Using density functional theory (DFT) computations, we have demonstrated a substantial skeletal relaxation when the structure of 2,5-[bis-(4-anthracene-9-yl-phenyl]-1,1-dimethyl-3,4-diphenyl-silole (BAS) is optimized in the gas-phase comparing with the molecular structure determined from monocrystal x-ray diffraction. The origin of such a relaxation is explained by a strong environmental strains induced by the presence of anthracene entities. Moreover, the estimation of the frontier orbital levels showed that this structural relaxation affects mainly the LUMO that is lowered of $190\mathrm{meV}$ in the gas phase. To check if these theoretical findings would be confirmed for thin films of BAS, we turned to ultraviolet photoemission spectroscopy and/or inverse photoemission spectroscopy and electro-optical measurements. Interestingly, the study of the current density or voltage and luminance or voltage characteristics of an $\mathrm{ITO}∕\mathrm{PEDOT}∕\mathrm{BAS}∕\mathrm{Au}$ device clearly demonstrated a very unusual temperature-dependent behavior. Using a thermally assisted tunnel transfer model, we found that this behavior likely originated from the variation of the electronic affinity of the silole derivative with the temperature. The thermal agitation relaxes the molecular strains in thin films as it is shown when passing from the crystalline to the gas phase. The relaxation of the intramolecular thus induces an increase of the electronic affinity and, as a consequence, the more efficient electron injection in organic light-emitting diodes.

• Received 19 July 2006

DOI:https://doi.org/10.1103/PhysRevB.75.115416