The optical properties of pentacene (PEN) and perfluoropentacene(PFP) thin films on various SiO2 substrates were studied using variable angle spectroscopic ellipsometry. Structural characterization was performed using X-ray reflectivity and atomic force microscopy. A uniaxial model with the optic axis normal to the sample surface was used to analyze the ellipsometry data. A Strong optical anisotropy was observed and enabled the direction of the transition dipole of the absorption bands to be determined. Furthermore, comparison of the optical constants of PEN and PFP thin films with the absorption spectra of the monomers in solution shows significant changes due to the crystalline environment. Relative to the monomer spectrum the HOMO-LUMO transition observed in PEN (PFP) thin film is reduced by 210 meV (280 meV). Surprisingly, a second absorption band in the PFP thin film shows a slight blueshift (40 meV) compared to the spectrum of the monomer with its transition dipole perpendicular to that of the first absorption band.

We investigate exciton-phonon coupling and exciton transfer in diindenoperylene ͑DIP͒ thin films on oxidized Si substrates by analyzing the dielectric function determined by variable-angle spectroscopic ellipsometry. Since the molecules in the thin-film phase form crystallites that are randomly oriented azimuthally and highly oriented along the surface normal, DIP films exhibit strongly anisotropic optical properties with uniaxial symmetry. This anisotropy can be determined by multiple sample analysis. The thin-film spectrum is compared with a monomer spectrum in solution, which reveals similar vibronic subbands and a Huang-Rhys parameter of S Ϸ 0.87 for an effective internal vibration at ប eff = 0.17 eV. However, employing these parameters the observed dielectric function of the DIP films cannot be described by a pure Frenkel exciton model, and the inclusion of charge-transfer ͑CT͒ states becomes mandatory. A model Hamiltonian is parametrized with density-functional theory calculations of single DIP molecules and molecule pairs in the stacking geometry of the thin-film phase, revealing the vibronic coupling constants of DIP in its excited and charged states together with electron and hole transfer integrals along the stack. From a fit of the model calculation to the observed dielectric tensor, we find the lowest CT transition E 00 CT at 0.26Ϯ 0.05 eV above the neutral molecular excitation energy E 00 F , which is an important parameter for device applications.

We report detailed temperature dependent photoluminescence (PL) spectra of pentacene (PEN), perfluoropentacene (PFP), and PEN:PFP mixed thin films grown on SiO2. PEN and PFP are particularly suitable for this study, since they are structurally compatible for good intermixing and form a model donor/acceptor system. The PL spectra of PEN are discussed in the context of existing literature and compared to the new findings for PFP. We analyze the optical transitions observed in the spectra of PEN and PFP using time-dependent density functional theory (TD-DFT) calculations. Importantly, for the mixed PEN:PFP film we observe an optical transition in PL at 1.4 eV providing evidence for coupling effects in the blend. We discuss a possible charge-transfer (CT) and provide a tentative scheme of the optical transitions in the blended films.

We present real-time in situ studies of optical spectra during thin film growth of several prototype organic semiconductors (pentacene, perfluoropentacene, and diindenoperylene) on SiO2. These data provide insight into surface and interface effects that are of fundamental importance and of relevance for applications in organic electronics. With respect to the bulk, the different molecular environment and structural changes within the first few monolayers can give rise to significant optical changes. Similar to interface-driven phenomena in, e.g., magnetism, spectral changes as a function of thickness d are a very general effect, decaying as 1/d in the simplest approximation. We observe energy shifts of 50-100 meV, rather small changes of the exciton-phonon coupling, and new transitions in specific systems, which should be considered as general features of the growth of organics.

We present optical absorption spectra of mixed films of pentacene (PEN) and perfluoropentacene (PFP) grown on SiO 2 . We investigated the influence of intermolecular coupling between PEN and PFP on the optical spectra by analyzing samples with five different mixing ratios of PFP:PEN with variable angle spectroscopic ellipsometry and differential reflectance spectroscopy. The data show how the spectral shape is influenced by changes in the volume ratio of the two components. By comparison with the pure film spectra an attempt is made to distinguish transitions due to intermolecular coupling between PEN and PFP from transitions caused by interactions of PEN (PFP) with other molecules of the same type. We observe a new transition at 1.6 eV which is not found in the pure film spectra and which we assign to the coupling of PFP and PEN.