HOMO band structure and anisotropic effective hole mass in thin crystalline Pentacene films

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The band dispersion of the two highest occupied molecular orbital (HOMO)-derived bands in thin crystalline Pentacene films grown on Bi(001) was determined by photoemission spectroscopy. Compared to first-principles calculations our data show a significantly smaller band width and a much larger band separation indicating that the molecular interactions are weaker than predicted by theory--a direct contradiction to previous reports by Kakuta et al. [Phys. Rev. Lett. 98, 247601 (2007)]. The effective hole mass m* at M-bar is found to be anisotropic and larger than theoretically predicted. Comparison of m* to field effect mobility measurements shows that the band structure has a strong influence on the mobility even at room temperature where we estimate the scattering rate to be tau 3 fs.