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Confirmation of direct photogeneration of intrinsic delocalized free carriers in small-molecule organic semiconductors has been a long-sought but unsolved issue, which is of fundamental significance to its application in photo-electric devices. Although the excitonic description of photoexcitation in these materials has been widely accepted, this concept is challenged by recently reported phenomena. Here we report observation of direct delocalized free carrier generation upon interband photoexcitation in highly crystalline zinc phthalocyanine films prepared by the weak epitaxy growth method using ultrafast spectroscopy. Transient absorption spectra spanning the visible to mid-infrared region revealed the existence of short-lived free electrons and holes with a diffusion length estimated to cross at least 11 molecules along the π−π stacking direction that subsequently localize to form charge transfer excitons. The interband transition was evidenced by ultraviolet-visible absorption, photoluminescence and electroluminescence spectroscopy. Our results suggest that delocalized free carriers photogeneration can also be achieved in organic semiconductors when the molecules are packed properly.

Nanocrystal Y2O3 powders with different grain sizes and various doping concentrations of Tb3+ were prepared by an autocombustion reaction. The size and surface effects on the 4f-5d transitions and energy transfers between Tb3+ ions were studied by using x-ray diffraction, transmission electron microscopy, fluorescent spectra, and luminescent decay. It was found that the excitation spectra are composed of two parts: one is the contribution from the Tb3+ at/near the nanoparticle surfaces; another is from the Tb3+ inside the nanoparticles. The study on the concentration quenching and luminescent decay indicated that the energy transfers depopulating the D53 and D54 level were assigned to the mechanisms of electric dipole-dipole and exchange interaction, respectively. The size confinement greatly affects the energy transfer quenching the emission from the D53 level, but slightly affects the energy transfer quenching the emission from the D54 level.