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 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.

The morphological, bipolar charge‐carrier transport, and photovoltaic characteristics of poly(3‐alkylthiophene) (P3AT):[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blends are studied as a function of alkyl side‐chain length m, where m equals the number of alkyl carbon atoms. The P3ATs studied are poly(3‐butylthiophene) (P3BT, m = 4), poly(3‐pentylthiophene) (P3PT, m = 5), and poly(3‐hexylthiophene) (P3HT, m = 6). Solar cells with these blends deliver similar order of photo‐current yield (exceeding 10 mA cm−2) irrespective of side‐chain length. Power conversion efficiencies of 3.2, 4.3, and 4.6% are within reach using solar cells with active layers of P3BT:PCBM (1:0.8), P3PT:PCBM (1:1), and P3HT:PCBM (1:1), respectively. A difference in fill factor values is found to be the main source of efficiency difference. Morphological studies reveal an increase in the degree of phase separation with increasing alkyl chain length. Moreover, while P3PT:PCBM and P3HT:PCBM films have similar hole mobility, measured by hole‐only diodes, the hole mobility in P3BT:PCBM lowers by nearly a factor of four. Bipolar measurements made by field‐effect transistor showed a decrease in the hole mobility and an increase in the electron mobility with increasing alkyl chain length. Balanced charge transport is only achieved in the P3HT:PCBM blend. This, together with better processing properties, explains the superior properties of P3HT as a solar cell material. P3PT is proved to be a potentially competitive material. The optoelectronic and charge transport properties observed in the different P3AT:PCBM bulk heterojunction (BHJ) blends provide useful information for understanding the physics of BHJ films and the working principles of the corresponding solar cells.

A new approach is presented in order to improve the thermal stability of polymer:PCBM bulk heterojunction solar cells. The central idea in this approach is the use of a polymer with high glass transition temperature (T g ), well above the normal operating temperatures of the devices. In this paper a PPV-derivative with a T g of 150°C was used as electron donor and the thermal stability of the obtained solar cells was compared with solar cells based on the reference material Poly[2methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) with a T g of 45°C.The use of the material with higher glass transition temperature resulted in a significant improvement of the thermal stability of the photovoltaic parameters. Furthermore, a systematic TEM study demonstrates that the better thermal stability of performance coincides with a more stable active layer morphology. Both improvements are attributed to the reduced free movement of the electron donor material ([6-6]-phenyl C 61 butyric acid methyl ester, PCBM) within the active layer of the solar cell.1

The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO2 gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.