changes in F as a function of T (ΔF/ΔT) increased
hydrogenated graphene, and partially hydrogenated gra-
with increasing levels of hydrogenation and suggest
phene with water without accounting for substrate
the opening of a band gap, Δε. An estimate of Δε is
effects) there is a negligible band gap, which has been
deduced from the T dependence of the intrinsic con-
further confirmed by orbital-based DFT calculations that
ductivity σ (1/F), which for a homogeneous semiconduc-
yield the same conclusion.19 Also, the zero band gap in
tor varies exponentially, as shown in eq 4. Figure 4a plots
graphene has been shown to be very robust toward defor-
the logarithmic behavior σ versus 1/2KBT, where the slope
mation and stress,22
24 so that the stress induced by the
of the line should be proportional to the band gap.
substrate (which should be higher upon hydrogenation)
σ  e
Δε=2kT (4) does not account for the band gap either. We conclude
that the observed band gap can be attributed to one or a
We find for each hydrogenated sample that the combination of the following factors: (a) long-range dis-
maximum band gap occurs at the CNP and decreases order, (b) the large electric fields that a positively charged
with Vg away from the CNP, as seen in Figure 4b. substrate such as thermal oxide would exert on the films,
Furthermore, on the basis of the data in Figure 4b we and (c) the electron density depletion/increase induced by
conclude that a larger D/G ratio in the Raman spectra, the difference in WF between substrate and film.
and therefore a higher concentration of hydrogen The ability to control the majority carrier type while
atoms adsorbed to the graphene, will lead to a larger introducing a band gap makes hydrogenated gra-
band gap opening at the CNP. Although a maximum phene a promising method for nanocircuit design
(e.g., p
n junctions) in a graphene-based system.
Δε of ∼50 meV is measured in our lightly hydroge-
Tunability of the carrier type via surface doping re-
nated devices, we note that this is not a limit, as the
moves the requirement for multiple gate electrodes for
calculated band gap for hydrogenated graphene in-
independent carrier type control, avoiding the need for
creases up to 5.4 eV as you increase the hydrogen high-quality dielectrics that are difficult to achieve on
coverage.9,14 We determine that the on/off ratio (the graphene and are susceptible to leakage currents. Our
ratio of the low vs high resistance points in the R vs Vg work also demonstrates how surface adsorbates can
plots) remains virtually fixed for graphene, but in- affect the electrical properties of hydrogenated gra-
creases with decreasing temperature for hydroge- phene, properties that would otherwise be negligible
nated graphene. For the data shown in Figure 2c the in bulk materials.

EXPERIMENTAL METHODS Raman spectra were collected using a Renishaw MicroRaman

The graphene devices listed in Table 1 were fabricated by spectrometer with a 514 nm laser excitation.
mechanical exfoliation of HOPG on a SiO2 (275 nm)/Si (n-type Electronic transport measurements were carried out in a
arsenic doped) substrate,25 followed by the deposition of Cr cryogenic probe station, using ac lock-in techniques at a
(10 nm)/Au (50 nm) contact electrodes. For devices that re- frequency of 13.7 Hz. A four-wire configuration is used in all
of our measurements, as seen in Figure 1a. An excitation current
quired additional geometrical patterning a low-power O2 plas-
of 10 nA was used for the hydrogenated devices (I = 31.6 nA for
ma treatment was used to etch the film into the desired shape.
pristine graphene), and the voltage drop across the device was
Hydrogenation of the graphene was performed according to ref
monitored and kept below KBT/e to prevent charge carrier
13 under the following conditions: 15
30 W, 1.5 Torr H2, 100
heating, where KB is the Boltzmann constant and e the funda-
sccm, 32 C, for 15
30 s. The hydrogenation conditions (time and
mental unit of electric charge. F for each device is found using
power) varied depending upon the desired level of hydrogenation.
eq 1, where Iab is the source current along one edge of the
Raman spectroscopy was used to determine the relative defect
sample and Vcd the voltage drop measured across the opposite
densities in the films by a ratio of the G-mode intensity (1588 cm
1,
edge (except for the Hall bar device G-Hb, in which case F is
E2g phonon mode) and the D-mode intensity (1345 cm
1, appear-
calculated from the resistance R via F = RW/L, where W and L are
ing due to symmetry breaking at defect sites). The D/G ratio is
sample width and length, respectively).
related to the defect-free domain size of graphitic materials,26,27 in
this case caused by hydrogen addition to the graphene sheet. With  
the reactor conditions stated, the resulting D/G ratios demonstrated π 1 V43 V14 V21 V32
F ¼ þ þ þ (1)
saturation for each power/time and were repeatable for all devices. ln 2 4 I12 I23 I34 I41

MATIS ET AL. VOL. 6 ’ NO. 1 ’ 17–22 ’ 2012 21

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 ARTICLE
8. Zhang, Y.; Tan, Y.-W.; Stormer, H. L.; Kim, P. Experimental
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