Graphene Nanoislands Research Articles

Half-metallicity of graphene nanoribbons and related systems: a new quantum mechanical El Dorado for nanotechnologies … or a hype for materials scientists?

In this work we discuss in some computational and analytical details the issue of half-metallicity in zig-zag graphene nanoribbons and nanoislands of finite width, i.e. the coexistence of metallic nature for electrons with one spin orientation and insulating nature for the electrons of opposite spin, which has been recently predicted from so-called first-principle calculations employing Density Functional Theory. It is mathematically demonstrated and computationally verified that, within the framework of non-relativistic and time-independent quantum mechanics, like the size-extensive spin-contamination to which it relates, half-metallicity is nothing else than a methodological artefact, due to a too approximate treatment of electron correlation in the electronic ground state.

Half-metallicity and spin-contamination of the electronic ground state of graphene nanoribbons and related systems: An impossible compromise?

An analysis using the formalism of crystalline orbitals for extended systems with periodicity in one dimension demonstrates that any antiferromagnetic and half-metallic spin-polarization of the edge states in n-acenes, and more generally in zigzag graphene nanoislands and nanoribbons of finite width, would imply a spin contamination <linear span>S(2)<linear span> that increases proportionally to system size, in sharp and clear contradiction with the implications of Lieb's theorem for compensated bipartite lattices and the expected value for a singlet (S = 0) electronic ground state. Verifications on naphthalene, larger n-acenes (n = 3-10) and rectangular nanographene islands of increasing size, as well as a comparison using unrestricted Hartree-Fock theory along with basis sets of improving quality against various many-body treatments demonstrate altogether that antiferromagnetism and half-metallicity in extended graphene nanoribbons will be quenched by an exact treatment of electron correlation, at the confines of non-relativistic many-body quantum mechanics. Indeed, for singlet states, symmetry-breakings in spin-densities are necessarily the outcome of a too approximate treatment of static and dynamic electron correlation in single-determinantal approaches, such as unrestricted Hartree-Fock or Density Functional Theory. In this context, such as the size-extensive spin-contamination to which it relates, half-metallicity is thus nothing else than a methodological artefact.

A spin-valve device based on dumbbell-shaped graphene nanoislands

Electron transport in a graphene nanoisland with mixed edge profiles is studied by using the spin-unrestricted Hubbard model. The dumbbell-shaped device consists of two hexagonal nanoislands with zigzag edges connected by a armchair nanoribbon. Including the nearest-neighbor hopping and on-site Coulomb repulsion, the self-consistent calculation shows that two distinct ferromagnetic configurations allowed for the proposed device act like ON and OFF states for spin-polarized electrons. Furthermore, the spin-valve effect is demonstrated, as a proof of concept, in the device occupied by one ferromagnetic configuration without resorting to external magnetic or electric fields.

Beryllium chains interacting with Graphene Nanoislands: From anti-ferromagnetic to ferromagnetic ground state

Electronic and magnetic properties of 1-D Beryllium chains interacting with Graphene nano-structures are studied at an ab initio level. In particular, linear Beryllium chains present significant dispersion interactions with Graphene Nanoislands. The magnetic properties of the 1-D Beryllium chains, are not destroyed by the interaction with the surface. However, the nature of the ground state depend strongly on the interaction: at long distance, the chain has an anti-ferromagnetic ground state; the ground state becomes ferromagnetic for distances from the surface shorter than about 3 Å. The behavior of the Beryllium system can shed light on the more general problem of the interaction of alkali-earth atoms in a 1-D arrangement and Graphene surfaces.

Structure and Electronic Properties of Graphene Nanoislands on Co(0001)

We have grown well-ordered graphene adlayers on the lattice-matched Co(0001) surface. Low-temperature scanning tunneling microscopy measurements demonstrate an on-top registry of the carbon atoms with respect to the Co(0001) surface. The tunneling conductance spectrum shows that the electronic structure is substantially altered from that of isolated graphene, implying a strong coupling between graphene and cobalt states. Calculations using density functional theory confirm that structures with on-top registry have the lowest energy and provide clear evidence for strong electronic coupling between the graphene pi-states and Co d-states at the interface.

In-plane conductance measurement of graphene nanoislands using an integrated nanogapprobe

The in-plane conductance of individual graphene nanoislands thermally grown on SiCsubstrate was successfully measured using an integrated nanogap probe withoutlithographic patterning. A Pt nanogap electrode with a 30 nm gap integrated on thecantilever tip of a scanning probe microscope enables us to image a conductance map ofgraphene nanoislands with nanometer resolution. Single- and double-layer graphene islandsare clearly distinguished in the conductance image. The size dependence of the conductanceof the nanoislands suggests that the band gap opening is due to the lateral confinementeffect.

Periodically Rippled Graphene: Growth and Spatially Resolved Electronic Structure

We grow epitaxial graphene monolayers on Ru(0001) that cover uniformly the substrate over lateral distances larger than several microns. The weakly coupled graphene monolayer is periodically rippled and it shows charge inhomogeneities in the charge distribution. Real space measurements by scanning tunneling spectroscopy reveal the existence of electron pockets at the higher parts of the ripples, as predicted by a simple theoretical model. We also visualize the geometric and electronic structure of edges of graphene nanoislands.

Magnetism in Graphene Nanoislands

We study the magnetic properties of nanometer-sized graphene structures with triangular and hexagonal shapes terminated by zigzag edges. We discuss how the shape of the island, the imbalance in the number of atoms belonging to the two graphene sublattices, the existence of zero-energy states, and the total and local magnetic moment are intimately related. We consider electronic interactions both in a mean-field approximation of the one-orbital Hubbard model and with density functional calculations. Both descriptions yield values for the ground state total spin S consistent with Lieb's theorem for bipartite lattices. Triangles have a finite S for all sizes whereas hexagons have S=0 and develop local moments above a critical size of approximately 1.5 nm.