The optoelectronic landscape of conjugated polymers is intimately related to their molecular arrangement and packing, with minute changes in local order, such as chain conformation and torsional backbone order/disorder, frequently having a substantial effect on macroscopic properties. While many of these local features can be manipulated via chemical design, the synthesis of a series of compounds is often required to elucidate correlations between chemical structure and macromolecular ordering. Here, we show that blending semiconducting polymers with insulating commodity plastics enables controlled manipulation of the semiconductor backbone planarity. The key is to create a polarity difference between the semiconductor backbone and its side chains, while matching the polarity of the side chains and the additive. We demonstrate the applicability of this approach through judicious comparison of regioregular poly(3-hexylthiophene) (P3HT) with two of its more polar derivatives, namely the diblock copolymer poly(3hexylthiophene)-block-poly(ethylene oxide) (P3HT-b-PEO) and the graft polymer poly[3-but(ethylene oxide)thiophene] (P3BEOT), as well as their blends with poly(ethylene oxide) (PEO). Proximity between polar side chains and a similarly polar additive reduces steric hindrance between individual chain segments by essentially 'expelling' the side chains away from the semiconducting backbones. This process, which has been shown to be facilitated via exposure to polar environments

Self-generated interlayers provide insight on the energy level alignment at the organic semiconductor/back contact interface in organic solar cells.

A new two-electron photosensitizer, HBBQ[ZnCl]/[(ZnCl)(μ-BBH)] (BBQ stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-quinone and BBH stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-hydroquinone), has been synthesized and the oxidation state of the ligand was determined by X-ray crystallography and NMR spectroscopy. Under light illumination the HBBQ[ZnCl] + ZnCl is reduced quantitatively to [(ZnCl)(μ-BBH)] (pH ∼ 5) oxidizing HO to HO as is evident by trap experiments. Electrochemistry gave a reversible two-electron ligand-centered redox wave for [(ZnCl)(μ-BBH)]. UV-Vis, luminescence and EPR spectroscopies reveal the slow formation of a stable quinone diradical, intermediate of the reaction. DFT calculations are in agreement with the proposed mechanism. Based on this property an aqueous {[(ZnCl)(μ-BBH)]||HO} solar rechargeable galvanic cell has been constructed.

The formation of different types of structural polymorphs of poly(3-hexylthiophene) (P3HT) affects the performance of organic photovoltaic (OPV) devices that use thermally-annealed P3HT:PCBM[60] blend films as photoactive layer. Here it is demonstrated that, when densely-packed and non-densely packed P3HT polymorphs co-exist in the P3HT:PCBM[60] layer, non-geminate charge recombination is fast; however, in a device nongeminate recombination is effectively overruled by efficient and fast charge carrier extraction. In stark contrast, when only a less-densely packed P3HT polymorph is present in the blend, non-geminate charge recombination losses are less pronounced, and the charge carrier extraction efficiency is lower. The antagonistic non-geminate charge recombination and charge carrier extraction processes in these systems are monitored by time-delayed-collection field (TDCF) and ultrafast transient absorption (TA) experiments. Furthermore, resonance Raman spectroscopy reveals that in the absence of the densely-packed P3HT polymorph, the energetic disorder present in the P3HT:PCBM[60] blend is higher. High-resolution atomic force microscopy imaging further identifies pronounced differences in the layer morphology when the polymorph distribution varies between unimodal and bimodal. These results indicate that less-densely packed P3HT polymorphs increase disorder and impede charge collection, leading to a reduction of the device fill factor.

The optoelectronic landscape of conjugated polymers is intimately related to their molecular arrangement and packing, with minute changes in local order, such as chain conformation and torsional backbone order/disorder, frequently having a substantial effect on macroscopic properties. While many of these local features can be manipulated via chemical design, the synthesis of a series of compounds is often required to elucidate correlations between chemical structure and macromolecular ordering. Here, we show that blending semiconducting polymers with insulating commodity plastics enables controlled manipulation of the semiconductor backbone planarity. The key is to create a polarity difference between the semiconductor backbone and its side chains, while matching the polarity of the side chains and the additive. We demonstrate the applicability of this approach through judicious comparison of regioregular poly(3-hexylthiophene) (P3HT) with two of its more polar derivatives, namely the diblock copolymer poly(3hexylthiophene)-block-poly(ethylene oxide) (P3HT-b-PEO) and the graft polymer poly[3-but(ethylene oxide)thiophene] (P3BEOT), as well as their blends with poly(ethylene oxide) (PEO). Proximity between polar side chains and a similarly polar additive reduces steric hindrance between individual chain segments by essentially 'expelling' the side chains away from the semiconducting backbones. This process, which has been shown to be facilitated via exposure to polar environments