Optical absorptions of polyfluorene transistors

Conjugated polymers are a promising class of materials for organic electronics. While the progress in device performance is impressive, the basics of charge transport still pose many open questions. Specifically, conduction at the comparatively rough polymer-polymer interface in an all-polymer field-effect transistor is expected to be different from a sharp interface with an inorganic dielectric, such as silicon dioxide. In this work, charge modulation spectroscopy (CMS) is used to study the optical absorptions in the presence of charges in situ in the transistor structure. This allows direct observation of the charge carriers in the operational device via their spectroscopic signature; the technique is by design very sensitive to the properties of the semiconductor-dielectric interface. The semiconducting copolymer poly(9,9(')-dioctyl-fluorene-co-bithiophene) (F8T2) is incorporated into a top-gate thin-film transistor structure with a polymer dielectric layer deposited by spin coating and inkjet-printed polymer electrodes. A prominent charge-induced absorption at 1.65 eV is observed as well as a shoulder at 1.3 eV and a tail extending toward the absorption edge. The bias dependence of the CMS signature confirms that intermixing of the polymer layers is minimal, as expected from the excellent transistor characteristics. Polarization-dependent CMS measurements on aligned transistors show that the main feature at 1.65 eV is strongly polarized whereas the shoulder is unpolarized. This observation, as well as further experimental evidence, lead to the conclusion that while the main absorption is attributable to the intrinsic, polaronic absorption in F8T2, the shoulder is likely to originate from a defect state.