PCBM Aggregates Research Articles

Improving the photovoltaic performance of inverted perovskite solar cells via manipulating the molecular packing structure of PCBM

In this study, the molecular packing structure of solution-processed phenyl-C61-butyric acid methyl ester (PCBM) thin film was manipulated by varying the volume ratio of chlorobenzene (CB) to bromobenzene (BrB) from 100:0 to 50:50, which largely influences the device performance of the PCBM/perovskite heterojunction solar cells. Absorbance spectra, photoluminescence spectra, atomic force microscopic images and contact angle images were used to investigate the molecular packing structure effects of the PCBM thin films on the device performance of the inverted perovskite solar cells. Our experimental results show that the formation of PCBM aggregates and the contact quality at the PCBM/perovksite interface significantly influence the open-circuit voltage, short-circuit current density and fill factor of the resultant solar cells simultaneously. It is noted that the PCE of the encapsulated inverted CH3NH3PbI3 (MAPbI3) solar cells exhibited a stable and high power conversion efficiency of 18%.

Thermo-Optical and Structural Studies of Iodine-Doped Polymer: Fullerene Blend Films, Used in Photovoltaic Structures.

Optical and structural properties of a blend thin film of (1:1 wt.) of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) doped with iodine (I2) and then exposed to a stepwise heating were reported and compared with the properties of doped P3HT films. The UV-Vis(T) absorption measurements were performed in situ during annealing runs, at the precisely defined temperatures, in a range of 20–210 °C. It was demonstrated that this new method allows one to observe the changes of absorption spectra, connected with the iodine release and other structural processes upon annealing. In addition, the thermally-induced changes of the exciton bandwidth (W) and the absorption edge parameters, i.e., the energy gap (EG) and the Urbach energy (EU) were discussed in the context of different length of conjugation and the structural disorder in polymers and blends films. During annealing, several stages were distinguished and related to the following processes as: the iodine escape and an increase in P3HT crystallinity, the orderly stacking of polymer chains, the thermally inducted structural defects and the phase separation caused by an aggregation of PCBM in the polymer matrix. Moreover, the detailed X-ray diffraction studies, performed for P3HT and P3HT:PCBM films, before and after doping and then after their thermal treatment, allowed us to consider the structural changes of polymer and blend films. The effect of iodine content and the annealing process on the bulk heterojunction (BHJ) solar cells parameters was checked, by the impedance spectroscopy (IS) measurements and the J-V characteristics registration. All of the investigated P3HT:PCBM blend films showed the photovoltaic effect; the increase in power conversion efficiency (PCE) upon iodine doping was demonstrated.

In situ thermo-optical studies of polymer:fullerene blend films

Optical properties of a blend thin film (1:1 wt) of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) exposed to a stepwise heating and cooling, have been reported and compared with the properties of pure PCBM and P3HT films. The UV–Vis(T) absorption measurements were performed in situ, during annealing and cooling runs, at the precisely defined temperatures, in a range of 20–210 °C. It was demonstrated that this new method allows to observe the changes of absorption coefficient spectra and absorption edge parameters: the energy gap (EG) and the Urbach energy (EU), connected with the length of conjugation and structural disorder of thin film, respectively. Several stages, during annealing/cooling runs, were distinguished for the P3HT:PCBM blend film and related to the following processes, as an increase of P3HT crystallinity in the blend, the orderly stacking of polymer chains, thermally induced structural defects and the phase separation, caused by an aggregation of PCBM in the polymer matrix. These changes were also observed on the P3HT:PCBM film surface, by means to the microscopic studies.

Mechanistic Insights into the Effect of Polymer Regioregularity on the Thermal Stability of Polymer Solar Cells.

Thermal stability is a bottleneck toward commercialization of polymer solar cells (PSCs). The effect of PCBM aggregation on a multilength scale on the bulk-heterojunction (BHJ) structure, performance, and thermal stability of PSCs is studied here by grazing-incidence small- and wide-angle X-ray scattering. The evolution of hierarchical BHJ structures of a blend film tuned by regioregularity of polymers from the as-cast state to the thermally unstable state is systematically investigated. The thermal stability of PSCs with high polymer regioregularity values can be improved because of the good mutual interaction between polymer crystallites and fullerene aggregates. The insights obtained from this study provide an approach to manipulate the film structure on a multilength scale and to enhance the thermal stability of P3HT-based PSCs.

Long-term thermally stable nanoconfining networks for efficient fully conjugated semicrystalline/amorphous diblock copolymer photovoltaics

Abstract In this study, a new fully π-conjugated diblock copolymer comprising of major semicrystalline poly(3-butyl thiophene) (P3BT) and minor amorphous poly(2,5-dihexyloxy-p-phenylene) (PPP) block chains was rationally designed and further used as synergistic charge-transporting networks for PCBM based solar cells. The light-harvesting P3BT block was carefully chosen due to its high melting temperature and greater hole mobility to afford better thermal stability. Despite lower molecular weight P3BT block in the copolymer compared with that of a P3BT homopolymer counterpart, the copolymer exhibited long-range ordered fibrils with larger P3BT crystals and higher total crystallinity, indicating that the minor PPP chains promote the ordering and crystallization of P3BT. In addition, the strong immiscibility and difference in the crystallographic kinetics among the two main-chain moieties allow the copolymer/PCBM hybrid to spontaneously self-assemble into an interpenetrating nanostructure, while permitting PCBM nanoparticles to preferentially locate in the amorphous PPP domains to form bicontinuous conduits for efficient dual-charge transport. Notably, the copolymer/PCBM hybrids exhibited superior long term thermal stability against degradation and PCBM aggregation upon accelerated aging of the devices. At stringently high aging temperature of 180 °C for 4 h for a thermal stress test, the copolymer devices retain nearly 90% of their maximum PCE, whereas those of the reference P3BT/PCBM solar cells decrease severely to be less than 50% of their maximum. These results demonstrate the advantage of using thermally stable all π-conjugated block copolymers to provide substantial enhancement in charge dissociation, transport as well as extended thermal stability due to the nanoconfining effect of its self-assembled copolymer structure.

Elaboration of PCBM Coated P3HT Nanoparticles: Understanding the Shell Formation

Solvent displacement, or nanoprecipitation, is a well-known process to develop colloidal dispersions in water. Using two successive and selective nanoprecipitation steps, we developed a method to generate [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) shell on poly(3-hexylthiophene) (P3HT) core nanoparticles (P3HT@PCBM). We report herein on the understanding of the shell formation during this process. Using several techniques (dynamic light scattering, zeta-potential, photoluminescence), we evidenced that after the first solvent displacement with dimethyl sulfoxide (DMSO), the PCBM molecules still dissolved in the medium are already in close interaction with the P3HT nanoparticles (NP). Such proximity of the P3HT core with PCBM molecules in the DMSO dispersion explains why PCBM aggregates around the nanoparticles during the second solvent displacement with water. A fast electron transfer from P3HT to PCBM was identified by transient absorption spectroscopy, confirming the core-shell morphology even for low PCBM concentration. This study opens the route for the development of well-defined nano-objects dispersed in water for fabrication of organic photovoltaic devices with eco-friendly processes.

Beyond Fullerenes: Indacenodithiophene-Based Organic Charge-Transport Layer toward Upscaling of Low-Cost Perovskite Solar Cells.

Phenyl-C61-butyric acid methyl ester (PCBM) is universally used as the electron-transport layer (ETL) in the low-cost inverted planar structure of perovskite solar cells (PeSCs). PCBM brings tremendous challenges in upscaling of PeSCs using industry-relevant methods due to its aggregation behavior, which undermines the power conversion efficiency and stability. Herein, we highlight these, seldom reported, challenges with PCBM. Furthermore, we investigate the potential of nonfullerene indacenodithiophene (IDT)-based molecules by employing a commercially available variant, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3- d:2',3'- d']- s-indaceno[1,2- b:5,6- b'] dithiophene (ITIC), as a PCBM replacement in ambient-processed PeSCs. Films fabrication by laboratory-based spin-coating and industry-relevant slot-die coating methods are compared. Although similar power-conversion efficiencies are achieved with both types of ETL in a simple device structure fabricated by spin-coating, the nanofibriller morphology of ITIC compared to the aggregated morphology of PCBM films enables improved mechanical integrity and stability of ITIC devices. Upon slot-die coating, the aggregation of PCBM is exacerbated, leading to significantly lower power-conversion efficiency of devices than spin-coated PCBM as well as slot-die-coated ITIC devices. Our results clearly indicate that IDT-based molecules have great potential as an ETL in PeSCs, offering superior properties and upscaling compatibility than PCBM. Thus, we present a short summary of recently emerged nonfullerene IDT-based molecules from the field of organic solar cells and discuss their scope in PeSCs as electron or hole-transport layer.

Morphology of a Ternary Blend Solar Cell Based on Small Molecule:Conjugated Polymer:Fullerene Fabricated by Blade Coating

AbstractHere, conjugated polymer is added as third component to tune the solution viscosity, morphology, and function of small molecule (SM) based bulk‐heterojunction (BHJ) solar cells, which are fabricated using blade coating. Novel information about the effect of blade coating speed on the nanoscale morphology and function of ternary blend solar cells is provided. The crystal sizes increase with an increase of coating speed for both binary and ternary blends, while the addition of the third component tends to favor smaller SM crystal grains and improves the connectivity of SM crystals. Small angle neutron scattering experiments provide the first clear experimental evidence that the addition of the third component would significantly impact the fullerene phase separation, which is crucial for bimolecular recombination and charge transport. It shows that for both binary and ternary blends, the concentration and sizes of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) aggregates increase with an increase of coating speed, while addition of third component does not affect the volume fraction of PCBM aggregates but impacts the size of PCBM aggregates. It is demonstrated that the judicious selection of blade coating speed and addition of conjugated polymer optimize the morphology of SM‐BHJ, providing guidelines for high performance SM‐BHJs from roll‐to‐roll production.

Effects of neat C60 doping on the performance of bulk-heterojunction solar cells based on P3HT:PCBM

ABSTRACTWe explored the effect of neat C60 doping on the performance of bulk heterojunction (BHJ) organic photovoltaic cells (OPVs) based on poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl C61 butyric acid methyl ester (PCBM). The power conversion efficiencies (PCEs) were found to gradually decrease as the relative concentration of C60 increased. This PCE decrease is mainly due to the reduction in short-circuit current density (Jsc). Atomic force microscopy images revealed that C60-doped BHJ films consisted of unformed large P3HT crystals and many small PCBM aggregates. This morphology leads to a decrease in the effective P3HT conjugation length and an enhancement of absorption bleaching in neutral P3HT chains. These results explain well the blue-shift absorption spectra, the decrease of absorption coefficients, and the reduction in Jsc found in C60-doped BHJ OPVs.

The Study of Crystallization of Polyfluorene and Fullerene Derivatives in Semiconducting Layer of Organic Solar Cells

This research was focused on the effect of solid crystallization additive namely 1,4-dichlorobenzene (PDCB) in the 1:2 (w/w) active layer of benzothiadiazole/thiophene-based copolymers (PFTBzTT) to [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) on the morphology and performance of bulk heterojunction (BHJ) organic solar cells. The active layer was deposited by spin-coating with chloroform solutions by different PDCB additive concentrations from 0-52 mg/ml. The inclusion of additive into the polymer solution was able to improve the performance of BHJ solar cells. The maximum power conversion efficiency (PCE) of 0.84% achieved for a cell with PDCB concentration of 36 mg/ml after annealing at 180 °C for 20 min. The XRD and TEM techniques used to analyse the crystal structure and morphology of the thin films. From these results were found that PDCB additive presented higher level of PCBM crystal structure by more aggregation of PCBM and a larger extent of phase separation than those of the films without additive. The AFM results demonstrated that the optimum PDCB concentration and annealing process helped PCBM aggregated into micron sized crystal rods.

Enhanced Long-term and Thermal Stability of Polymer Solar Cells in Air at High Humidity with the Formation of Unusual Quantum Dot Networks.

Due to the practical applications of polymer solar cells (PSCs), their stability recently has received increasing attention. Herein, a new strategy was developed to largely enhance the long-term and thermal stability of PSCs in air with a relatively high humidity of 50-60% without any encapsulation. In this strategy, semiconductor PbS/CdS core/shell quantum dots (QDs) were incorporated into the photoactive blend of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM). By replacing the initial ligands of oleic acid with halide ligands on the surface of PbS/CdS QDs via solution-phase ligand exchange, we were able to form unusual, continuous QD networks in the film of P3HT:PCBM, which effectively stabilized the photoactive layer. Air-processed PSCs based on the stabilized P3HT:PCBM film showed excellent long-term stability under high humidity, providing over 3% of power conversion efficiency (PCE) simultaneously. Around 91% of pristine PCE was retained after 30 days storage in high-humidity air without encapsulation. This constitutes a remarkable improvement compared to ∼53% retained PCE for the QD-free devices, which can be ascribed to the efficient suppression of both PCBM aggregation and oxidation of the thiophene ring in P3HT, thanks to the formation of robust QD networks. Furthermore, the presence of QD networks was able to enhance the stability of the P3HT:PCBM film against thermal stress/oxidation under high-humidity environment (50-60%) as well. The device kept 60% of pristine PCE after thermal treatment for 12 h at 85 °C in air, which is more than twice higher than that for the QD-free device. To the best of our knowledge, the work represents the first unambiguous demonstration of the formation of QD networks in the photoactive layer and of their important contribution to the stability of PSCs. This strategy is highly promising for other fullerene-based PSCs and opens a new avenue toward achieving PSCs with high PCE and excellent stability.

Morphological and micro-structural interface characterization in multilayer inverted polymer-fullerene bulk heterojunction solar cells

Inverted polymer solar cells based on P3HT/PCBM bulk heterojunction were prepared on flexible polyethylene naphthalate (PEN) substrate. The effect of annealing of the PEN/ITO/ZnO multilayer and ZnO/P3HT:PCBM on the structural, morphological, photophysical and photovoltaic properties was investigated and scrutinized directly on the OPV devices using atom probe tomography (APT), scanning electron microscopy (SEM) and microfocus X-ray techniques. We carried out a 3D reconstruction of the interfaces of the multilayer containing PEN/ITO, ZnO/ITO and P3HT:PCBM/ZnO to address the interface micro-structure and its influence on the morphology of the photoactive film. The analyses show that the morphology of the interfaces is affected by the structure of each layer of the BHJ devices causing orientation of P3HT crystals with PCBM aggregates and ZnO, which in turn leads to a significant change of the charge transport across each layer and therefore photovoltaic performances.

Laser-induced crystallization and conformation control of poly(3-hexylthiophene) for improving the performance of organic solar cells

Abstract Femto-second laser irradiation on P3HT:PCBM solutions have been demonstrated to have a significant impact on the conformational structures and photovoltaic performance of the resultant thin films. The crystallinity and edge-on/face-on conformations of P3HT and the aggregation of PCBM can be manipulated by controlling the wavelength (400–800 nm) and illumination duration (1–3 h) of the lasers. Grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS) have been simultaneously utilized to characterize the nanostructures of the P3HT:PCBM blend films spin-cast from pristine and laser-irradiated solutions. The results show that the crystallinity, π-π* stacking and face-on conformations of P3HT can be enhanced as a result of the laser irradiation at 500 nm for 3 h. Furthermore, the diffusion and aggregation of PCBM molecules are suppressed by the photo-induced dimerization, as evidenced by the Raman spectra of the films cast from laser-irradiated PCBM solutions. The time-resolved fluorescence decay profiles show the charge transfer efficiency is improved, which may correlate to the supramolecular ordering of the polythiophene chains and the optimized phase separation in P3HT:PCBM composite. In the P3HT:PCBM active layer of the organic solar cells, more efficient charge transport and fine interpenetrating networks can be achieved due to the improved conformational microstructures. Consequently, the short-circuit current densities and power conversion efficiencies can be enhanced in organic solar cells based on the laser-irradiation processed P3HT:PCBM solutions.

Suppression of Thermally Induced Fullerene Aggregation in Polyfullerene-Based Multiacceptor Organic Solar Cells.

A novel main-chain polyfullerene, poly[fullerene-alt-2,5-bis(octyloxy)terephthalaldehyde] (PPC4), is investigated for its hypothesized superior morphological stability as an electron-accepting material in organic photovoltaics relative to the widely used fullerene phenyl-C61-butyric acid methyl ester (PCBM). When mixed with poly(3-hexylthiophene-2,5-diyl) (P3HT), PPC4 affords low-charge-generation yields because of poor intermixing within the blend. The adoption of a multiacceptor system, by introducing PCBM into the P3HT:polyfullerene blend, was found to lead to a 3-fold enhancement in charge generation, affording power conversion efficiencies very close to that of the prototypical P3HT:PCBM binary control. Upon thermal stressing and in contrast to the P3HT:PCBM binary, photovoltaic devices based on the multiacceptor system demonstrated significantly improved stability, outperforming the control because of suppression of the PCBM migration and aggregation processes responsible for rapid device failure. We rationalize the influence of the fullerene miscibility and its implications on the device performance in terms of a thermodynamic model based on Flory-Huggins solution theory. Finally, the potential universal applicability of this approach for thermal stabilization of organic solar cells is demonstrated, utilizing an alternative low-band-gap polymer-donor system.

Formation of phenyl-C61-butyric acid methyl ester nanoscale aggregates after supercritical carbon dioxide annealing

In this study, we successfully developed a novel method to create [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) nanoscale aggregates using supercritical carbon dioxide (scCO2) annealing and fabricated bulk heterojunction (BHJ) solar cells with the nanoscale PCBM to improve device performance. PCBM forms nanoscale aggregates with a size of approximately 70 nm after scCO2 annealing at 11 MPa and 50 °C for 60 min. However, PCBM remains amorphous after thermal annealing (TA) at 150 °C for 5 min. The morphology, structure, and crystallinity of poly(3-hexylthiophene) (P3HT) in the scCO2-treated P3HT film are nearly the same as those in the TA-treated P3HT film. In the P3HT/PCBM blend, the formation of PCBM nanoscale aggregates by scCO2 treatment decreases the disturbance for P3HT crystallization and improves diffusion and regular packing of P3HT molecular chains. This increases the crystallinity of P3HT so that it becomes higher than that in the TA-treated blend film. The nanoscale aggregates of PCBM and the higher crystallinity of P3HT give the scCO2-treated P3HT/PCBM BHJ solar cells a maximum power conversion efficiency (PCE) of 2.74%, which is much higher than that of the as-cast device (PCE is 1.70%) and a little higher than the highest PCE (2.64%) of thermally annealed devices. These results indicate that scCO2 is an effective, mild, and environmental method to modulate the nanoscale aggregates of PCBM and to improve the PCE of BHJ solar cells. However, the size of the PCBM aggregates is a little larger than the most suitable size of the exciton diffusion length, leading to limited improvement of the PCE.

Solvent‐Dependent Structure Formation in Drying P3HT:PCBM Films Studied by Molecular Dynamics Simulations

Phase separation in the donor‐acceptor blend poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) during evaporation of a solvent using coarse‐grained molecular dynamics simulations is studied here. To this end, an equilibrated P3HT:PCBM:solvent mixture is placed in an elongated simulation box, after which solvent molecules are removed at regular time intervals from a region above the film. Three often‐used solvents are considered: chloroform (CFM), chlorobenzene (CLB), and orthodichlorobenzene (oDCB). The coarse‐grained solvent–solvent interaction parameters are tuned to reproduce the atmospheric boiling temperatures, while the PCBM–solvent interaction parameters are tuned to reproduce the PCBM solubilities. Other parameters are taken from the literature. During evaporation, the formation of a crust that is depleted of solvent, in which aggregation of P3HT and PCBM occurs, is observed. In agreement with experiment, the top region of the dry film is rich in PCBM for the cases of CLB and oDCB, and rich in P3HT for the case of CFM, while the very top layer of the film is always rich in P3HT. This vertical separation is ascribed to a competition between the tendency of P3HT to move to the surface due to its low surface energy and the different tendencies of PCBM to be dragged along to the surface by the evaporating solvent depending on its solubility. Also in agreement with experiment, the P3HT–PCBM interface area is larger for CLB and oDCB than for CFM. For CLB and oDCB, an indication for a spinodal P3HT–PCBM decomposition starting from the top and bottom surface is found, whereas for CFM the phase separation appears to be initiated in the bulk of the film. image

A thermodynamic and kinetic description of PCBM phase segregation and aggregation in P3HT:PCBM blends

The kinetics and thermodynamics of PCBM phase segregation and aggregation in P3HT:PCBM blends has been studied. We develop a thermodynamic model for PCBM phase segregation in P3HT:PCBM blends which explains the formation of nanoscale crystallites which subsequently diffuse and coalesce into larger PCBM aggregates. We show that the formation of nanoscale crystallites during the film making process prevents spinodal decomposition of the P3HT:PCBM blends even at PCBM weight fractions above the spinodal decomposition boundary for the system. Finally, we demonstrate that the observed aggregate morphology can be understood in terms of a kinetic model based on the diffusional flux lines of PCBM crystallite which, in turn, govern the evolution of the macroscopic growth front.

Spectroelectrochemical evidence for the effect of phase structure and interface on charge behavior in poly(3-hexylthiophene): Fullerene active layer

To investigate the correlation between morphology of active layer and performance of polymer solar cells (PSCs). Poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) were selected as research object and five PSCs based on active layers with varied morphology were fabricated. The results showed that P3HT crystalline phase and donor-acceptor (D-A) interface had an important influence on PSCs performance, which was revealed by structure characterization and J-V measurement. To further understanding the effect of phase structure and D-A interface on charge behavior. Spectroelectrochemistry measurement (SEC) was performed to characterize the steady-state optical absorption of P3HT, PCBM cation and anion in varied active layers, and the spectra difference of cations and anions was analyzed. The results were found that D-A interface could promote charge generation. P3HT crystalline phase and PCBM aggregation phase were beneficial for improving the charge transport ability. Meanwhile, the non-equilibrium transport of electron and hole in PSCs was corroborated by SEC.

X-Ray Nanoscopy of a Bulk Heterojunction.

Optimizing the morphology of bulk heterojunctions is known to significantly improve the photovoltaic performance of organic solar cells, but available quantitative imaging techniques are few and have severe limitations. We demonstrate X-ray ptychographic coherent diffractive imaging applied to all-organic blends. Specifically, the phase-separated morphology in bulk heterojunction photoactive layers for organic solar cells, prepared from a 50:50 blend of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) and thermally treated for different annealing times is imaged to high resolution. Moreover, using a fast-scanning calorimetry chip setup, the nano-morphological changes caused by repeated thermal annealing applied to the same sample could be monitored. X-ray ptychography resolves to better than 100 nm the phase-segregated domains of electron donor and electron acceptor materials over a large field of view within the active layers. The quantitative phase contrast images further allow us to estimate the local volume fraction of PCBM across the photovoltaically active layers. The volume fraction gradient for different regions provides insight on the PCBM diffusion across the depletion zone surrounding PCBM aggregates. Phase contrast X-ray microscopy is under rapid development, and the results presented here are promising for future studies of organic-organic blends, also under in situ conditions, e.g., for monitoring the structural stability during UV-Vis irradiation.

Synthesis and characterization of poly(3-hexylthiophene)-block-poly(dimethylsiloxane) for photovoltaic application

A diblock copolymer poly(3-hexylthiophene)-block-poly(dimethylsiloxane) (P3HT-b-PDMS) was synthesized as a donor material for organic photovoltaic devices. The regioregular poly(3-hexylthiophene) (P3HT) with a bromo-terminal was prepared via Grignard metathesis polymerization, and poly(dimethylsiloxane) (PDMS) with a silane terminal was obtained by anionic polymerization. Finally, the coupling reaction of these homopolymers via hydrosilylation afforded P3HT-b-PDMSs with different lengths of the PDMS segment. Device evaluation of photovoltaic cells based on P3HT-b-PDMS blended with [6,6]-phenyl-C61-butylic acid methyl ester (PCBM) revealed that the incorporation of PDMS segment effectively increase the photocurrent compared to a P3HT/PCBM system. From AFM and SEM observations for P3HT-b-PDMS/PCBM blend films, it was clearly revealed that the phase-separated structure within several tens nanometer scale was obtained, and that the aggregation of PCBM was sufficiently suppressed by the introduction of PDMS. These facts indicate that the PDMS segment is probably assembled into the interface between P3HT and PCBM to relieve the mismatch of the surface free energy.