We have studied the structure of ultrathin MgO films grown on a single crystal Mo(001) surface. Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to investigate the effect of substrate temperature and oxygen partial pressure on the growth and morphology of these films. LEED indicates the growth of (100) films with MgO (110) directions oriented along (100) directions of the substrate. Despite the insulating nature of bulk MgO, films up to 25-Angstrom thick are sufficiently conducting to perform STM measurements. STM reveals Mg deposition in an oxygen ambient at substrate temperatures from 300 to 900 K produces uniform films. Films as thick as eight atomic layers typically have only three layers exposed. These films consist of small domains between 20 and 60 Angstrom in diameter. The domain shapes are random and the perimeters show no preferred orientation. In contrast, films grown at temperatures in excess of 1000 K exhibit larger three-dimensional MgO islands (Volmer-Weber growth). Steps on these high temperature films orient preferentially along thermodynamically favored MgO <100> directions. STM images of films deposited at high temperature exhibit a checkerboard pattern. The dimensions and symmetry of this pattern are consistent with the coincidence arising from the mismatch of the MgO(100) and Mo(001) lattice. Annealing room temperature deposited films results in island coalescence and produces uniform films with domains in excess of 100 A. The perimeters of these domains are oriented along MgO (100) directions. (C) 2003 Elsevier Science B.V. All rights reserved.