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.

Photocurrent generation by charge-transfer (CT) absorption is detected in a range of conjugated polymer: [6,6]-phenyl C 61 butyric acid methyl ester (PCBM) based solar cells. The low intensity CT absorption bands are observed using a highly sensitive measurement of the external quantum efficiency (EQE) spectrum by means of Fourier-transform photocurrent spectroscopy (FTPS). The presence of these CT bands implies the formation of weak groundstate charge-transfer complexes in the studied polymer:fullerene blends. The effective band gap (E g ) of the material blends used in these photovoltaic devices is determined from the energetic onset of the photocurrent generated by CT absorption. It is shown that for all

In this article we report the weak but omnipresent electroluminescence (EL) from several types of organic polymer:fullerene bulk heterojunction solar cells biased in the forward direction. The light emitted from blends of some commonly used polymers and the fullerene molecule is significantly different from that of any of the pure materials comprising the blend. The lower energy of the blend EL is found to correlate with both the voltage onset of emission and the open-circuit voltage of the photovoltaic cell under solar illumination. We accordingly interpret the emission to originate from interfacial charge transfer state recombination and emphasize EL as a very valuable tool to characterize the charge transfer state present in donor/acceptor organic photovoltaic (OPV) cells.

The photovoltaic parameters of donor/acceptor blend organic solar cells are highly influenced by several parameters, such as the strength of the acceptor species, the morphology of the film due to the solvent, and the mobility of the free charge carriers. In this work, the open-circuit voltage (Voc) of solar cells based on series of conjugated polythiophene polymers were measured and compared. In every cell, the donor polymer was blended with an electron acceptor fullerene molecule. The devices were constructed in a sandwich structure with indium tin oxide (ITO)/metallic polymer (PEDOT:PSS) acting as an anode and Al or LiF/Al acting as a cathode. Comparing the Voc of all the cells shows that this important photovoltaic parameter is systematically varying with the polymer. The variation of photovoltage is attributed to the variation of the oxidation potential of the donor conjugated polymers after due consideration of the different injection conditions in the varying polymers.

In high performance polymer:fullerene bulk heterojunction solar cells the nanoscale morphology of interpenetrating acceptor:donor materials is optimised through appropriate preparation conditions such as annealing and choice of solvent, but this initial state-of-the-art morphology will not remain stable during long term operation. We report the effects of prolonged storage at elevated temperatures on both the morphology and the photovoltaic performance for the model systems MDMO-PPV:PCBM and P3HT:PCBM as compared to 'High T g PPV':PCBM based solar cells, where the 'High T g PPV' is characterised by its high glass transition temperature (138°C). In-situ monitoring of the photo-current-voltage characteristics at elevated temperatures, in combination with a systematic Transmission Electron Microscopy (TEM) study and complementary optical spectroscopy, reveals distinct degradation 1 kinetics and morphological changes that indicate the occurrence of different underlying physico-chemical mechanisms.

A new alternating polyfluorene copolymer poly[2,7‐(9,9‐dioctylfluoren)‐alt‐5,5‐(5′,8′‐di‐2‐thienyl‐(2′,3′‐bis‐(3′′‐octyloxyphenyl)‐quinoxaline))] (APFO‐15), which has electron donor–acceptor–donor units in between the fluorene units, is synthesized and characterized. This polymer has a strong absorption and emission in the visible range of the solar spectrum. Its electroluminescence and photoluminescence emissions extend from about 560 to 900 nm. Moreover, solar cells with efficiencies in excess of 3.5 % have been realized from blends of APFO‐15 and an electron acceptor molecule, a methanofullerene [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM). It has also been observed that electron and hole transport is balanced both in the pure polymer phase and in polymer/PCBM bulk heterojunction films, which makes this material quite attractive for applications in opto‐electronic devices.

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