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. In spite of the impressive development achieved by organic photovoltaics throughout the last decades, especially in terms of reported power conversion efficiencies, there are still important technological and fundamental obstacles to circumvent before they can be implemented into reliable and long-lasting applications. Regarding device processing, the synthesis of highly soluble polymeric semiconductors first, and then fullerene derivatives, was initially considered as an important breakthrough that would definitely change the fabrication of photovoltaics once and for all. The potential and the expectation raised by this technology is such that it is very difficult to keep track of the most significant progresses being now published in different and even monographic journals. In this paper, we review the development of polymeric solar cells from its origin to the most efficient devices published to date. We separate these achievements into three different categories traditionally followed by the scientific community to push devices over 10% power conversion efficiency: active materials, strategies—fabrication/processing procedures—that can mainly modify the active film morphology, and all the different cell layout/architectures that have been used in order to extract as high a photocurrent as possible from the Sun. The synthesis of new donors, the use of additives and postprocessing techniques, buffer interlayers, inverted and tandem designs are some of the most important aspects that are reviewed in detail in this paper. All have equally contributed to develop this technology and bring it at the doors of commercialization.

Polymer:fullerene solar cells: materials, processing issues, and cell layouts to reach power conversion efficiency over 10%, a review