J. K. J. van Duren

Abstract The performance of bulk‐heterojunction solar cells based on a phase‐separated mixture of donor and acceptor materials is known to be critically dependent on the morphology of the active layer. Here we use a combination of techniques to resolve the morphology of spin cast films of poly( p ‐phenylene vinylene)/methanofullerene blends in three dimensions on a nanometer scale and relate the results to the performance of the corresponding solar cells. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and depth profiling using dynamic time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) clearly show that for the two materials used in this study, 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene (PCBM) and poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV), phase separation is not observed up to 50 wt.‐% PCBM. Nanoscale phase separation throughout the film sets in for concentrations of more than 67 wt.‐% PCBM, to give domains of rather pure PCBM in a homogenous matrix of 50:50 wt.‐% MDMO‐PPV/PCBM. Electrical characterization, under illumination and in the dark, of the corresponding photovoltaic devices revealed a strong increase of power conversion efficiency when the phase‐separated network develops, with a sharp increase of the photocurrent and fill factor between 50 and 67 wt.‐% PCBM. As the phase separation sets in, enhanced electron transport and a reduction of bimolecular charge recombination provide the conditions for improved performance. The results are interpreted in terms of a model that proposes a hierarchical build up of two cooperative interpenetrating networks at different length scales.

Abstract The current–voltage characteristics of methanofullerene [6,6]‐phenyl C 61 ‐butyric acid methyl ester (PCBM)‐based devices are investigated as a function of temperature. The occurrence of space–charge limited current enables a direct determination of the electron mobility. At room temperature, an electron mobility of μ e = 2 × 10 –7 m 2 V –1 s –1 has been obtained. This electron mobility is more than three orders of magnitude larger than the hole mobility of donor‐type conjugated polymer poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐ p ‐phenylene vinylene) (OC 1 C 10 ‐PPV). As a result, the dark current in PCBM/OC 1 C 10 ‐PPV based devices is completely dominated by electrons. The observed field and temperature‐dependence of the electron mobility of PCBM can be described with a Gaussian disorder model. This provides information about the energetic disorder and average transport‐site separation in PCBM.

Abstract The dependence of the performance of OC 1 C 10 ‐PPV:PCBM (poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐ p ‐phenylene vinylene):methanofullerene [6,6]‐phenyl C 61 ‐butyric acid methyl ester)‐based bulk heterojunction solar cells on their composition has been investigated. With regard to charge transport, we demonstrate that the electron mobility gradually increases on increasing the PCBM weight ratio, up to 80 wt.‐%, and subsequently saturates to its bulk value. Surprisingly, the hole mobility in the PPV phase shows an identical behavior and saturates beyond 67 wt.‐% PCBM, a value which is more than two orders of magnitude higher than that of the pure polymer. The experimental electron and hole mobilities were used to study the photocurrent generation of OC 1 C 10 ‐PPV:PCBM bulk‐heterojunction (BHJ) solar cells. From numerical calculations, it is shown that for PCBM concentrations exceeding 80 wt.‐% reduced light absorption is responsible for the loss of device performance. From 80 to 67 wt.‐%, the decrease in power conversion efficiency is mainly due to a decreased separation efficiency of bound electron–hole (e–h) pairs. Below 67 wt.‐%, the performance loss is governed by a combination of a reduced generation rate of e–h pairs and a strong decrease in hole transport.

The morphology of composite thin films consisting of a conjugated polymer (poly[2-methoxy-5-(3‘,7‘-dimethyloctyloxy)-1,4-phenylenevinylene], MDMO-PPV) and methanofullerene ([6,6]-phenyl C61 butyric acid methyl ester, PCBM), which are used as the active layer in polymer photovoltaic devices, has been extensively studied using transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). Composite MDMO-PPV:PCBM films have been prepared with PCBM concentrations varying from 20 to 90 wt %. PCBM-rich clusters are clearly observed in TEM bright-field mode when the PCBM concentration is increased to ca. 75 wt % in the composite film. The SAED analysis shows that these clusters consist of many PCBM nanocrystals with random crystallographic orientations. Furthermore, we show that these nanocrystals are also present in the homogeneous matrix at PCBM concentrations below 75 wt %. Annealing of the blend films has been performed at temperatures between 60 and 130 °C for different times. In all cases, but especially when the annealing temperature is above the glass transition temperature of MDMO-PPV (∼80 °C), PCBM molecules show high diffusion mobility, resulting in accelerated phase segregation and in the formation of large PCBM single crystals in the film. The observed phase segregation, even at temperatures as low as 60 °C, indicates that the thermal stability of MDMO-PPV:PCBM films will likely limit the long-term performance of solar cells based on these materials.

Low optical bandgap conjugated polymers may improve the efficiency of organic photovoltaic devices by increasing the absorption in the visible and near infrared region of the solar spectrum. Here we demonstrate that condensation polymerization of 2,5-bis(5-trimethylstannyl-2-thienyl)-N-dodecylpyrrole and 4,7-dibromo-2,1,3-benzothiadiazole in the presence of Pd(PPh3)2Cl2 as a catalyst affords a novel conjugated oligomeric material (PTPTB), which exhibits a low optical bandgap as a result of the alternation of electron-rich and electron-deficient units along the chain. By varying the molar ratio of the monomers in the reaction and fractionation of the reaction product, two different molecular weight fractions (PTPTB-I and PTPTB-II, see Experimental section) were isolated, containing 5–17 and 13–33 aromatic units respectively, as inferred from matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Thin films of PTPTB-I and PTPTB-II exhibit an optical bandgap of 1.60 and 1.46 eV, respectively. Photoinduced absorption (PIA) and photoluminescence spectroscopy of blends of PTPTB-I and a methanofullerene (1-(3-methoxycarbonyl)-propyl-1-phenyl-[6,6]C61, PCBM) gave direct spectral evidence of the photoinduced electron-transfer reaction from PTPTB-I as a donor to the fullerene derivative as an acceptor. Thin PTPTB-I:PCBM composite films were sandwiched between indium tin oxide/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (ITO/PEDOT:PSS) and Al electrodes to prepare working photovoltaic devices, which show an open circuit voltage of 0.67 V under white-light illumination. The spectral dependence of the device shows an onset of the photocurrent at 1.65 eV (750 nm).