We report the first observation of the n-type nature of hydrogenated graphene on SiO(2) and demonstrate the conversion of the majority carrier type from electrons to holes using surface doping. Density functional calculations indicate that the carrier type reversal is directly related to the magnitude of the hydrogenated graphene's work function relative to the substrate, which decreases when adsorbates such as water are present. Additionally, we show by temperature-dependent electronic transport measurements that hydrogenating graphene induces a band gap and that in the moderate temperature regime [220-375 K], the band gap has a maximum value at the charge neutrality point, is tunable with an electric field effect, and is higher for higher hydrogen coverage. The ability to control the majority charge carrier in hydrogenated graphene, in addition to opening a band gap, suggests potential for chemically modified graphene p-n junctions.

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We have investigated the use of the average local ionization energy, I[combining overline](S)(r), as a means for rapidly predicting the relative reactivities of different sites on two model graphene surfaces toward the successive addition of one, two, and three hydrogen or fluorine atoms. The I[combining overline](S)(r) results were compared with directly computed interaction energies, at the B3LYP/6-311G(d,p) level. I[combining overline](S)(r) correctly predicts that the edges of graphene sheets are more reactive than the interior portions. It shows that added hydrogens activate the adjoining (ortho) sites and deactivate those that are separated by one site (meta). Overall, I[combining overline](S)(r) is effective for rapidly (single calculations) estimating the relative site reactivities of these large systems, although it reflects only the system prior to an interaction and cannot take into account postinteraction factors, e.g., structural distortion.

We demonstrate the first successful growth of large-area (200 × 200 μm(2)) bilayer, Bernal stacked, epitaxial graphene (EG) on atomically flat, 4H-SiC (0001) step-free mesas (SFMs) . The use of SFMs for the growth of graphene resulted in the complete elimination of surface step-bunching typically found after EG growth on conventional nominally on-axis SiC (0001) substrates. As a result heights of EG surface features are reduced by at least a factor of 50 from the heights found on conventional substrates. Evaluation of the EG across the SFM using the Raman 2D mode indicates Bernal stacking with low and uniform compressive lattice strain of only 0.05%. The uniformity of this strain is significantly improved, which is about 13-fold decrease of strain found for EG grown on conventional nominally on-axis substrates. The magnitude of the strain approaches values for stress-free exfoliated graphene flakes. Hall transport measurements on large area bilayer samples taken as a function of temperature from 4.3 to 300 K revealed an n-type carrier mobility that increased from 1170 to 1730 cm(2) V(-1) s(-1), and a corresponding sheet carrier density that decreased from 5.0 × 10(12) cm(-2) to 3.26 × 10(12) cm(-2). The transport is believed to occur predominantly through the top EG layer with the bottom layer screening the top layer from the substrate. These results demonstrate that EG synthesized on large area, perfectly flat on-axis mesa surfaces can be used to produce Bernal-stacked bilayer EG having excellent uniformity and reduced strain and provides the perfect opportunity for significant advancement of epitaxial graphene electronics technology.