Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials.

The increasing amount of research on solution-processable, organic donor-acceptor bulk heterojunction photovoltaic systems, based on blends of conjugated polymers and fullerenes has resulted in devices with an overall power-conversion efficiency of 6%. For the best devices, absorbed photon-to-electron quantum efficiencies approaching 100% have been shown. Besides the produced current, the overall efficiency depends critically on the generated photovoltage. Therefore, understanding and optimization of the open-circuit voltage (Voc) of organic solar cells is of high importance. Here, we demonstrate that charge-transfer absorption and emission are shown to be related to each other and Voc in accordance with the assumptions of the detailed balance and quasi-equilibrium theory. We underline the importance of the weak ground-state interaction between the polymer and the fullerene and we confirm that Voc is determined by the formation of these states. Our work further suggests alternative pathways to improve Voc of donor-acceptor devices.

The open-circuit voltage ͑V oc ͒ of polymer:fullerene bulk heterojunction solar cells is determined by the interfacial charge-transfer ͑CT͒ states between polymer and fullerene. Fourier-transform photocurrent spectroscopy and electroluminescence spectra of several polymer:fullerene blends are used to extract the relevant interfacial molecular parameters. An analytical expression linking these properties to V oc is deduced and shown to be valid for photovoltaic devices comprising three commonly used conjugated polymers blended with the fullerene derivative ͓6,6͔-phenyl-C61-butyric acid methyl ester ͑PCBM͒. V oc is proportional to the energy of the CT states E CT . The energetic loss q⌬V between E CT and qV oc vanishes when approaching 0 K. It depends linearly on T and logarithmically on illumination intensity. Furthermore q⌬V can be reduced by decreasing the electronic coupling between polymer and fullerene or by reducing the nonradiative recombination rate. For the investigated devices we find a loss q⌬V of ϳ0.6 eV at room temperature and under solar illumination conditions, of which ϳ0.25 eV is due to radiative recombination via the CT state and ϳ0.35 eV is due to nonradiative recombination.

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.

Organic solar cells demonstrate external quantum efficiencies and fill factors approaching those of conventional photovoltaic technologies. However, as compared to the optical gap of the absorber materials, their open-circuit voltage is much lower, largely due to the presence of significant nonradiative recombination. In this work, we study a large data set of published and new material combinations and find that non-radiative voltage losses decrease with increasing charge-transfer state energies. This observation is explained by considering non-radiative charge-transfer state decay as electron transfer in the Marcus inverted regime, being facilitated by a common skeletal molecular vibrational mode. Our results suggest an intrinsic link between non-radiative voltage losses and electron-vibration coupling, indicating that these losses are unavoidable. Accordingly, the theoretical upper limit for the power conversion efficiency of single junction organic solar cells would be reduced to about 25.5% and the optimal optical gap increases to (1.45-1.65) eV, i.e. (0.2-0.3) eV higher than for technologies with minimized non-radiative voltage losses. Manuscript: "Intrinsic Non-Radiative Voltage Losses in Fullerene-Based OSCs" J. Benduhn et al.