The surface crystallography and chemistry of a LaAlO 3 single crystal, a material mainly used as a substrate to deposit technol ogically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surfa ce was determined to be terminated by Al-O species, and was significantly different from th e idealised bulk structure. Termination reversal was not observed at higher temperature (600°C) and chamber pressure of 10 -10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10 -6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO 2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO 3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures
