We investigate thin poly(3‐hexylthiophene‐2,5‐diyl)/[6,6]‐phenyl C61 butyric acid methyl ester (P3HT/PCBM) films, which are widely used as active layers in plastic solar cells. Their structural properties are studied by grazing‐incidence X‐ray diffraction (XRD). The size and the orientation of crystalline P3HT nanodomains within the films are determined. PCBM crystallites are not detected in thin films by XRD. Upon annealing, the P3HT crystallinity increases, leading to an increase in the optical absorption and spectral photocurrent in the low‐photon‐energy region. As a consequence, the efficiency of P3HT/PCBM solar cells is significantly increased. A direct relation between efficiency and P3HT crystallinity is demonstrated.

The evolution of nanomorphology within thin solid‐state films of poly(3‐alkylthiophene):[6,6]‐phenyl‐C61 butyric acid methyl ester (P3AT:PCBM) blends during the film formation and subsequent thermal annealing is reported. In detail, the influence of the P3AT's alkyl side chain length on the polymer/fullerene phase separation is discussed. Butyl, hexyl, octyl, decyl, and dodecyl side groups are investigated. All of the P3ATs used were regioregular. To elucidate the nanomorphology, atomic force microscopy (AFM), X‐ray diffraction, and optical spectroscopy are applied. Furthermore, photovoltaic devices of each of the different P3ATs have been constructed, characterized, and correlated with the nanostructure of the blends. It is proposed that the thermal‐annealing step, commonly applied to these P3AT:PCBM blend films, controls two main issues at the same time: a) the crystallization of P3AT and b) the phase separation and diffusion of PCBM. The results show that PCBM diffusion is the main limiting process for reaching high device performances.

The preparation of 27 different derivatives of C60 and C70 fullerenes possessing various aryl (heteroaryl) and/or alkyl groups that are appended to the fullerene cage via a cyclopropane moiety and their use in bulk heterojunction polymer solar cells is reported. It is shown that even slight variations in the molecular structure of a compound can cause a significant change in its physical properties, in particular its solubility in organic solvents. Furthermore, the solubility of a fullerene derivative strongly affects the morphology of its composite with poly(3‐hexylthiophene), which is commonly used as active material in bulk heterojunction organic solar cells. As a consequence, the solar cell parameters strongly depend on the structure and the properties of the fullerene‐based material. The power conversion efficiencies for solar cells comprising these fullerene derivatives range from negligibly low (0.02%) to considerably high (4.1%) values. The analysis of extensive sets of experimental data reveals a general dependence of all solar cell parameters on the solubility of the fullerene derivative used as acceptor component in the photoactive layer of an organic solar cell. It is concluded that the best material combinations are those where donor and acceptor components are of similar and sufficiently high solubility in the solvent used for the deposition of the active layer.

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Polymer solar cells based on poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) were fabricated using two different solvents. P3HT:PCBM films casted from chlorobenzene solution absorb more red light than the films casted from chloroform solution. After thermal annealing, the films casted from chloroform show higher absorption than the films casted from chlorobenzene. Solar cells made from P3HT:PCBM chlorobenzene solution show no change in the white light power conversion efficiency (2.2%) after annealing. Solar cells processed from P3HT:PCBM chloroform solution show a white light power conversion efficiency of 1.5% without thermal annealing and 3.4% after the thermal annealing. The stated efficiencies are not corrected for the spectral mismatch.

While organic semiconductors used in polymer:fullerene photovoltaics are generally not intentionally doped, significant levels of unintentional doping have previously been reported in the literature. Here, we explain the differences in photocurrent collection between standard (transparent anode) and inverted (transparent cathode) low band-gap polymer:fullerene solar cells in terms of unintentional p-type doping. Using capacitance/voltage measurements, we find that the devices exhibit doping levels of order 10 16 cm 23 , resulting in space-charge regions ,100 nm thick at short circuit. As a result, low field regions form in devices thicker than 100 nm. Because more of the light is absorbed in the low field region in standard than in inverted architectures, the losses due to inefficient charge collection are greater in standard architectures. Using optical modelling, we show that the observed trends in photocurrent with device architecture and thickness can be explained if only charge carriers photogenerated in the depletion region contribute to the photocurrent.T he record power conversion efficiency (PCE) achieved by polymer:fullerene solar cells has increased considerably in the past 4 years to a record published value of 9.2% 1 for a single bulk heterojunction and efficiencies of 10.6% for tandem solar cells 2 . This is despite the fact that organic semiconductors are known to be both structurally and electronically disordered, have lower dielectric constants inhibiting separation of the photogenerated excitonic species and have charge carrier mobilities orders of magnitude lower than inorganic semiconductors.Whilst charge mobilities are low in organic semiconductors and collection losses have been shown to limit the fill factor (FF) 3-5 and short circuit current density (J SC ) 6-10 of certain devices, low mobilities do not necessarily prevent devices from performing efficiently. However the lower charge mobilities and diffusion coefficients in organic semiconductors do mean that diffusion alone is insufficient for charge carrier collection and drift must account for a large proportion of the generated photocurrent. Additionally, polymer:fullerene solar cells are not intentionally doped like their inorganic counterparts or like many small molecule solar cells 11 and therefore rely on selective contacts and the difference in work function between electrodes for efficient charge collection. However, several studies have found evidence for unintentional doping [12][13][14][15][16][17][18][19] and discussed the consequences for device behaviour 6,[20][21][22][23][24][25][26][27][28][29][30] . Whilst the origin of this doping is unclear 15 , its effects on photovoltaic performance can be substantial; however many recent analyses of device performance neglect doping 8,[31][32][33] despite the fact that the influence of doping and the electric field on charge carrier collection is well known for a long time 34 and wellstudied for instance in the field of quantum dot photovoltaics 35,36 .In this paper, we address the...