The trend to reduce device dimensions demands increasing attention to atomic-scale details of structure of thin films as well as to pathways to control it. This is of special importance in the systems with multiple competing interactions. We have used in situ scanning tunneling microscopy to image surfaces of La5/8Ca3/8MnO3 films grown by pulsed laser deposition. The atomically resolved imaging was combined with in situ angle-resolved X-ray photoelectron spectroscopy. We find a strong effect of the background oxygen pressure during deposition on structural and chemical features of the film surface. Deposition at 50 mTorr of O-2 leads to mixed-terminated film surfaces, with B-site (MnO2) termination being structurally imperfect at the atomic scale. A relatively small reduction of the oxygen pressure to 20 mTorr results in a dramatic change of the surface structure leading to a nearly perfectly ordered B-site terminated surface with only a small fraction of A-site (La,Ca)O termination. This is accompanied, however, by surface roughening at a mesoscopic length scale. The results suggest that oxygen has a strong link to the adatom mobility during growth. The effect of the oxygen pressure on dopant surface segregation is also pronounced: Ca surface segregation is decreased with oxygen pressure reduction. ; ISI Document Delivery No.: CH2PL Times Cited: 0 Cited Reference Count: 67 Tselev, Alexander Vasudevan, Rama K. Gianfrancesco, Anthony G. Qiao, Liang Ganesh, P. Meyer, Tricia L. Lee, Ho Nyung Biegalski, Michael D. Baddorf, Arthur P. Kalinin, Sergei V. U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division; U.S. Department of Energy, Office of Basic Energy Sciences, Scientific User Facilities Division This research was sponsored by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division (A.T, R.K.V., A.G.G., T.L.M., H.N.L., S.V.K.). Research was conducted at CNMS, which also provided support (A.P.B., M.D.B., L.Q., P.G.) and which is sponsored at Oak Ridge National Laboratory by the U.S. Department of Energy, Office of Basic Energy Sciences, Scientific User Facilities Division. Amer chemical soc Washington