Atomic-scale view of the photoinduced structural transition to form sp3-like bonded order phase in graphite.

Photoexcitation of solids often induces structural phase transitions between different ordered phases, some of which are unprecedented and thermodynamically inaccessible. The phenomenon, known as photoinduced structural phase transition (PSPT), is of significant interest to the technological progress of advanced materials processing and the fundamental understanding of material physics. Here, we applied scanning tunnelling microscopy (STM) to directly characterise the primary processes of the PSPT in graphite to form a sp3-like carbon nano-phase called diaphite. The primary challenge was to provide microscopic views of the graphite-to-diaphite transition. On an atomic scale, STM imaging of the photoexcited surface revealed the nucleation and proliferation processes of the diaphite phase; these were governed by the formation of sp3-like interlayer bonds. The growth mode of the diaphite phase depends strongly on the photon energy of excitation laser light. Different dynamical pathways were proposed to explain the formation of a sp3-like interlayer bonding. Potential mechanisms for photon-energy-dependent growth were examined based on the experimental and calculated results. The present results provide insight towards realising optical control of sp2-to-sp3 conversions and the organisation of nanoscale structures in graphene-related materials.

Anomalous Flexural Elasticities of Graphene Membranes Unveiled by Manipulating Topology.

Mechanical behavior of atomically thin membranes is governed by bending rigidity and the Gaussian modulus. However, owing to methodological drawbacks, these two parameters have not been investigated sufficiently. We employed atomic force microscopy to demonstrate that the bending rigidity can be extracted from a quadratic relationship of adhesion energy with monolayer curvatures of rolled and unrolled graphene. The tip-induced topological defects revealed the Gaussian modulus; to the best of our knowledge, this is the first study on these parameters. Our study may hold great significance because existing investigations have been performed only on flat graphene. The configurational (strain) energy was evaluated via changes in the surface geometry, with subatomic resolution, by three-dimensional analyses of attractive interatomic forces. The mechanical parameters, evaluated at the hollow sites of the honeycomb lattice, were consistent with the isotropic elastic attributes. The remarkably large negative Gaussian modulus, observed when a single carbon atom was located at the center of the tip-induced bump, revealed attractive interactions between the topological defects and geometric potentials of the Gaussian curvature. Our approach will aid in developing two-dimensional materials and understanding cell biology.

Two-pulse excitation for efficient formation of an sp3 nanodomain with frozen shear in a graphite crystal.

We propose a two-pulse excitation to efficiently form a novel sp(3)-bonded nanosize domain with frozen shear in a graphite crystal. This sp(3) structure is well stabilized by shear displacement between two neighboring graphite layers. The shearing motion is induced transiently by the first laser pulse, and is frozen by the second pulse before disappearing, resulting in the efficient formation of the sp(3)-bonded domain with frozen shear. We show this dynamical process qualitatively by molecular dynamics calculations.

Dynamics of unidirectional exciton migration to the molecular periphery in a photoexcited compact dendrimer.

We have studied dynamical natures of electronic excited states in a compact series of phenylacetylene dendrimers. So as to clarify the mechanism of unidirectional migration of a photogenerated exciton in a compact dendrimer, we theoretically investigated the temporal behavior of the photogenerated exciton in the molecule by numerically solving the time-dependent Schrodinger equation for the electronic excited states. The structure of the dendrimers is optimized in the ground state, and it is fixed during the calculation of the exciton dynamics. The calculated results show that the exciton generated in the dendrimeric framework tends to migrate toward the outside of the molecule rather than the inside, and to itinerate around the periphery via the through-space interaction between the outer crowding benzene units. This is one of the intrinsic properties that originates from a highly branched treelike structure of the compact dendrimers.