We have used scanning tunneling microscopy (STM) to investigate two types of hydrogen defect structures on monolayer graphene supported by hexagonal boron nitride (h-BN) in a gated field-effect transistor configuration. The first H-defect type is created by bombarding graphene with 1-keV ionized hydrogen and is identified as two hydrogen atoms bonded to a graphene vacancy via comparison of experimental data to first-principles calculations. The second type of H defect is identified as dimerized hydrogen and is created by depositing atomic hydrogen having only thermal energy onto a graphene surface. Scanning tunneling spectroscopy (STS) measurements reveal that hydrogen dimers formed in this way open a new elastic channel in the tunneling conductance between an STM tip and graphene.
The ability of atomic hydrogen to chemisorb on graphene makes the latter a promising material for hydrogen storage. Based on scanning tunneling microscopy techniques, we report on site-selective adsorption of atomic hydrogen on convexly curved regions of monolayer graphene grown on SiC(0001). This system exhibits an intrinsic curvature owing to the interaction with the substrate. We show that at low coverage hydrogen is found on convex areas of the graphene lattice. No hydrogen is detected on concave regions. These findings are in agreement with theoretical models which suggest that both binding energy and adsorption barrier can be tuned by controlling the local curvature of the graphene lattice. This curvature-dependence combined with the known graphene flexibility may be exploited for storage and controlled release of hydrogen at room temperature making it a valuable candidate for the implementation of hydrogen-storage devices.
Using density functional theory (DFT), Hartree-Fock, exact diagonalization, and numerical renormalization group methods we study the electronic structure of diluted hydrogen atoms chemisorbed on graphene. A comparison between DFT and Hartree-Fock calculations allows us to identify the main characteristics of the magnetic structure of the defect. We use this information to formulate an Anderson-Hubbard model that captures the main physical ingredients of the system, while still allowing a rigorous treatment of the electronic correlations. We find that the large hydrogen-carbon hybridization puts the structure of the defect half-way between the one corresponding to an adatom weakly coupled to pristine graphene and a carbon vacancy. The impuritys magnetic moment leaks into the graphene layer where the electronic correlations on the C atoms play an important role in stabilizing the magnetic solution. Finally, we discuss the implications for the Kondo effect.
In order to realize applications of hydrogen-adsorbed graphene, a main issue is how to control hydrogen adsorption/desorption at room temperature. In this study, we demonstrate the possibility to tune hydrogen adsorption on graphene by applying a gate voltage. The influence of the gate voltage on graphene and its hydrogen adsorption properties was investigated by electrical transport measurements, scanning tunneling microscopy, and density functional theory calculations. We show that more hydrogen adsorbs on graphene with negative gate voltage (p-type doping), compared to that without gate voltage or positive gate voltage (n-type doping). Theoretical calculations explain the gate voltage dependence of hydrogen adsorption as modifications of the adsorption energy and diffusion barrier of hydrogen on graphene by charge doping.
The sticking probability of cold atomic hydrogen on suspended graphene calculated by Lepetit and Jackson [Phys. Rev. Lett. {bf 107}, 236102 (2011)] does not include the effect of fluctuations from low-frequency vibrations of graphene. These fluctuations suppress the sticking probability for low incident energies ($lesssim 15$ meV).
We investigate the quality of hydrogen plasma defined graphene edges by Raman spectroscopy, atomic resolution AFM and low temperature electronic transport measurements. The exposure of graphite samples to a remote hydrogen plasma leads to the formation of hexagonal shaped etch pits, reflecting the anisotropy of the etch. Atomic resolution AFM reveals that the sides of these hexagons are oriented along the zigzag direction of the graphite crystal lattice and the absence of the D-peak in the Raman spectrum indicates that the edges are high quality zigzag edges. In a second step of the experiment, we investigate hexagon edges created in single layer graphene on hexagonal boron nitride and find a substantial D-peak intensity. Polarization dependent Raman measurements reveal that hydrogen plasma defined edges consist of a mixture of zigzag and armchair segments. Furthermore, electronic transport measurements were performed on hydrogen plasma defined graphene nanoribbons which indicate a high quality of the bulk but a relatively low edge quality, in agreement with the Raman data. These findings are supported by tight-binding transport simulations. Hence, further optimization of the hydrogen plasma etching technique is required to obtain pure crystalline graphene edges.