Abstract
The electronic structure of Cu(111)/pentacene and Ag(111)/pentacene interfaces were investigated with photoelectron spectroscopy and the hole barrier heights were determined to be 0.74 and 0.90 eV, respectively. When combined with previous measurements of the Au(111)/pentacene interface, the slope of the plot of metal work function against barrier height for Schottky barrier formation was determined to be 0.36, in agreement with current-voltage (I−V) measurements in the literature. However, the absolute barrier heights from photoemission measurements are 0.16 eV higher. The offset between the I−V measurement and the x-ray and ultraviolet photoelectron spectroscopy measurements was attributed to differences in how the highest occupied molecular orbital position is determined. Photoemission data indicates that at low coverages the pentacene molecules lie flat on the metal substrates, whereas at higher coverages the molecular orientation changes to orient the long molecular axis normal to the surface. Thicker films then tend to form three-dimensional islands, resulting in structured rather than flat films forming on clean Ag(111) and Cu(111) at room temperature.
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