The unique chemical reactivity of a graphene nanoribbon's zigzag edge

The zigzag edge of a graphene nanoribbon possesses a unique electronic state that is near the Fermi level and localized at the edge carbon atoms. We investigate the chemical reactivity of these zigzag edge sites by examining their reaction energetics with common radicals from first principles. A "partial radical" concept for the edge carbon atoms is introduced to characterize their chemical reactivity, and the validity of this concept is verified by comparing the dissociation energies of edge-radical bonds with similar bonds in molecules. In addition, the uniqueness of the zigzag-edged graphene nanoribbon is further demonstrated by comparing it with other forms of sp2 carbons, including a graphene sheet, nanotubes, and an armchair-edged graphene nanoribbon.Comment: 24 pages, 9 figure

Thermodynamic effects in morphological evolution of polymer-fullerene nanocomposites for photovoltaic applications

Polymer based photovoltaic devices promise solar technologies that are inexpensive enough to be widely exploited and therefore provide a significant fraction of the future energy needs. There are many promising polymer-fullerene mixtures that are promising materials candidates for achieving high performance devices, but their exploitation requires and improved understanding of their structure-property relationships. Of particular relevance is the phase behavior of the mixtures. The phase behavior of donor-acceptor materials for photovoltaic applications is of key importance [1,2]: i) to gain a fundamental understanding and control of morphology development in the donor-acceptor blends; ii) to appropriately choose the operating window for thermal annealing; iii) to understand the long-term stability of the blended film morphology and consequently of the photovoltaic performance of the corresponding solar cells. In this work the phase behavior of polymer-fullerene mixtures is being studied using Differential Scanning Calorimetry (DSC), Wide-Angle X-Ray Scattering (WAXS), Small-Angle Neutron Scattering (SANS) and theoretical ab initio Density Functional Theory (DFT) calculations

Scale-free switching of polarization in the layered ferroelectric material CuInP2_2S6_6

Using first-principles calculations we model the out-of-plane switching of local dipoles in CuInP$_2$S$_6$ (CIPS) that are largely induced by Cu off-centering. Previously, a coherent switching of polarization via a quadruple-well potential was proposed for these materials. In the super-cells we considered, we find multiple structures with similar energies but with different local polar order. Our results suggest that the individual dipoles are weakly coupled in-plane and under an electric field at very low temperatures these dipoles in CIPS should undergo incoherent disordered switching. The barrier for switching is determined by the single Cu-ion switching barrier. This in turn suggests a scale-free polarization with a switching barrier of $\sim$ 203.6-258.0 meV, a factor of five smaller than that of HfO$_2$ (1380 meV) a prototypical scale-free ferroelectric. The mechanism of polarization switching in CIPS is mediated by the switching of each weakly interacting dipole rather than the macroscopic polarization itself as previously hypothesized. These findings reconcile prior observations of a quadruple well with sloping hysteresis loops, large ionic conductivity even at 250~K well below the Curie temperature (315~K), and a significant wake-up effects where the macroscopic polarization is slow to order and set-in under an applied electric field. We also find that computed piezoelectric response and the polarization show a linear dependence on the local dipolar order. This is consistent with having scale-free polarization and other polarization-dependent properties and opens doors for engineering tunable metastability by-design in CIPS (and related family of materials) for neuromorphic applications