Positron beam experiments have been performed for the first time on a self-supporting polymethyl metacrylate (PMMA) film of 310 nm-thick made by spin coating. The positronium (Ps) emission from the PMMA surface is studied as a function of the positron implantation energy by using Doppler pro. le spectroscopy and Compton-to-peak ratio analysis. When the sample and the Ge-detector are perpendicular to the positron beam, the emission of para-positronium (p-Ps) is detected as a narrow central peak. By rotating the sample 458 with respect to the beam, the emission of p-Ps is detected as a blue-shifted fly-away peak. The bulk Ps fraction, the efficiency for the emission of Ps by picking up an electron from the surface, and the diffusion lengths of positrons (thermal and or epithermal), p-Ps and ortho-positronium (o-Ps) are obtained. (c) 2008 Elsevier B.V. All rights reserved.