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The application of new polymer materials for organic solar cells requires a detailed understanding of the orientation and the electronic properties of the system because these have a dramatic effect on the device performance and efficiency. The films were prepared by doctor blade casting, a simple preparation route from solution. We study the orientation of the low band gap polymers poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and poly-[2,6-(4,4-bis(2-ethyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene)-alt-5,8-(2,3-dioctylquinoxaline)] (PCPDTQ) as well as of the state of the art polymer poly(3-hexyl-thiophene) (P3HT) using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Clear angular dependence in the NEXAFS spectra is observed for P3HT and PCPDTBT pointing to well-orientated films.

We report on the efficiency enhancement for bulk-heterojunction hybrid solar cells based on hexanoic acid treated trioctylphosphine/oleic acid-capped CdSe quantum dots (QDs) and low bandgap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4 H -cyclopenta[2,1- b ;3,4- b ′]-dithiophene)- alt -4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) compared to devices based on poly(3-hexylthiophene) (P3HT). Photovoltaic devices with optimized polymer:QD weight ratio, photoactive film thickness, thermal annealing treatment, and cathode materials exhibited a power conversion efficiency of 2.7% after spectral mismatch correction, which is the highest reported value for spherical CdSe QD based photovoltaic devices. The efficiency enhancement is attributed to the surface treatment of the QDs together with the use of the low bandgap polymer PCPDTBT leading to an increased short-circuit current density due to additional light absorption between 650 and 850 nm. Our results suggest that the hexanoic acid treatment is generally applicable to various ligand-capped CdSe and confirm that low bandgap polymers with adequate HOMO and LUMO levels are promising to be incorporated into hybrid solar cells for further device performance improvement.

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (eta=8%). pi-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.