Bernard R. Matis ACS Nano 6 17
Bernard R. Matis ACS Nano 6 17
Bernard R. Matis ACS Nano 6 17
G
raphene lacks a band gap in its elec-
tronic spectrum; thus graphene's ABSTRACT
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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
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 cm2. 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 cm2). ior fits well to the two-dimensional variable range