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.     

Entanglement of Conjugated Polymer Chains Influences Molecular Self‐Assembly and Carrier Transport

The influence of polymer entanglement on the self‐assembly, molecular packing structure, and microstructure of low‐M_w (lightly entangled) and high‐M_w (highly entangled) poly (3‐hexylthiophene) (P3HT), and the carrier transport in thin‐film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self‐assembly of well‐ordered and highly textured fibrils at the solid–liquid interface. In low‐M_w P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high‐M_w P3HT solutions increases carrier mobility up to ≈20‐fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high‐M_w P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low‐M_w P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport.     

Aligned Polythiophene and its Blend Film by Direct‐Writing for Anisotropic Charge Transport

A combination of patterning and film alignment techniques helps to build multi‐order polymer architecture for application in flexible electronics. A direct‐writing method is employed using microcapillary arrays to prepare semiconducting polymer films with both optical and electrical anisotropy. Not only aligned poly(3‐butylthiophene) (P3BT) nanowires in neat P3BT films, but also aligned P3BT nanowires within a polystyrene (PS) matrix are obtained, which yields an aligned semiconductor/insulator polymer blend with anisotropic charge transport. The field‐effect transistor (FET) mobilities/threshold voltages from both vertical and parallel to alignment directions as well as their dependence on blending ratio are studied. The increased mobility of P3BT/PS blends, as compared with neat P3BT, is observed in both vertical and parallel directions. Using this alignment method, FET mobility and threshold voltage of the semiconductor/insulator polymer blends are comprehensively tuned, from which a digital inverter with gain up to 80 is realized. Therefore, this work not only helps understanding the charge transport mechanism in semiconducting/insulating polymer blends, but also provides an effective approach towards high‐performance field‐effect transistors with tunable mobility and threshold voltage.     

The Impact of Polymer Regioregularity on Charge Transport and Efficiency of P3HT:PCBM Photovoltaic Devices

The charge transport in pristine poly(3‐hexylthiophene) (P3HT) films and in photovoltaic blends of P3HT with [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) is investigated to study the influence of charge‐carrier transport on photovoltaic efficiency. The field‐ and temperature dependence of the charge‐carrier mobility in P3HT of three different regioregularities, namely, regiorandom, regioregular with medium regioregularity, and regioregular with very high regioregularity are investigated by the time‐of‐flight technique. While medium and very high regioregularity polymers show the typical absorption features of ordered lamellar structures of P3HT in the solid state even without previous annealing, films of regiorandom P3HT are very disordered as indicated by their broad and featureless absorption. This structural difference in the solid state coincides with partially non‐dispersive transport and hole mobilities µ_h of around 10^?4 and 10^?5 cm² V^?1 s^?1 for the high and medium regioregularity P3HT, respectively, and a slow and dispersive charge transport for the regiorandom P3HT. Upon blending the regioregular polymers with PCBM, the hole mobilities are typically reduced by one order of magnitude, but they do not significantly change upon additional post‐spincasting annealing. Only in the case of P3HT with high regioregularity are the electron mobilities similar to the hole mobilities and the charge transport is, thus, balanced. Nonetheless, devices prepared from both materials exhibit similar power conversion efficiencies of 2.5%, indicating that very high regioregularity may not substantially improve order and charge‐carrier transport in P3HT:PCBM and does not lead to significant improvements in the power‐conversion efficiency of photovoltaic devices.     

Planarization of Polymeric Field‐Effect Transistors: Improvement of Nanomorphology and Enhancement of Electrical Performance

The planarization of bottom‐contact organic field‐effect transistors (OFETs) resulting in dramatic improvement in the nanomorphology and an associated enhancement in charge injection and transport is reported. Planar OFETs based on regioregular poly(3‐hexylthiophene) (rr‐P3HT) are fabricated wherein the Au bottom‐contacts are recessed completely in the gate‐dielectric. Normal OFETs having a conventional bottom‐contact configuration with 50‐nm‐high contacts are used for comparison purpose. A modified solvent‐assisted drop‐casting process is utilized to form extremely thin rr‐P3HT films. This process is critical for direct visualization of the effect of planarization on the polymer morphology. Atomic force micrographs (AFM) show that in a normal OFET the step between the surface of the contacts and the gate dielectric disrupts the self‐assembly of the rr‐P3HT film, resulting in poor morphology at the contact edges. The planarization of contacts results in notable improvement of the nanomorphology of rr‐P3HT, resulting in lower resistance to charge injection. However, an improvement in field‐effect mobility is observed only at short channel lengths. AFM shows the presence of well‐ordered nanofibrils extending over short channel lengths. At longer channel lengths the presence of grain boundaries significantly minimizes the effect of improvement in contact geometry as the charge transport becomes channel‐limited.     

2D Versus 3D Crystalline Order in Thin Films of Regioregular Poly(3‐hexylthiophene) Oriented by Mechanical Rubbing and Epitaxy

Highly oriented films of regioregular poly(3‐hexylthiophene) (P3HT) are prepared by two methods: mechanical rubbing and directional epitaxial crystallization. The structure, nanomorphology, and optical and charge‐transport properties of the oriented films are investigated by electron diffraction, high resolution transmission electron microscopy (HR‐TEM), absorption spectroscopy, and transistor field‐effect measurements. In rubbed films, P3HT chains align parallel to the rubbing direction and the crystalline domains orientation changes from preferential edge‐on to flat‐on orientation. The maximum in‐plane orientation probed by absorption spectroscopy is a function of the polymer molecular weight M_w; the lower the M_w, the higher the in‐plane orientation induced by rubbing. The anisotropy of field‐effect mobility measured parallel and perpendicular to the rubbing shows the same trend as the absorption. The M_w‐dependence of the orientation is explained in terms of chain folding and entanglement that prevent the reorientation and reorganization of the π‐stacked chains, especially when M_w ≥ 50 kDa. For comparison, P3HT films are oriented by directional epitaxial crystallization using a zone‐melting technique. Electron diffraction and HR‐TEM show that epitaxial and rubbed films differ in terms of intralamellar order within layers of π‐stacked chains. Comparison of UV‐vis absorption spectra for the different samples suggests that the vibronic structure is sensitive to intralamellar disorder.     

Temperature‐Resolved Local and Macroscopic Charge Carrier Transport in Thin P3HT Layers

Previous investigations of the field‐effect mobility in poly(3‐hexylthiophene) (P3HT) layers revealed a strong dependence on molecular weight (MW), which was shown to be closely related to layer morphology. Here, charge carrier mobilities of two P3HT MW fractions (medium‐MW: M_n = 7 200 g mol^?1; high‐MW: M_n = 27 000 g mol^?1) are probed as a function of temperature at a local and a macroscopic length scale, using pulse‐radiolysis time‐resolved microwave conductivity (PR‐TRMC) and organic field‐effect transistor measurements, respectively. In contrast to the macroscopic transport properties, the local intra‐grain mobility depends only weakly on MW (being in the order of 10^?2 cm² V^?1 s^?1) and being thermally activated below the melting temperature for both fractions. The striking differences of charge transport at both length scales are related to the heterogeneity of the layer morphology. The quantitative analysis of temperature‐dependent UV/Vis absorption spectra according to a model of F. C. Spano reveals that a substantial amount of disordered material is present in these P3HT layers. Moreover, the analysis predicts that aggregates in medium‐MW P3HT undergo a “pre‐melting” significantly below the actual melting temperature. The results suggest that macroscopic charge transport in samples of short‐chain P3HT is strongly inhibited by the presence of disordered domains, while in high‐MW P3HT the low‐mobility disordered zones are bridged via inter‐crystalline molecular connections.     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

Anisotropy of Charge Transport in a Uniaxially Aligned and Chain‐Extended,High‐Mobility,Conjugated Polymer Semiconductor

Charge transport in the ribbon phase of poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT)—one of the most highly ordered, chain‐extended crystalline microstructures available in a conjugated polymer semiconductor—is studied. Ribbon‐phase PBTTT has previously been found not to exhibit high carrier mobilities, but it is shown here that field‐effect mobilities depend strongly on the device architecture and active interface. When devices are constructed such that the ribbon‐phase films are in contact with either a polymer gate dielectric or an SiO₂ gate dielectric modified by a hydrophobic, self‐assembled monolayer, high mobilities of up to 0.4 cm² V^?1 s^?1 can be achieved, which is comparable to those observed previously in terrace‐phase PBTTT. In uniaxially aligned, zone‐cast films of ribbon‐phase PBTTT the mobility anisotropy is measured for transport both parallel and perpendicular to the polymer chain direction. The mobility anisotropy is relatively small, with the mobility along the polymer chain direction being higher by a factor of 3–5, consistent with the grain size encountered in the two transport directions.     

In‐Plane Alignment in Organic Solar Cells to Probe the Morphological Dependence of Charge Recombination

Bulk heterojunction (BHJ) organic solar cells are fabricated with the polymer semiconductor aligned in the plane of the film to probe charge recombination losses associated with aggregates characterized by varying degrees of local order. 100% uniaxial strain is applied on ductile poly(3‐hexylthiophene):phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) BHJ films and characterize the resulting morphology with ultraviolet‐visible absorption spectroscopy and grazing incidence X‐ray diffraction. It is found that the strained films result in strong alignment of the highly ordered polymer aggregates. Polymer aggregates with lower order and amorphous regions also align but with a much broader orientation distribution. The solar cells are then tested under linearly polarized light where the light is selectively absorbed by the appropriately oriented polymer, while maintaining a common local environment for the sweep out of photogenerated charge carriers. Results show that charge collection losses associated with a disordered BHJ film are circumvented, and the internal quantum efficiency is independent of P3HT local aggregate order near the heterojunction interface. Uniquely, this experimental approach allows for selective excitation of distinct morphological features of a conjugated polymer within a single BHJ film, providing insight into the morphological origin of recombination losses.     

Understanding Lattice Strain‐Controlled Charge Transport in Organic Semiconductors: A Computational Study

The softness and anisotropy of organic semiconductors offer unique properties. Recently, solution‐sheared thin‐films of 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐P) with nonequilibrium single‐crystal domains have shown much higher charge mobilities than unstrained ones (Nature 2011 , 480, 504). However, to achieve efficient and targeted modulation of charge transport in organic semiconductors, a detailed microscopic understanding of the structure–property relationship is needed. In this work, motivated by the experimental studies, the relationship between lattice strain, molecular packing, and charge carrier mobility of TIPS‐P crystals is elucidated. By employing a multiscale theoretical approach combining nonequilibrium molecular dynamics, first‐principles calculations, and kinetic Monte Carlo simulations using charge‐transfer rates based on the tunneling enabled hopping model, charge‐transport properties of TIPS‐P under various lattice strains are investigated. Shear‐strained TIPS‐P indeed exhibits one‐dimensional charge transport, which agrees with the experiments. Furthermore, either shear or tensile strain lead to mobility enhancement, but with strong charge‐transport anisotropy. In addition, a combination of shear and tensile strains could not only enhance mobility, but also decrease anisotropy. By combining the shear and tensile strains, almost isotropic charge transport could be realized in TIPS‐P crystal with the hole mobility improved by at least one order of magnitude. This approach enables a deep understanding of the effect of lattice strain on charge carrier transport properties in organic semiconductors.     

The Effect of Poly(3‐hexylthiophene) Molecular Weight on Charge Transport and the Performance of Polymer:Fullerene Solar Cells

The time‐of‐flight method has been used to study the effect of P3HT molecular weight (M_n = 13–121 kDa) on charge mobility in pristine and PCBM blend films using highly regioregular P3HT. Hole mobility was observed to remain constant at 10^?4 cm²V^?1s^?1 as molecular weight was increased from 13–18 kDa, but then decreased by one order of magnitude as molecular weight was further increased from 34–121 kDa. The decrease in charge mobility observed in blend films is accompanied by a change in surface morphology, and leads to a decrease in the performance of photovoltaic devices made from these blend films.     

Solubility‐Induced Ordered Polythiophene Precursors for High‐Performance Organic Thin‐Film Transistors

With the aim of enhancing the field‐effect mobility of self‐assembled regioregular poly(3‐hexylthiophene), P3HT, by promoting two‐dimensional molecular ordering, the organization of the P3HT in precursor solutions is transformed from random‐coil conformation to ordered aggregates by adding small amounts of the non‐solvent acetonitrile to the solutions prior to film formation. The ordering of the precursor in the solutions significantly increases the crystallinity of the P3HT thin films. It is found that with the appropriate acetonitrile concentration in the precursor solution, the resulting P3HT nanocrystals adopt a highly ordered molecular structure with a field‐effect mobility dramatically improved by a factor of approximately 20 depending on the P3HT concentration. This improvement is due to the change in the P3HT organization in the precursor solution from random‐coil conformation to an ordered aggregate structure as a result of the addition of acetonitrile. In the good solvent chloroform, the P3HT molecules are molecularly dissolved and adopt a random‐coil conformation, whereas upon the addition of acetonitrile, which is a non‐solvent for aromatic backbones and alkyl side chains, 1D or 2D aggregation of the P3HT molecules occurs depending on the P3HT concentration. This state minimizes the unfavorable interactions between the poorly soluble P3HT and the acetonitrile solvent, and maximizes the favorable π–π stacking interactions in the precursor solution, which improves the molecular ordering of the resulting P3HT thin film and enhances the field‐effect mobility without post‐treatment.     

Precise Control of Lamellar Thickness in Highly Oriented Regioregular Poly(3‐Hexylthiophene) Thin Films Prepared by High‐Temperature Rubbing: Correlations with Optical Properties and Charge Transport

Precise control of orientation and crystallinity is achieved in regioregular poly(3‐hexylthiophene) (P3HT) thin films by using high‐temperature rubbing, a fast and effective alignment method. Rubbing P3HT films at temperatures T_R ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar morphology with a dichroic ratio reaching 25. The crystallinity and the average crystal size along the chain axis direction, l_c, are determined by high‐resolution transmission electron microscopy and differential scanning calorimetry. The inverse of the lamellar period l scales with the supercooling and can accordingly be controlled by the rubbing temperature T_R. Uniquely, the observed exciton coupling in P3HT crystals is correlated to the length of the average planarized chain segments l_c in the crystals. The high alignment and crystallinity observed for T_R > 200 °C cannot translate to high hole mobilities parallel to the rubbing because of the adverse effect of amorphous zones interrupting charge transport between crystalline lamellae. Although tie chains bridge successive P3HT crystals through amorphous zones, their twisted conformation restrains interlamellar charge transport. The evolution of charge transport anisotropy is correlated to the evolution of the dominant contact plane from mainly face‐on (T_R ≤ 100 °C) to edge‐on (T_R ≥ 170 °C).     

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.     

Tunable Crystallinity in Regioregular Poly(3‐Hexylthiophene) Thin Films and Its Impact on Field Effect Mobility

The properties of poly(alkylthiophenes) in solution are found to have a profound impact on the self assembly process and thus the microstructural and electrical properties of the resultant thin films. Ordered supramolecular precursors can be formed in regioregular poly(3‐hexylthiophene) (P3HT) solutions through the application of low intensity ultrasound. These precursors survive the casting process, resulting in a dramatic increase in the degree of crystallinity of the thin films obtained by spin coating. The crystallinity of the films is tunable, with a continuous evolution of mesoscale structures observed as a function of ultrasonic irradiation time. The photophysical properties of P3HT in solution as well in the solid state suggest that the application of ultrasound leads to a π stacking induced molecular aggregation resulting in field effect mobilities as high as 0.03 cm² V^?1 s^?1. A multiphase morphology, comprising short quasi‐ordered and larger, ordered nanofibrils embedded in a disordered amorphous phase is formed as a result of irradiation for at least 1 min. Two distinct regions of charge transport are identified, characterized by an initial sharp increase in the field effect mobility by two orders of magnitude due to an increase in crystallinity up to the percolation limit, followed by a gradual saturation where the mobility becomes independent of the thin film microstructure.     

Enhanced Vertical Charge Transport in a Semiconducting P3HT Thin Film on Single Layer Graphene

The crystallization and electrical characterization of the semiconducting polymer poly(3‐hexylthiophene) (P3HT) on a single layer graphene sheet is reported. Grazing incidence X‐ray diffraction revealed that P3HT crystallizes with a mixture of face‐on and edge‐on lamellar orientations on graphene compared to mainly edge‐on on a silicon substrate. Moreover, whereas ultrathin (10 nm) P3HT films form well oriented face‐on and edge‐on lamellae, thicker (50 nm) films form a mosaic of lamellae oriented at different angles from the graphene substrate. This mosaic of crystallites with π–π stacking oriented homogeneously at various angles inside the film favors the creation of a continuous pathway of interconnected crystallites, and results in a strong enhancement in vertical charge transport and charge carrier mobility in the thicker P3HT film. These results provide a better understanding of polythiophene crystallization on graphene, and should help the design of more efficient graphene based organic devices by control of the crystallinity of the semiconducting film.     

Probing the Anisotropic Field‐Effect Mobility of Solution‐Deposited Dicyclohexyl‐α‐quaterthiophene Single Crystals

Measuring the anisotropy of the field‐effect mobility provides insight into the correlation between molecular packing and charge transport in organic semiconductor materials. Single‐crystal field‐effect transistors are ideal tools to study intrinsic charge transport because of their high crystalline order and chemical purity. The anisotropy of the field effect mobility in organic single crystals has previously been studied by lamination of macroscopically large single crystals onto device substrates. Here, a technique is presented that allows probing of the mobility anisotropy even though only small crystals are available. Crystals of a soluble oligothiophene derivative are grown in bromobenzene and drop‐cast onto substrates containing arrays of bottom‐contact gold electrodes. Mobility anisotropy curves are recorded by measuring numerous single crystal transistor devices. Surprisingly, two mobility maxima occur at azimuths corresponding to both axes of the rectangular cyclohexyl‐substituted quaterthiophene (CH4T) in‐plane unit cell, in contrast to the expected tensorial behavior of the field effect mobility.     

Efficient Polythiophene/Polyfluorene Copolymer Bulk Heterojunction Photovoltaic Devices: Device Physics and Annealing Effects

Here the influence of annealing on the operational efficiency of all‐polymer solar cells based on blends of the polymers poly(3‐hexylthiophene) (P3HT) and poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthiophen‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2″‐diyl) (F8TBT) is investigated. Annealing of completed devices is found to result in an increase in power conversion efficiency from 0.14 to 1.20%, while annealing of films prior to top electrode deposition increases device efficiency to only 0.19% due to a lowering of the open‐circuit voltage and short‐circuit current. By studying the dependence of photocurrent on intensity and effective applied bias, annealing is found to increase charge generation efficiency through an increase in the efficiency of the separation of bound electron‐hole pairs following charge transfer. However, unlike many other all‐polymer blends, this increase in charge separation efficiency is not only due to an increase in the degree of phase separation that assists in the spatial separation of electron‐hole pairs, but also due to an order of magnitude increase in the hole mobility of the P3HT phase. The increase in hole mobility with annealing is attributed to the ordering of P3HT chains evidenced by the red‐shifting of P3HT optical absorption in the blend. We also use X‐ray photoelectron spectroscopy (XPS) to study the influence of annealing protocol on film interface composition. Surprisingly both top and bottom electrode/blend interfaces are enriched with P3HT, with the blend/top electrode interface consisting of more than 95% P3HT for as‐spun films and films annealed without a top electrode. Films annealed following top electrode deposition, however, show an increase in F8TBT composition to ～15%. The implications of interfacial composition and the origin of open‐circuit voltage in these devices are also discussed.     

Effect of Alkyl Side‐Chain Length on Photovoltaic Properties of Poly(3‐alkylthiophene)/PCBM Bulk Heterojunctions

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.