Chemically treating poly(3-hexylthiophene) defects to improve bulk heterojunction photovoltaics

Defect engineering has been of vital importance to the development of inorganic semiconductors. Here, we report the chemical modification of electrical defects in the prototypical organic semiconductor, regioregular poly(3-hexylthiophene), P3HT. Previously, we have covalently treated defect sites with either a nucleophile or an electrophile, leaving the defects of primarily opposite polarity. Consecutively using both nucleophilic and electrophilic treatments allows us to covalently fix both positively and negatively charged defect sites in a single procedure. Here we describe the effects of treating P3HT first with lithium aluminum hydride, LAH, to decrease the overall defect density, and then with dimethylsulfate, Me(2)SO(4), to eliminate some of the remaining n-type defects (equivalent to a p-type doping process). The resulting polymer, P3HT_LAH_Me(2)SO(4), behaves differently than the polymer obtained when the order of treatments is reversed, P3HT_Me(2)SO(4)_LAH. Slightly improved structural and optical differences between these two new polymers and the starting P3HT are observed, whereas greatly improved electrical differences are found. Both treatments improve the performance of the photovoltaic cells, especially the short circuit current and the fill factor, and increase the stability against photodegradation. The significantly decreased series resistance and increased shunt resistance with a combined treatment suggest improved charge transport in the cell. The effective doping density can be increased or decreased with these treatments while the carrier mobility and the exciton diffusion length increase. It should be possible to employ these simple chemical treatments with any π-conjugated polymer to beneficially modify, or eliminate, some of its electronic defects. As a consequence, our approach provides a new method of improving the air-stability and electrical characteristics for organic photovoltaic and other electronic applications.