Abstract
By means of Penning-ionization electron spectroscopy the outermost surface layer of a pentacene film on a graphite substrate (cleavage plane) was selectively observed. Ultraviolet photoelectron spectroscopy was also applied to observe several layers from the surface. From the analyses of the two types of spectra the subtle changes in the electronic state and the molecular orientation of the outermost layer and also those of inner layers were probed separately during the layer-by-layer epitaxial growth of the film.