The use of diiodooctane as processing additive for construction of PCPDTBT:PCBM solar cells results in a profound change in photophysical behavior of this blend. In the improved morphology obtained with the additive, recombination of charge carriers to the lowest triplet excited state is suppressed. This contributes to the boost in solar power conversion efficiency induced by the use of the processing agent.

Mixtures of conjugated polymers and fullerenes command considerable attention for application in organic solar cells. To increase their efficiency, the design of new materials that absorb at longer wavelengths is of substantial interest. We have prepared such low band gap polymers using the donor-acceptor route, which is based on the concept that the interaction between alternating donors and acceptors results in a compressed band gap. Furthermore, for application in photovoltaic devices, sufficient polymer solubility is required. We have prepared four low band gap conjugated polymers, with a bis(1-cyano-2-thienylvinylene)phenylene base structure, and achieved an excellent solubility by the introduction of long alkoxy and alkyl side chains. The polymers were synthesized via an oxidative polymerization. Their electronic properties were determined from electrochemical and optical measurements, which confirm that they indeed have a low band gap. In the blend of such a low band gap polymer with PCBM, evidence for efficient charge transfer was obtained from PL and EPR measurements. However, bulk heterostructure solar cells made of such blends display only low efficiencies, which is attributed to low charge carrier mobilities.

The W-band continuous-wave electron paramagnetic resonance (EPR) analysis of chemically induced polarons in drop-cast and spin-coated polyphenylenevinylene-type and polythiophene-type polymer films reveals rhombic g tensors in both cases. The dependence of the W-band EPR signals on the orientation of the spin-coated films with respect to the magnetic field indicates a high degree of backbone alignment with the substrate and allows a partial assignment of the g tensor orientation. The derived molecular orientations of the polymer chains in the spin-coated films show clear differences between the two types of polymers. The proton hyperfine interactions obtained from X-band HYSCORE (hyperfine sublevel correlation) and Q- and W-band pulsed ENDOR (electron-nuclear double resonance) experiments are interpreted in terms of earlier theoretical studies on the extension of the polarons.

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Conjugated polymers with strongly twisted backbones, such as MEHPPV with fluorinated vinylene units (F-MEHPPV), demand a redefinition of the all-important 'effective conjugation length' ECL, which we extract here by a facile graphical method. In MEHPPV (being essentially planar), the ECL coincides with the 'maximum conducive chainlength'MCC and extends over about n  9 repetition units (RU). In F-MEHPPV, the MCC is similarly long with n  8, while ECL localizes on just one RU. The strong twist in F-MEHPPV persists in the excited state, broadening the emission spectrum and quenching the fluorescence by reduced radiative and enhanced non-radiative rates.The strong twist in F-MEHPPV persists in the excited state, broadening the emission spectrum, reducing the radiative rate, and enhancing the non-radiative deactivation, so that the fluorescence quantum yield of 30% in MEHPPV drops to 4% in F-MEHPPV. This example strikingly demonstrates how already small geometrical distortions (substitution of H by F) can lead to strong sterical effects, generating dramatic changes in the optical absorption and emission process.

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A low band-gap copolymer PDTBTFV alternating bis-thienyl-(bis-alkoxy)-benzothiadiazole blocks with difluorovinylene units and its non-fluorinated counterpart PDTBTV have been synthesized and characterized as donor materials in bulk heterojunction (BHJ) solar cells with PCBM as the acceptor. The solar cells with the fluorinated polymer show better photovoltaic performances than those recorded with the non-fluorinated material. Comparative spectroscopic and computational studies, together with morphological, electrical and optical characterization of thin films, have been carried out to shed light on the reasons for the improvement of performances as induced by the double bond fluorination. Our study introduces the fluorinated double bond as a new conjugated unit in donor polymers for BHJ solar cells