Nanostructured phase-separated blends, or bulk heterojunctions, of conjugated polymers and fullerene derivatives form a very attractive approach to large-area, solid-state organic solar cells. The key feature of these cells is that they combine easy processing from solution on a variety of substrates with good performance. Efficiencies of up to 5% in solar light have been achieved, and lifetimes are increasing to thousands of hours. Further improvements can be expected and some of the promising strategies towards that goal are presented in this article.

Thermal deposition of small amounts of various salts at the interface between the active layer and the aluminum cathode was shown to alter the performance of bulk heterojunction photovoltaic devices. LiF and LiBr were found to enhance the power conversion efficiency as compared to devices with no interfacial salt, but Cs and K compounds were found to severely diminish the device performance. It is suggested that the Li compounds preferentially align to produce a bulk dipole moment at the interface, whereas the Cs and K compounds do not.

The preparation of double-cable polymers, which consist of a hole conducting conjugated chain carrying pendant electron accepting/conducting moieties, is a promising strategy to prevent donor/acceptor phase segregation and to achieve defined microscopic structure in organic bulk heterojunction solar cells. In this paper we report the electrochemical synthesis and the investigation of a double-cable consisting of a polythiophene backbone bearing, via covalent bonds, electron accepting tetracyanoanthraquinodimethane (TCAQ) type moieties. Electrochemical studies and UV- VIS absorption spectroscopy reveal, that in dark, the polythiophene chain and the TCAQ moieties retain their individual ground-state properties. Upon illumination photoinduced electron transfer occurs, which is studied by photoinduced VIS-NIR absorption spectroscopy.

Difference infrared spectra between illumination and dark of a polyethylenedioxythiophene (PEDOT) covered germanium electrode in contact with the electrolyte solution and under applied potential are shown. The spectra show a different behavior at different redox (doping) states of the polymer. The photoinduced formation of positive charge carriers was found by illumination of the neutral (undoped) form, wheras no significant spectral changes occur in the oxidized (p-doped) and reduced (n-doped) form of PEDOT.

Regioregular polythiophenes baring 3-(p-methoxyethoxyethoxy)-phenyl substituents (PEOPT) show high photoluminescence efficiencies. Exposing thin films of this polymer to vapors of chloroform or annealing them by heat treatment results in a red shift of the absorption maximum due to solvent or heat induced ordering which gives rise to more planar conformations. The fact, that annealed thin films of PEOPT exhibit absorption edges at relatively low energies and thus have an enhanced spectral range makes them suitable for use in photodiodes / solar cells. The photoinduced charge generation efficiency in PEOPT is significantly enhanced by the addition of a strong electron acceptor like fullerene, as observed by quenching of the luminescence and by photoinduced absorption measurements in the infrared and UV-Vis regime. The efficiency of the photoinduced charge transfer from PEOPT to a methanofullerene is found to depend on the ordering of PEOPT in thin films.

Using the ultrafast photoinduced electron transfer with long-living charge separation in the conjugated polymer/fullerene thin films, photovoltaic devices have been fabricated. The photoinduced charge separation happens with internal quantum efficiency near unity. The performance of such “bulk heterojunction” photovoltaic devices is critically dependent on the transport properties of the interpenetrating network. The influence of the variation of different donor / acceptor materials on the sample morphology is monitored by atomic force microscopy (AFM), while I/V characteristics have been studied to evaluate the conversion efficiency.

Homogenous blends of a processable methanofullerene, [6,6]-Phenyl C61 - butyric acid methyl ester (PCBM), with poly (p-phenylene vinylene) (PPV) made from a novel nonionic precursor route were investigated by optical spectroscopy and by photocurrent measurements. The conversion process of the precursor polymer to the PPV in the blends with PCBM was monitored by IR absorption. In composites of PPV/PCBM strong quenching of the PPV luminescence was observed. LESR (light induced electron spin resonance) and PIA (photoinduced absorption) studies confirmed the occurrence of photoinduced electron transfer from the PPV to PCBM. Photovoltaic devices made from PPV/PCBM blends showed monochromatic power conversion efficiencies of app. 0.3%. The spectral photocurrent was observed to follow the absorption profile of the PPV.