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Polymer/fullerene bulk heterojunction solar cells consisting of PDDTP:PCBM blends have been investigated and optimized. The structural properties of the photoactive layers were studied by GID-XRD, which revealed a pronounced response of photovoltaic parameters on the polymer crystallinity. In addition to P3HT, another donor polymer was found that develops crystalline domains upon annealing. We found a clear correlation between annealing time, power conversion efficiency, and polymer crystallinity. The PDDTP crystallization ability is a promising property. This is a first step toward the synthesis of low-bandgap polymers, which likewise show the ability to form crystalline domains and may therefore lead to a substantial increase in efficiency.

The evolution of nanomorphology within thin solid-state films of poly(3-alkylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester (P3AT:PCBM) blends during the film formation and subsequent thermal annealing is reported. In detail, the influence of the P3AT's alkyl side chain length on the polymer/fullerene phase separation is discussed. Butyl, hexyl, octyl, decyl, and dodecyl side groups are investigated. All of the P3ATs used were regioregular. To elucidate the nanomorphology, atomic force microscopy (AFM), X-ray diffraction, and optical spectroscopy are applied. Furthermore, photovoltaic devices of each of the different P3ATs have been constructed, characterized, and correlated with the nanostructure of the blends. It is proposed that the thermal-annealing step, commonly applied to these P3AT:PCBM blend films, controls two main issues at the same time: a) the crystallization of P3AT and b) the phase separation and diffusion of PCBM. The results show that PCBM diffusion is the main limiting process for reaching high device performances.

We investigate thin poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl C61 butyric acid methyl ester (P3HT/PCBM) films, which are widely used as active layers in plastic solar cells. Their structural properties are studied by grazing-incidence X-ray diffraction (XRD). The size and the orientation of crystalline P3HT nanodomains within the films are determined. PCBM crystallites are not detected in thin films by XRD. Upon annealing, the P3HT crystallinity increases, leading to an increase in the optical absorption and spectral photocurrent in the low-photon-energy region. As a consequence, the efficiency of P3HT/PCBM solar cells is significantly increased. A direct relation between efficiency and P3HT crystallinity is demonstrated.