Photo‐induced Charge Transfer and Relaxation of Persistent Charge Carriers in Polymer/Nanocrystal Composites for Applications in Hybrid Solar Cells

The photo‐induced charge transfer and the dynamics of persistent charge carriers in blends of semiconducting polymers and nanocrystals are investigated. Regioregular poly(3‐hexylthiophene) (P3HT) is used as the electron donor material, while the acceptor moiety is established by CdSe nanocrystals (nc‐CdSe) prepared via colloidal synthesis. As a reference system, organic blends of P3HT and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) are studied as well. The light‐induced charge transfer between P3HT and the acceptor materials is studied by photoluminescence (PL), photo‐induced absorption (PIA) and light‐induced electron spin resonance spectroscopy (LESR). Compared to neat P3HT samples, both systems show an intensified formation of polarons in the polymer upon photo‐excitation, pointing out successful separation of photogenerated charge carriers. Additionally, relaxation of the persistent charge carriers is investigated, and significant differences are found between the hybrid composite and the purely organic system. While relaxation, reflected in the transient signal decay of the polaron signal, is fast in the organic system, the hybrid blends exhibit long‐term persistence. The appearance of a second, slow recombination channel indicates the existence of deep trap states in the hybrid system, which leads to the capture of a large fraction of charge carriers. A change of polymer conformation due to the presence of nc‐CdSe is revealed by low temperature LESR measurements and microwave saturation techniques. The impact of the different recombination behavior on the photovoltaic efficiency of both systems is discussed.     

Comparison of the Operation of Polymer/Fullerene,Polymer/Polymer,and Polymer/Nanocrystal Solar Cells: A Transient Photocurrent and Photovoltage Study

We utilize transient techniques to directly compare the operation of polymer/fullerene, polymer/nanocrystal, and polymer/polymer bulk heterojunction solar cells. For all devices, poly(3‐hexylthiophene) (P3HT) is used as the electron donating polymer, in combination with either the fullerene derivative phenyl‐C₆₁‐butyric acid methyl ester (PCBM) in polymer/fullerene cells, CdSe nanoparticles in polymer/nanocrystal cells, or the polyfluorene copolymer poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2,2‐diyl) (F8TBT) in polymer/polymer cells. Transient photocurrent and photovoltage measurements are used to probe the dynamics of charge‐separated carriers, with vastly different dynamic behavior observed for polymer/fullerene, polymer/polymer, and polymer/nanocrystal devices on the microsecond to millisecond timescale. Furthermore, by employing transient photocurrent analysis with different applied voltages we are also able to probe the dynamics behavior of these cells from short circuit to open circuit. P3HT/F8TBT and P3HT/CdSe devices are characterized by poor charge extraction of the long‐lived carriers attributed to charge trapping. P3HT/PCBM devices, in contrast, show relatively trap‐free operation with the variation in the photocurrent decay kinetics with applied bias at low intensity, consistent with the drift of free charges under a uniform electric field. Under solar conditions at the maximum power point, we see direct evidence of bimolecular recombination in the P3HT/PCBM device competing with charge extraction. Transient photovoltage measurements reveal that, at open circuit, photogenerated charges have similar lifetimes in all device types, and hence, the extraction of these long‐lived charges is a limiting process in polymer/nanocrystal and polymer/polymer devices.     

Spatially Resolved STM Spectroscopy of Charge Injection at the Ladder‐Type Poly(para‐phenylene)/Au(111) Interface

The effect of the morphology on charge‐carrier injection into methyl‐substituted ladder‐type poly(para‐phenylene) (Me‐LPPP) thin films deposited on a Au(111) substrate has been studied by scanning‐tunneling‐microscope‐based spectroscopy. We find that the charge‐carrier injection barrier as well as the single‐particle bandgap, E_gsp, of the polymer show significant variations at different locations of the sample surface. Normally, we find that the values of E_gsp are larger than the optical absorption edge, the energy difference being attributed to the exciton binding energy. In some regions of the sample, however, E_gsp appears to be close to or below the optical absorption edge, pointing to the effect of aggregates within the polymer film which act as hole‐trapping centers with a depth of a few 100 meV. Density functional calculations are used to elucidate the dependence of the electronic states on the polymer packing density. Our results show that in this polymer morphological inhomogeneities strongly influence the charge carrier injection and transport properties. This points to a common behavior of materials exhibiting a tendency to form aggregates. In addition, the exciton binding energy of Me‐LPPP is determined to be approx. 0.85 eV. Moreover, the comparison between the charge‐injection energy gap and the photocurrent action spectrum indicates that the photoionization threshold is not directly related to the exciton binding energy.     

High‐Conductivity Poly(3,4‐ethylenedioxythiophene):Poly(styrene sulfonate) Film and Its Application in Polymer Optoelectronic Devices

The conductivity of a poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film can be enhanced by more than two orders of magnitude by adding a compound with two or more polar groups, such as ethylene glycol, meso‐erythritol (1,2,3,4‐tetrahydroxybutane), or 2‐nitroenthanol, to an aqueous solution of PEDOT:PSS. The mechanism for this conductivity enhancement is studied, and a new mechanism proposed. Raman spectroscopy indicates an effect of the liquid additive on the chemical structure of the PEDOT chains, which suggests a conformational change of PEDOT chains in the film. Both coil and linear conformations or an expanded‐coil conformation of the PEDOT chains may be present in the untreated PEDOT:PSS film, and the linear or expanded‐coil conformations may become dominant in the treated PEDOT:PSS film. This conformational change results in the enhancement of charge‐carrier mobility in the film and leads to an enhanced conductivity. The high‐conductivity PEDOT:PSS film is ideal as an electrode for polymer optoelectronic devices. Polymer light‐emitting diodes and photovoltaic cells fabricated using such high‐conductivity PEDOT:PSS films as the anode exhibit a high performance, close to that obtained using indium tin oxide as the anode.     

Improved conversion efficiency of a‐Si:H/µc‐Si:H thin‐film solar cells by using annealed Al‐doped zinc oxide as front electrode material

In recent years, zinc oxide has been investigated as a front electrode material in hydrogenated amorphous silicon/hydrogenated microcrystalline silicon (a‐Si:H/µc‐Si:H) tandem solar cells. Such as for other transparent conducting oxide materials and applications, a proper balancing of transparency and conductivity is necessary. The latter is directly related to the density and the mobility of charge carriers. A high density of charge carriers increases conductivity but leads to a higher absorption of light in the near‐infrared part of the spectrum due to increased free‐carrier absorption. Hence, the only way to achieve high conductivity while keeping the transparency as high as possible relies on an increase of carrier mobility. The carrier density and the mobility of sputtered Al‐doped zinc oxide (ZnO:Al) can be tailored by a sequence of different annealing steps. In this work, we implemented such annealed ZnO:Al films as a front electrode in a‐Si:H/µc‐Si:H tandem solar cells and compared the results with those of reference cells grown on as‐deposited ZnO:Al. We observed an improvement of short‐circuit current density as well as open‐circuit voltage and fill factor. The gain in current density could be attributed to a reduction of both sub‐band‐gap absorption and free‐carrier absorption in the ZnO:Al. The higher open‐circuit voltage and fill factor are indicators of a better device quality of the silicon for cells grown on annealed ZnO:Al. Altogether, the annealing led to an improved initial conversion efficiency of 12.1%, which was a gain of +0.7% in absolute terms. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of Photo‐oxidation on the Performance of Poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene]:[6,6]‐Phenyl C61‐Butyric Acid Methyl Ester Solar Cells

A study of the photo‐oxidation of films of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV) blended with [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM), and solar cells based thereon, is presented. Solar‐cell performance is degraded primarily through loss in short‐circuit current density, J_SC. The effect of the same photodegradation treatment on the optical‐absorption, charge‐recombination, and charge‐transport properties of the active layer is studied. It is concluded that the loss in J_SC is primarily due to a reduction in charge‐carrier mobility, owing to the creation of more deep traps in the polymer during photo‐oxidation. Recombination is slowed down by the degradation and cannot therefore explain the loss in photocurrent. Optical absorption is reduced by photo‐bleaching, but the size of this effect alone is insufficient to explain the loss in device photocurrent.     

Anisotropic Structure and Charge Transport in Highly Strain‐Aligned Regioregular Poly(3‐hexylthiophene)

A novel method of strain‐aligning polymer films is introduced and applied to regioregular poly(3‐hexylthiophene) (P3HT), showing several important features of charge transport. The polymer backbone is shown to align in the direction of applied strain resulting in a large charge‐mobility anisotropy, where the in‐plane mobility increases in the applied strain direction and decreases in the perpendicular direction. In the aligned film, the hole mobility is successfully represented by a two‐dimensional tensor, suggesting that charge transport parallel to the polymer backbone within a P3HT crystal is strongly favored over the other crystallographic directions. Hole mobility parallel to the backbone is shown to be high for a mixture of plane‐on and edge‐on packing configurations, as the strain alignment is found to induce a significant face‐on orientation of the originally highly edge‐on oriented crystalline regions of the film. This alignment approach can achieve an optical dichroic ratio of 4.8 and a charge‐mobility anisotropy of 9, providing a simple and effective method to investigate charge‐transport mechanisms in polymer semiconductors.     

Dispersion‐Dominated Photocurrent in Polymer:Fullerene Solar Cells

Organic bulk heterojunction solar cells are often regarded as near‐equilibrium devices, whose kinetics are set by well‐defined charge carrier mobilities, and relaxation in the density of states is commonly ignored or included purely phenomenologically. Here, the motion of photocreated charges is studied experimentally with picosecond time resolution by a combination of time‐resolved optical probing of electric field and photocurrent measurements, and the data are used to define parameters for kinetic Monte Carlo modelling. The results show that charge carrier motion in a prototypical polymer:fullerene solar cell under operational conditions is orders of magnitude faster than would be expected on the basis of corresponding near‐equilibrium mobilities, and is extremely dispersive. There is no unique mobility. The distribution of extraction times of photocreated charges in operating organic solar cells can be experimentally determined from the charge collection transients measured under pulsed excitation. Finally, a remarkable distribution of the photocurrent over energy is found, in which the most relaxed charge carriers in fact counteract the net photocurrent.     

Amplified Spontaneous Emission of Poly(ladder‐type phenylene)s – The Influence of Photophysical Properties on ASE Thresholds

Amplified spontaneous emission (ASE) of a series of blue‐emitting poly(ladder‐type phenylene)s (LPPP)s has been studied in thin film polymer waveguide structures. The chemically well‐defined step‐ladder polymers consist of an increasing number of bridged phenylene rings per monomer unit starting from fully arylated poly(ladder‐type indenofluorene) up to poly(ladder‐type pentaphenylene). The ASE characteristics of the polymers including the onset threshold values for ASE, the gain and loss coefficients as well as the photoluminescence (PL) properties, i.e., the solid state fluorescence lifetimes, decay kinetics and solid state quantum efficiencies have been studied by time‐resolved PL spectroscopy. A fully arylated polyfluorene has been synthesized and its photophysical properties were compared to the step‐ladder polymers. Steady‐state photoinduced absorption and ultrafast transient absorption spectroscopy have been used to study excited state absorption of singlet and triplet states and polarons present in the solid state. The results demonstrate a minimum regarding the onset threshold value of ASE for a fully arylated poly(ladder‐type indenofluorene) and a successive increase of the ASE threshold for the step‐ladder polymers with more bridged phenylene rings. In particular, carbazole‐containing step‐ladder LPPPs exhibit significantly increased ASE threshold values as compared to their carbazole‐free analogues due to a pronounced overlap of stimulated emission (SE) and photoinduced absorption (PA).     

Luminescent Poly(p‐phenylenevinylene) Hole‐Transport Layers with Adjustable Solubility

The active part of present polymer light‐emitting diodes (PLEDs) consists of only a single layer. Multilayer devices have the advantage that the electron and hole transport can be balanced and that the recombination can be removed from the metallic cathode, leading to higher efficiencies. A major problem for polymer‐based multilayer devices is the solubility of the materials used; a multilayer can not be fabricated when a spin‐cast layer dissolves in the solvent of the subsequent layer. We demonstrate the development of high‐mobility poly(p‐phenylenevinylene) (PPV)‐based hole‐transport layers with tunable solubility by chemical modification. Enhanced charge‐transport properties are achieved by using symmetrically substituted PPVs; copolymers of long and short side chains enable us to tune the solubility without loss of the enhanced charge transport. Dual‐layer PLEDs, in which the holes are efficiently transported via this copolymer towards the luminescent layer, exhibit an enhanced efficiency at high voltages (> 10 V) and a strongly improved robustness against electrical breakdown.     

The Effect of Nanoparticle Shape on the Photocarrier Dynamics and Photovoltaic Device Performance of Poly(3‐hexylthiophene):CdSe Nanoparticle Bulk Heterojunction Solar Cells

The charge separation and transport dynamics in CdSe nanoparticle:poly(3‐hexylthiophene) (P3HT) blends are reported as a function of the shape of the CdSe‐nanoparticle electron acceptor (dot, rod, and tetrapod). For optimization of organic photovoltaic device performance it is crucial to understand the role of various nanostructures in the generation and transport of charge carriers. The sample processing conditions are carefully controlled to eliminate any processing‐related effects on the carrier generation and on device performance with the aim of keeping the conjugated polymer phase constant and only varying the shape of the inorganic nanoparticle acceptor phase. The electrodeless, flash photolysis time‐resolved microwave conductivity (FP‐TRMC) technique is used and the results are compared to the efficiency of photovoltaic devices that incorporate the same active layer. It is observed that in nanorods and tetrapods blended with P3HT, the high aspect ratios provide a pathway for the electrons to move away from the dissociation site even in the absence of an applied electric field, resulting in enhanced carrier lifetimes that correlate to increased efficiencies in devices. The processing conditions that yield optimum performance in high aspect ratio CdSe nanoparticles blended with P3HT result in poorly performing quantum dot CdSe:P3HT devices, indicating that the latter devices are inherently limited by the absence of the dimensionality that allows for efficient, prolonged charge separation at the polymer:CdSe interface.     

A Highly Stable,New Electrochromic Polymer: Poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy) thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene)

A highly stable new electrochromic polymer, poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy)thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene) (P(BEDOT‐MEHB)) was synthesized and its electrochemical and electrochromic properties are reported. P(BEDOT‐MEHB) showed a very well defined electrochemistry with a relatively low oxidation potential of the monomer at + 0.44 V versus Ag/Ag⁺, E_1/2 at – 0.35 V versus Ag/Ag⁺ and stability to long‐term switching up to 5000 cycles. A high level of stability to over‐oxidation has also been observed as this material shows limited degradation of its electroactivity at potentials 1.4 V above its half‐wave potential. Spectroelectrochemistry showed that the absorbance of the π–π* transition in the neutral state is blue‐shifted compared to PEDOT, displaying a maximum at 538 nm (onset at 640 nm), thus giving an almost colorless, highly transparent oxidized polymer with a bandgap of 1.95 eV. Different colors observed at different oxidation levels and strong absorption in the near‐IR make this polymer a good candidate for several applications.     

The Locus of Free Charge‐Carrier Generation in Solution‐Cast Zn1–xMgxO/Poly(3‐hexylthiophene) Bilayers for Photovoltaic Applications

The photoconductivity of solution‐cast Zn_1–xMg_xO (x=0‐0.4) and poly(3‐hexylthiophene) (P3HT) thin films, and Zn_1‐xMg_xO/P3HT bilayers is investigated using Time‐Resolved Microwave Conductivity (TRMC) with the aim of determining the locus of free charge carrier generation in the bilayer system. The photoconductivity of Zn_1–xMg_xO thin films, under illumination with 300 nm laser pulses, is limited by the formation of stable excitons and by scattering of the carriers at grain boundaries. The electron mobility in Zn_1–xMg_xO films decreases exponentially with Mg concentration, up to x=0.4. In agreement with previous work, free carriers are observed in the P3HT film under illumination with 500 nm pulses in the absence of an acceptor. Under illumination with 500 nm pulses, where only the polymer absorbs, the TRMC signal for the Zn_1–xMg_xO/P3HT bilayers for x≥0.2 is the same as that of pure P3HT, indicating that free carrier generation in these bilayers occurs predominately by exciton dissociation in the polymer bulk, and not at the interface between the polymer and the solution‐cast oxide. At lower Mg concentrations (x<0.2) the TRMC signal increases with decreasing x following the dependence of the electron mobility in the oxide but its light intensity dependence remains consistent with free carrier generation in the polymer bulk. To explain these results and previously published photovoltaic device data (Adv. Funct. Mater. 2007 , 17, 264) we propose that free carrier generation in the bilayers predominantly occurs in the bulk of P3HT, and is followed by electron injection to the oxide to yield photocurrent in photovoltaic cells. The dependence of the TRMC signal of the bilayers on Mg concentration is explained in terms of the yield for free carrier generation in the polymer and the relative contributions of electrons in the oxide and holes in the polymer.     

High‐Efficiency Organic Solar Cells Based on Preformed Poly(3‐hexylthiophene) Nanowires

Bulk heterojunction solar cells based on blends of poly(3‐hexylthiophene) (P3HT) and phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) are fabricated using self‐assembled P3HT nanowires in a marginal solvent without post‐treatments. The interconnected network structures of self‐organized P3HT nanowires create continuous percolation pathways through the active layer and contribute to enhanced carrier mobility. The morphology and photovoltaic properties are studied as a function of ageing time of the P3HT precursor solution. Optimal photovoltaic properties are found at 60 h ageing time, which increases both light absorption and charge balance. Multilayered solar cells with a compositionally graded structure are fabriacted using preformed P3HT nanowires by inserting a pure P3HT donor phase onto the hole‐collecting electrode. Applying optimized annealing conditions to the P3HT buffer layer achieves an enhanced hole mobility and a power conversion efficiency of 3.94%. The introduction of a compositionally graded device structure, which contains a P3HT‐only region, reduces charge recombination and electron injection to the indium tin oxide (ITO) electrode and enhances the device properties. These results demonstrate that preformed semiconductor nanowires and compositionally graded structures constitute a promising approach to the control of bulk heterojunction morphology and charge‐carrier mobility.     

Using Molecular Design to Increase Hole Transport: Backbone Fluorination in the Benchmark Material Poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]‐thiophene (pBTTT)

The synthesis of a novel 3,3′‐difluoro‐4,4′‐dihexadecyl‐2,2′‐bithiophene monomer and its copolymerization with thieno[3,2‐b]thiophene to afford the fluorinated analogue of the well‐known poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]‐thiophene) (PBTTT) polymer is reported. Fluorination is found to have a significant influence on the physical properties of the polymer, enhancing aggregation in solution and increasing melting point by over 100 °C compared to nonfluorinated polymer. On the basis of DFT calculations these observations are attributed to inter and intramolecular S…F interactions. As a consequence, the fluorinated polymer PFBTTT exhibits a fourfold increase in charge carrier mobility compared to the nonfluorinated polymer and excellent ambient stability for a nonencapsulated transistor device.     

Organic Light‐Emitting Diodes Based on Poly(9,9‐dioctylfluorene‐co‐bithiophene) (F8T2)

A study of the optical properties of poly(9,9‐dioctylfluorene‐co‐bithiophene) (F8T2) is reported, identifying this polymer as one that possesses a desirable combination of charge transport and light emission properties. The optical and morphological properties of a series of polymer blends with F8T2 dispersed in poly(9,9‐dioctylfluorene) (PFO) are described and almost pure‐green emission from light emitting diodes (LEDs) based thereon is demonstrated. High luminance green electroluminescence from LEDs using only a thin film of F8T2 for emission is also reported. The latter demonstration for a polymer previously primarily of interest for effective charge transport constitutes an important step in the development of emissive materials for applications where a union of efficient light emission and effective charge transport is required.     

Electrochromic Window Based on Conducting Poly(3,4‐ethylenedioxythiophene)–Poly(styrene sulfonate)

A short survey of technological aspects of electrochromism with various electroactive species is given. Different approaches with inorganic and organic materials have been pursued in the past. So far widespread usage of this technology for large area applications has not been achieved. Nevertheless one major technical product, self‐darkening rear‐view mirrors for cars, is already well established. This article reviews some research results on electroactive polythiophenes, especially poly(3,4‐alkylenedioxythiophenes). Some promising results with the commercially available electrically conducting polymer Baytron P (PEDT/PSS) are presented. It is demonstrated that an all solid‐state electrochromic multilayer assembly based on a polymeric electrochromic material might be close to technical realization. The coating of large area substrates with aqueous poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) dispersion can be a way to an economically viable product.     

Charge Photogeneration for a Series of Thiazolo‐Thiazole Donor Polymers Blended with the Fullerene Electron Acceptors PCBM and ICBA

Photoinduced charge separation in bulk heterojunction solar cells is studied using a series of thiazolo‐thiazole donor polymers that differ in their side groups (and bridging atoms) blended with two acceptor fullerenes, phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) and a fullerene indene‐C60 bisadduct (ICBA). Transient absorption spectroscopy is used to determine the yields and lifetimes of photogenerated charge carriers, complimented by cyclic voltammetry studies of materials energetics, wide angle X‐ray diffraction and transmission electron microscopy studies of neat and blend film crystallinity and photoluminescence quenching studies of polymer/fullerene phase segregation, and the correlation of these measurements with device photocurrents. Good correlation between the initial polaron yield and the energetic driving force driving charge separation, ΔE_CS is observed. All blend films exhibit a power law transient absorption decay phase assigned to non‐geminate recombination of dissociated charges; the amplitude of this power law decay phase shows excellent correlation with photocurrent density in the devices. Furthermore, for films of one (relatively amorphous) donor polymer blended with ICBA, we observe an additional 100 ns geminate recombination phase. The implications of the observations reported are discussed in terms of the role of materials' crystallinity in influencing charge dissociation in such devices, and thus materials design requirements for efficient solar cell function.     

Effect of Mesoscale Crystalline Structure on the Field‐Effect Mobility of Regioregular Poly(3‐hexyl thiophene) in Thin‐Film Transistors

Regioregular poly(3‐hexyl thiophene) (RR P3HT) is drop‐cast to fabricate field‐effect transistor (FET) devices from different solvents with different boiling points and solubilities for RR P3HT, such as methylene chloride, toluene, tetrahydrofuran, and chloroform. A Petri dish is used to cover the solution, and it takes less than 30 min for the solvents to evaporate at room temperature. The mesoscale crystalline morphology of RR P3HT thin films can be manipulated from well‐dispersed nanofibrils to well‐developed spherulites by changing solution processing conditions. The morphological correlation with the charge‐carrier mobility in RR P3HT thin‐film transistor (TFT) devices is investigated. The TFT devices show charge‐carrier mobilities in the range of 10^–4 ～ 10^–2 cm² V^–1 s^–1 depending on the solvent used, although grazing‐incidence X‐ray diffraction (GIXD) reveals that all films develop the same π–π‐stacking orientation, where the <100>‐axis is normal to the polymer films. By combining results from atomic force microscopy (AFM) and GIXD, it is found that the morphological connectivity of crystalline nanofibrils and the <100>‐axis orientation distribution of the π–π‐stacking plane with respect to the film normal play important roles on the charge‐carrier mobility of RR P3HT for TFT applications.     

Compositional Dependence of the Performance of Poly(p‐phenylene vinylene):Methanofullerene Bulk‐Heterojunction Solar Cells

The dependence of the performance of OC₁C₁₀‐PPV:PCBM (poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐p‐phenylene vinylene):methanofullerene [6,6]‐phenyl C₆₁‐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 OC₁C₁₀‐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.