Au3-Decorated graphene as a sensing platform for O2 adsorption and desorption kinetics.

The adsorption and desorption kinetics of molecules is of significant fundamental and applied interest. In this paper, we present a new method to quantify the energy barriers for the adsorption and desorption of gas molecules on few-atom clusters, by exploiting reaction induced changes of the doping level of a graphene substrate. The method is illustrated for oxygen adsorption on Au3 clusters. The gold clusters were deposited on a graphene field effect transistor and exposed to O2. From the change in graphene's electronic properties during adsorption, the energy barrier for the adsorption of O2 on Au3 is estimated to be 0.45 eV. Electric current pulses increase the temperature of the graphene strip in a controlled way and provide the required thermal energy for oxygen desorption. The oxygen binding energy on Au3/graphene is found to be 1.03 eV and the activation entropy is 1.4 meV K-1. The experimental values are compared and interpreted on the basis of density functional theory calculations of the adsorption barrier, the binding energy and the activation entropy. The large value of the activation entropy is explained by the hindering effect that the adsorbed O2 has on the fluxional motion of the Au3 cluster.

Interaction of graphene with Aunclusters: a first-principles study.

The interaction between Aun(n= 1-6) clusters and graphene is studied using first-principles simulations, based on density functional theory. The computed binding energy between Aunand graphene depends on the number of atoms in the cluster and lies between -0.6 eV and -1.7 eV, suggesting (weak) chemisorption of the clusters on graphene, rather than physisorption. Overall, the electronic properties, spin-orbit interaction and spin texture, as well as the transport properties of graphene strongly depend on the precise size of the Aunclusters. Doping of graphene is predicted for clusters with an odd number of Au atoms, due to overlap between Ausand carbonpzstates close to the Fermi level. On the other hand, there is no charge transfer between even size Au clusters and graphene, but a gap is formed at the Dirac cone, due to the breaking of the pseudo spin inversion symmetry of graphene's lattice. The adsorbed Aunclusters induce spin-orbit interactions as well as spin and pseudo spin interactions in graphene, as indicated by the splitting of the electronic band structure. A hedgehog spin texture is also predicted for adsorbed clusters with an even number of Au atoms. Ballistic transport simulations are performed to study the influence of the adsorbed clusters on graphene's electronic transport properties. The influence of the cluster on the electron transmission across the structure depends on the mixing of the valence orbitals in the transport energy window. In the specific case of the Au3/graphene system, the adsorbed clusters reduce the transmission and the conductance of graphene. The Au3clusters act as 'scattering centers' for charge carriers, in agreement with recent experimental studies.