Liang Feng Huang

Modulation of the thermodynamic, kinetic, and magnetic properties of the hydrogen monomer on graphene by charge doping

The thermodynamic, kinetic, and magnetic properties of the hydrogen monomer on doped graphene layers were studied by ab initio simulations. Electron doping heightens the diffusion potential barrier, while hole doping lowers it. However, both kinds of dopings heighten the desorption potential barrier. The underlying mechanism was revealed by investigating the effect of charge doping on the bond strength of graphene and on the electron transfer and the coulomb interaction between the hydrogen monomer and graphene. The kinetic properties of H and D monomers on doped graphene layers during both the annealing process (annealing time t(0) = 300 s) and the constant-rate heating process (heating rate α = 1.0 K/s) were simulated. Macroscopic diffusion of hydrogen monomers on graphene can be achieved when the doping-hole density reaches 5.0 × 10(13) cm(-2). Both electron and hole dopings linearly reduce the total magnetic moment and exchange splitting, which was explained by a simple exchange model. The laws found in this work had been generalized to explain many phenomena reported in literature. This study can further enhance the understanding of the interaction between hydrogen and graphene and was expected to be helpful in the design of hydrogenated-graphene-based devices.

Ab Initio Simulations of the Kinetic Properties of the Hydrogen Monomer on Graphene

The understanding of the kinetic properties of hydrogen (isotopes) adatoms on graphene is important in many fields. The kinetic properties of hydrogen-isotope (H, D, and T) monomers were simulated using a composite method consisting of density functional theory, density functional perturbation theory, and harmonic transition state theory. The kinetic changes of the magnetic property and the aromatic π bond of the hydrogenated graphene during the desorption and diffusion of the hydrogen monomer were discussed. The vibrational zero-point energy corrections in the activation energies were found to be significant ranging from 0.072 to 0.205 eV. The results obtained from quantum mechanically modified harmonic transition state theory were compared with the ones obtained from classical-limit harmonic transition state theory over a wide temperature range. The phonon spectra of hydrogenated graphene were used to closely explain the (reversed) isotope effects in the prefactor, the activation energy, and the jump fr...

Understanding and tuning the quantum-confinement effect and edge magnetism in zigzag graphene nanoribbon

The electronic structure of zigzag graphene nanoribbon (ZGNR) is studied using density functional theory. The mechanisms underlying the quantum-confinement effect and edge magnetism in ZGNR are systematically investigated by combining the simulated results and some useful analytic models. The quantum-confinement effect and the inter-edge superexchange interaction can be tuned by varying the ribbon width, and the spin polarization and direct exchange splitting of the edge states can be tuned by varying their electronic occupations. The two edges of ZGNR can be equally or unequally tuned by charge doping or Li adsorption, respectively. The Li adatom has a site-selective adsorption on ZGNR, and it is a nondestructive and memorable approach to effectively modify the edge states in ZGNR. These systematic understanding and effective tuning of ZGNR electronics presented in this work are helpful for further investigation and application of ZGNR and other magnetic graphene systems.

Lattice dynamics and disorder-induced contraction in functionalized graphene

The lattice dynamics and disorder-induced contraction in hydrogenated, fluorinated, and chlorinated graphene are studied by first-principles simulation. The effects of the functionalization on the phonon dispersions, Gruneissen constants, vibrational thermodynamic functions (free energy, internal energy, entropy, and heat capacity), thermal-expansion coefficients, and bulk moduli are systematically investigated. Functionalization changes the chemical-bond length, mass, thickness, vibrational-mode symmetry, and mode number, and subsequently has significant effects on the phonon dispersions and Gruneissen constants. Functionalization generally increases the vibrational thermodynamic functions, and their temperature dependences all present conventional isotope effects. Functionalization suppresses (enhances) the thermal contraction (expansion) of the lattice, due to the increases in the system mass, membrane thickness, and the compressibility of the phonons. Both the lattice-constant variation and the phonon...

Patterning graphene nanostripes in substrate-supported functionalized graphene: A promising route to integrated, robust, and superior transistors

It is promising to apply quantum-mechanically confined graphene systems in field-effect transistors. High stability, superior performance, and large-scale integration are the main challenges facing the practical application of graphene transistors. Our understandings of the adatom-graphene interaction combined with recent progress in the nanofabrication technology indicate that very stable and high-quality graphene nanostripes could be integrated in substrate-supported functionalized (hydrogenated or fluorinated) graphene using electron-beam lithography. We also propose that parallelizing a couple of graphene nanostripes in a transistor should be preferred for practical application, which is also very useful for transistors based on graphene nanoribbon.

Understanding the stability and dynamical process of hydrogen trimers on graphene

With density functional theory calculations, the performance of hydrogen trimers on graphene including the structural stability and the dynamical evolution paths is systematically investigated. The stability of the trimer is closely related with its adsorption configuration. The configurations containing ortho-dimers and para-dimers are more stable than the others. Meanwhile, other nearby hydrogen clusters have different impacts on the stability of trimers, which is determined by the competition between lattice deformation and inter-cluster electronic pairing. Atomic diffusion and desorption are proved to be very important for the dynamical evolution paths of trimers, in which all trimers are first easily changed into stable dimers and then follow the desorption of dimers. Our results have well explained the phenomena given by the scanning tunneling microscopy experiments and are helpful for the understanding of the interaction between hydrogen and graphene, and for the application of hydrogenated graphene.

Adsorption configurations and scanning voltage determined STM images of small hydrogen clusters on bilayer graphene

By density functional theory calculations, the scanning tunneling microscopy (STM) images of various hydrogen clusters adsorbed on bilayer-graphene are systematically simulated. The hydrogen configurations of the STM images observed in the experiments have been thoroughly figured out. In particular, two kinds of hydrogen dimers (ortho-dimer, para-dimer) and two kinds of tetramers (tetramer-A, -B) are determined to be the hydrogen configurations corresponding to the ellipsoidal-like STM images with different structures and sizes. One particular hexamer (hexamer-B) is the hydrogen configuration generating the star-like STM images. For each hydrogen cluster, the simulated STM images show unique voltage-dependent features, which provides a feasible way to determine hydrogen adsorption states on graphene or graphite surface in the experiments by varying-voltage measurements. Stability analysis proves that the above determined hydrogen configurations are quite stable on graphene, hence they are likely to be detected in the STM experiments. Consequently, through systematic analysis of the STM images and the stability of hydrogen clusters on bilayer graphene, many experimental observations have been consistently explained.

The diffusion of hydrogen monomers on hole-doped graphitic lattices: over-barrier transition and quantum tunneling

The diffusion of hydrogen and deuterium monomers on hole-doped graphene (a planar graphitic lattice), the outside wall and the inside wall of hole-doped (6, 0) single-walled carbon nanotubes (a curved graphitic lattice) was investigated using density functional theory and density functional perturbation theory. The jump frequencies for the over-barrier transition and phonon-assisted quantum tunneling were calculated by transition state theory and small-polaron theory, respectively. The effects of the local curvature of the surface and the hole doping on the thermodynamic and kinetic properties of a hydrogen monomer on these graphitic lattices are discussed. Our results demonstrate that it is sufficient to judge the diffusional mobility of a hydrogen monomer on graphitic lattices from just the over-barrier transition, no matter how much it is curved and hole doped, while the quantum tunneling can be safely neglected because it is significantly suppressed by the covalent bonding of hydrogen with the graphitic lattice.