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.