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

The current–voltage characteristics of ITO/PEDOT:PSS/OC1C10‐PPV:PCBM/Al solar cells were measured in the temperature range 125–320 K under variable illumination, between 0.03 and 100 mW cm–2 (white light), with the aim of determining the efficiency‐limiting mechanism(s) in these devices, and the temperature and/or illumination range(s) in which these devices demonstrate optimal performance. (ITO: indium tin oxide; PEDOT:PSS: poly(styrene sulfonate)‐doped poly(ethylene dioxythiophene); OC1C10‐PPV: poly[2‐methoxy‐5‐(3,7‐dimethyl octyloxy)‐1,4‐phenylene vinylene]; PCBM: phenyl‐C61 butyric acid methyl ester.) The short‐circuit current density and the fill factor grow monotonically with temperature until 320 K. This is indicative of a thermally activated transport of photogenerated charge carriers, influenced by recombination with shallow traps. A gradual increase of the open‐circuit voltage to 0.91 V was observed upon cooling the devices down to 125 K. This fits the picture in which the open‐circuit voltage is not limited by the work‐function difference of electrode materials used. The overall effect of temperature on solar‐cell parameters results in a positive temperature coefficient of the power conversion efficiency, which is 1.9 % at T = 320 K and 100 mW cm–2 (2.5 % at 0.7 mW cm–2). The almost‐linear variation of the short‐circuit current density with light intensity confirms that the internal recombination losses are predominantly of monomolecular type under short‐circuit conditions. We present evidence that the efficiency of this type of solar cell is limited by a light‐dependent shunt resistance. Furthermore, the electronic transport properties of the absorber materials, e.g., low effective charge‐carrier mobility with a strong temperature dependence, limit the photogenerated current due to a high series resistance, therefore the active layer thickness must be kept low, which results in low absorption for this particular composite absorber.

In this work, the phase diagram of poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blends is measured by means of standard and modulated temperature differential scanning calorimetry. Blends were made by solvent-casting from chlorobenzene, as blends cast from toluene or 1,2-dichlorobenzene prove to retain effects of phase segregation during casting, hindering the determination of the phase diagram. The film morphology of P3HT/PCBM blends cast from chlorobenzene results from a dual crystallization behavior, in which the crystallization of each component is hindered by the other component. A single glass transition is observed for all compositions. The glass transition temperature (Tg) increases with increasing concentration of PCBM: from 12.1 degrees C for pure P3HT to 131.2 degrees C for pure PCBM. The observed Tg defines the operating window for the thermal annealing and explains the long-term instability of both the morphology and the photovoltaic performance of the P3HT/PCBM solar cells.

Evidence is presented for the formation of a weak ground‐state charge‐transfer complex in the blend films of poly[9,9‐dioctylfluorene‐co‐N‐(4‐methoxyphenyl)diphenylamine] polymer (TFMO) and [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM), using photothermal deflection spectroscopy (PDS) and photoluminescence (PL) spectroscopy. Comparison of this polymer blend with other polyfluorene polymer/PCBM blends shows that the appearance of this ground‐state charge‐transfer complex is correlated to the ionization potential of the polymer, but not to the optical gap of the polymer or the surface morphology of the blend film. Moreover, the polymer/PCBM blend films in which this charge‐transfer complex is observed also exhibit efficient photocurrent generation in photovoltaic devices, suggesting that the charge‐transfer complex may be involved in charge separation. Possible mechanisms for this charge‐transfer state formation are discussed as well as the significance of this finding to the understanding and optimization of polymer blend solar cells.