Influence of selenophene on the properties of semi-random polymers and their blends with PC61BM

In an effort to broaden the absorption of conjugated polymers, atomistic bandgap control was applied to the semi-random polymer architecture. Here, we report the physical properties of semi-random polyselenophenes as compared to analogous polythiophenes. In order to examine the effect of the selenium heteroatom on the optical properties of the polymers, UV-vis spectra were studied and it was found that all polyselenophenes exhibit lower bandgaps and higher absorption coefficients in thin films. Further, differential scanning calorimetry and grazing incidence x-ray diffraction results indicate that semi-random polyselenophenes are semicrystalline polymers and their (100) interchain distances are shorter than in the case of semi-random polythiophenes, which may be responsible for higher absorption coefficients. To probe the effect of the selenium heteroatom on the nano-organization of these polymers and their blends with PC61BM, thin films were studied by transmission electron microscopy (TEM). The TEM images show a segregation between more densely packed areas from less densely packed areas in the pristine polymer films, which is more pronounced for polyselenophenes than for polythiophenes. The blends of polyselenophenes with PC61BM do not show the well-defined segregation observed for the polythiophene analogues. However, the broadened and extended absorption of semi-random polyselenophenes translates into an extended photocurrent response in the photovoltaic devices, as evidenced by external quantum efficiency measurements.