V.D. Mihailetchi

Abstract Plastic solar cells bear the potential for large‐scale power generation based on materials that provide the possibility of flexible, lightweight, inexpensive, efficient solar cells. Since the discovery of the photoinduced electron transfer from a conjugated polymer to fullerene molecules, followed by the introduction of the bulk heterojunction (BHJ) concept, this material combination has been extensively studied in organic solar cells, leading to several breakthroughs in efficiency, with a power conversion efficiency approaching 5 %. This article reviews the processes and limitations that govern device operation of polymer:fullerene BHJ solar cells, with respect to the charge‐carrier transport and photogeneration mechanism. The transport of electrons/holes in the blend is a crucial parameter and must be controlled (e.g., by controlling the nanoscale morphology) and enhanced in order to allow fabrication of thicker films to maximize the absorption, without significant recombination losses. Concomitantly, a balanced transport of electrons and holes in the blend is needed to suppress the build‐up of the space–charge that will significantly reduce the power conversion efficiency. Dissociation of electron–hole pairs at the donor/acceptor interface is an important process that limits the charge generation efficiency under normal operation condition. Based on these findings, there is a compromise between charge generation (light absorption) and open‐circuit voltage ( V OC ) when attempting to reduce the bandgap of the polymer (or fullerene). Therefore, an increase in V OC of polymer:fullerene cells, for example by raising the lowest unoccupied molecular orbital level of the fullerene, will benefit cell performance as both fill factor and short‐circuit current increase simultaneously.

The open-circuit voltage Voc of polymer:fullerene bulk heterojunction solar cells is investigated as a function of light intensity for different temperatures. Devices consisted of a blend of a poly(p-phenylene vinylene) derivative as the hole conductor and 6,6-phenyl C61-butyric acid methyl ester as the electron conductor. The observed photogenerated current and Voc are at variance with classical p–n junction-based models. The influence of light intensity and recombination strength on Voc is consistently explained by a model based on the notion that the quasi-Fermi levels are constant throughout the device, including both drift and diffusion of charge carriers.

In 1971 Goodman and Rose predicted the occurrence of a fundamental electrostatic limit for the photocurrent in semiconductors at high light intensities. Blends of conjugated polymers and fullerenes are an ideal model system to observe this space-charge limit experimentally, since they combine an unbalanced charge transport, long lifetimes, high charge carrier generation efficiencies, and low mobility of the slowest charge carrier. The experimental photocurrents reveal all the characteristics of a space-charge limited photocurrent: a one-half power dependence on voltage, a three-quarter power dependence on light intensity, and a one-half power scaling of the voltage at which the photocurrent switches into full saturation with light intensity.

The photocurrent in conjugated polymer-fullerene blends is dominated by the dissociation efficiency of bound electron-hole pairs at the donor-acceptor interface. A model based on Onsager's theory of geminate charge recombination explains the observed field and temperature dependence of the photocurrent in PPV:PCBM blends. At room temperature only 60% of the generated bound electron-hole pairs are dissociated and contribute to the short-circuit current, which is a major loss mechanism in photovoltaic devices based on this material system.

We have developed a numerical device model that consistently describes the current-voltage characteristics of polymer:fullerene bulk heterojunction solar cells. Bimolecular recombination and a temperature- and field-dependent generation mechanism of free charges are incorporated. It is demonstrated that in poly[2-methoxy-5-(${3}^{\ensuremath{'}},{7}^{\ensuremath{'}}$-dimethyloctyloxy)-$p$-phenylene vinylene]- ($\mathrm{O}{\mathrm{C}}_{1}{\mathrm{C}}_{10}\text{\ensuremath{-}}\mathrm{PPV}$-) and [6,6]-phenyl ${\mathrm{C}}_{61}$-butyric acid methyl ester- (PCBM-) $(1:4\phantom{\rule{0.3em}{0ex}}\mathrm{wt.}\phantom{\rule{0.2em}{0ex}}%)$ based solar cells space-charge effects only play a minor role, leading to a relatively constant electric field in the device. Furthermore, at short-circuit conditions only 7% of all free carriers are lost due to bimolecular recombination. The model predicts that an increased hole mobility together with a reduction of the acceptor strength of $0.5\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ will lead to a maximum attainable efficiency of 5.5% in the PPV/PCBM-based solar cells.