A refractory-metal-free C40 TiSi2 phase formed by pulsed-laser annealing is identified experimentally by combined convergent beam electron diffraction (CBED) study and CBED pattern simulation. The simulation shows that the C40 TiSi2 has a hexagonal structure with the space group P6(2)22(180) and lattice parameters a = 0.471 nm and c = 0.653 nm. Upon further furnace annealing or rapid thermal annealing, C54 TiSi2 can be directly achieved from C40 TiSi2 at low temperatures (600-700 degreesC). This observation suggests that pulsed-laser annealing is promising for extension of TiSi2 into the subquarter micron region in semiconductor device fabrication. (C) 2001 American Institute of Physics.