The surface structure of Si(111) post-annealed at 980 °C after nitrogen ion induced nitridation has been investigated by using a scanning tunneling microscope (STM) and low energy electron diffraction (LEED). The LEED and STM results indicated the formation of ordered domain of quadruplet structure in the silicon nitride layer. The LEED pattern taken from the nitrated Si(111) surface showed a coexistence of 7×7 domain with quadruplet one. In the STM image taken from the same surface, a three directional periodicity with a periodic arrangement of white protrusions was observed in the local area of silicon nitride island and its symmetry directions were rotated about 10° with respect to those of Si(111) surface. In addition to the quadruplet structure of the silicon nitride island, meta-stable structures such as 9×9, c(4×2), and 2×2 as well as 7×7 phase boundaries were observed to have been formed on the Si(111) surface during the rapid cooling of nitrated surface from the post-annealing temperature of 980 °C. The investigation of the surface structure of nitrated Si(111) showed that the surface nitrated at high temperature had better epitaxial silicon nitride layer than that post-annealed after nitridation at room temperature.