Optoelectronic properties of sexithiophene single crystals

UV—Vis absorption, photoluminescence (PL) and photoconductivity (PC) measurements have been carried out on sexithiophene (α6T) single crystals grown from the vapor phase. UV—Vis absorption data were used to determine the absorption coefficient and refraction index under polarized light. The spectrum at polarization perpendicular to the unique axis b is similar to that measured on polycrystalline films, whereas that at light polarized parallel to b presents a weak structured absorption. The refractive index is 1.656, independent of the wavelength, under parallel polarization, and follows the Sellmeier equation, with n∞ = 1.867, under perpendicular polarization. The PL excitation spectrum with parallel polarization follows exactly the corresponding weak absorption, whereas, at perpendicular polarization, it saturates when the absorption length compares the crystal thickness, and then decreases down to a minimum at 3.5 eV. This lowering mirrors a decrease of the PL yield at higher energies. The PC action spectrum shows an opposite behavior: it presents first a rise at 2.4 eV, parallel to the absorption onset, then a second rise at 3.0 eV up to a maximum at 3.3 eV. The first rise corresponds to the generation of singlet excitons, which then give birth to charges, through either exciton breaking, or more likely charge detrapping. The second rise could correspond to a direct ionization process. The magnetic field effect on PC has been studied. A relative decrease of up to 6% at a field of 4000 G has been detected. The decrease is attributed to the lowering of the triplet—doublet interaction constant R.