The nature of in-plane skeleton Raman modes of P3HT and their correlation to the degree of molecular order in P3HT:PCBM blend thin films

The nature of main in-plane skeleton Raman modes (C=C and C-C stretch) of poly(3-hexylthiophene) (P3HT) in pristine and its blend thin films with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) is studied by resonant and nonresonant Raman spectroscopy and Raman simulations. Under resonant conditions, the ordered phase of P3HT with respect to its disordered phase is identified by (a) a large shift in the C=C mode peak position to lower wavenumber (~21 cm(-1) shift), (b) a narrower fwhm of the C=C mode (~9 cm(-1) narrower), (c) a larger intensity of the C-C mode relative to the C=C mode (~56% larger), and (d) a very small Raman dispersion (~5 cm(-1)) of the C=C mode. The behavior of the C=C and C-C modes of the ordered and disordered phases of P3HT can be explained in terms of different molecular conformations. The C=C mode of P3HT in P3HT:PCBM blend films can be reproduced by simple superposition of the two peaks observed in different phases of P3HT (ordered and disordered). We quantify the molecular order of P3HT after blending with PCBM and the subsequent thermal annealing to be 42 ± 5% and 94 ± 5% in terms of the fraction of ordered P3HT phase, respectively. The increased molecular order of P3HT in blends upon annealing correlates well with enhanced device performance (J(SC), -4.79 to -8.72 mA/cm(2) and PCE, 1.07% to 3.39%). We demonstrate that Raman spectroscopy (particularly under resonant conditions) is a simple and powerful technique to study molecular order of conjugated polymers and their blend films.     

Effect of multiple adduct fullerenes on charge generation and transport in photovoltaic blends with poly(3‐hexylthiophene‐2,5‐diyl)

The effect of replacing [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) by its multiadduct analogs (bis‐PCBM and tris‐PCBM) in bulk heterojunction organic solar cells with poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) is studied in terms of blend film microstructure, photophysics, electron transport properties, and device performance. Although the power conversion efficiency of the blend with bis‐PCBM is similar to the blend with PCBM, the performance of the devices with tris‐PCBM is considerably lower as a result of small photocurrent. Despite the lower electron affinity of the fullerene multiadducts, μs‐ms transient absorption measurements show that the charge generation efficiency is similar for all three fullerenes. The annealed blend films with multiadducts show a lower degree of fullerene aggregation and lower P3HT crystallinity than the annealed blend films with PCBM. We conclude that the reduction in performance is due largely to poorer electron transport in the blend films from higher adducts, due to the poorer fullerene network formation as well as the slower electron transport within the fullerene phase, confirmed here by field effect transistor measurements. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

给受体共混质量比对P3HT:PCBM薄膜结构和器件性能的影响

以聚3-己基噻吩(P3HT)为给体、[6,6]-苯基-C61-丁酸甲酯(PCBM)为受体的光伏体系作为研究对象,采用溶剂退火的后处理方法制备薄膜样品,利用紫外-可见(UV-Vis)吸收光谱、原子力显微镜(AFM)、X射线衍射(XRD)等测试手段分别对共混膜样品的形貌和结构进行表征,同时利用熵值统计方法对AFM形貌图像进行分析处理.并在此基础上制备太阳能电池器件,其结构为氧化铟锡导电玻璃/聚3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐/聚3-己基噻吩:[6,6]-苯基-C61-丁酸甲酯/金属铝(ITO/PEDOT:PSS/P3HT:PCBM/Al),研究了给受体共混比例(质量比)对活性层薄膜以及电池性能的影响.结果表明,受体PCBM含量的增加会影响P3HT给体相的有序结晶,当给受体比例为1:1时,活性层薄膜具有较宽的紫外-可见吸收特征,且具有较好的相分离和结晶度,基于该样品制备的电池器件其光电转换效率达到三种比例的最大值(2.77%).表明退火条件下,改变给受体比例可以影响活性层的微纳米结构而最终影响电池的光电转换效率.     

Conjugated polymer‐functionalized graphite oxide sheets thin films for enhanced photovoltaic properties of polymer solar cells

In this study, the maleimide‐thiophene copolymer‐functionalized graphite oxide sheets (PTM21‐GOS) and carbon nanotubes (PTM21‐CNT) were developed for polymer solar cell (PSC) applications. The grafting of PTM21‐OH onto the CNT and GO sheets was confirmed using FTIR spectroscopy. PTM21‐CNT and PTM21‐GOS exhibited excellent dispersal behavior in organic solvents. Better thermal stability was observed for PTM21‐CNT and PTM21‐GOS as compared with that for PTM21‐OH. In addition, the optical band gaps of PTM21‐GOS and PTM21‐CNT were lower than that of PTM21‐OH. We incorporated PTM21‐GOS and PTM21‐CNT individually into poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) blends for use as photoconversion layers of PSCs. Good distributional homogeneity was observed for PTM21‐GOS or PTM21‐CNT in the P3HT/PCBM blend film. The UV–vis absorption peaks of the blend films red‐shifted slightly upon increasing the content of PTM21‐GOS or PTM21‐CNT. The band gap energies and LUMO/HOMO energy levels of the P3HT/PTM21‐GOS and P3HT/PTM21‐CNT blend films were slightly lower than those of the P3HT film. The conjugated polymer‐functionalized PTM21‐GOS and PTM21‐CNT behaved as efficient electron acceptors and as charge‐transport assisters when incorporated into the photoactive layers of the PSCs. PV performance of the PSCs was enhanced after incorporating PTM21‐GOS or PTM21‐CNT in the P3HT/PCBM blend. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

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 (E_G) and the Urbach energy (E_U), 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.     

Understanding of morphology evolution in local aggregates and neighboring regions for organic photovoltaics

Fluorescence intensity and its ratio mapping combined with time-dependent optical microscopy and atomic force microscopy (AFM) were used to understand morphology evolution of local aggregates and neighboring regions for organic solar cells. Three solvents with different boiling points including chlorobenzene (CB), 1,3-dichlorobenzene (1,3-DCB) and 1,2-dichlorobenzene (1,2-DCB) were used to engineer morphology. These solvents affected morphology evolution factors such as solvent evaporation rate, formation (e.g., growth rate, size and/or quantity) of (6,6)-phenyl-C61-butric-acid methyl ester (PCBM)-rich aggregates, and packing/ordering of poly(3-hexylthiophene) (P3HT). Three local regions (1, 2 and 3) including microscale aggregates and their surrounding areas were identified to explore the mechanism of morphology evolution. Region 1 was the PCBM-rich aggregates; region 2 was the PCBM-deficient area; and region 3 was the area composed of a relatively normal P3HT/PCBM composite beyond region 2 for each solvent. The intensity of fluorescence spectra decreased as region 1 > region 2 > region 3 in thermally annealed (140 °C, 20 min) P3HT/PCBM blend film from each solvent. The highest fluorescence intensity in region 1 was probably caused by the relatively poor phase separation where both PCBM and P3HT formed large isolated domains. The higher fluorescence intensity ratio (720 nm/650 nm) suggested a larger relative amount of PCBM molecules, supported by similar morphologies in fluorescence intensity ratio mapping compared to those in optical images. The fluorescence intensity ratio was with the order of region 1 > region 3 > region 2 in both CB and 1,3-DCB based films, but with region 1 > region 2 > region 3 for the 1,2-DCB based film. The order of effective area taken up by aggregates was CB > 1,3-DCB > 1,2-DCB in annealed (140 °C, 10 min) bulk blend films. The final solar cell performance agreed with morphology results. This work is imperative with regards to revealing the mechanism of morphology evolution in local aggregates and surrounding regions for organic photovoltaic films.     

Photoluminescence Study on Charge Transfer Behavior of Poly(3‐hexylthiophene) and PCBM Blends

Charge transfer behavior of Poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl eser (PCBM) in solutions and in films were examined by photoluminescence (PL) spectroscopy. PL study in solutions indicated that separation distance between P3HT and PCBM affected charge transfer efficiency more seriously than the interface area issue between P3HT and PCBM. P3HT/PCBM film showed very effective photo‐induced charge transfer before post‐thermal annealing on the bi‐layer P3HT/PCBM film. Charge transfer efficiency was gradually diminished by the annealing‐induced phase separation between P3HT and PCBM as revealed by increasing PL emission intensity of P3HT.     

Vertical phase separation of conjugated polymer and fullerene bulk heterojunction films induced by high pressure carbon dioxide treatment at ambient temperature

The morphology of bulk-heterojunctions (BHJ) is critically important for conjugated polymer and fullerene blend solar cells. To alter the morphology, high pressure (gas phase) carbon dioxide (CO(2)) treatment is applied to poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) blend films under ambient temperature. This process can achieve vertically phase separated morphology such that PCBM distributes toward the film surface, which is suggested by secondary ion mass spectroscopy (SIMS), contact angle, X-ray photoelectron spectroscopy (XPS) and cross-sectional scanning electron microscope (SEM) studies. While pristine P3HT films do not show a significant change upon CO(2) treatment, pristine PCBM films are plasticized in high pressure CO(2). Thus, PCBM is selectively plasticized by CO(2) in the blend film and is drawn towards the surface due to depressed surface energy, although P3HT tends to distribute around the surface without CO(2). This stratification process can enhance solar cell performance. 55% improvement is achieved in the power conversion efficiency of the CO(2) treated device compared to the untreated one, indicating that CO(2) treatment can be a good candidate for optimizing the morphology and enhancing the performance of BHJ polymer solar cells.     

Controlling the surface composition of PCBM in P3HT/PCBM blend films by using mixed solvents with different evaporation rates

The surface composition of poly(3-hexylthiophene-2,5-diyl) and fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PCBM) blend films could be changed by controlling the film formation process via using mixed solvents with different evaporation rates. The second solvent, with a higher boiling point than that of the first solvent and much better solubility for PCBM than P3HT, is chosen to mix with the first solvent with a lower boiling point and good solubility for both PCBM and P3HT. The slow evaporation rate of the second solvent provides enough time for PCBM to diffuse upwards during the solvent evaporation. Thus, the weight ratio of PCBM and P3HT (m _PCBM/m _P3HT) at surface of the blend films was varied from ca. 0.1 to ca. 0.72, i.e., it increases about seven times by changing from single solvent to mixed solvents. Meanwhile, the mixed solvents were in favor to form P3HT naonofiber network and enhance phase separation of P3HT/PCBM blend films. As a result, the power conversion efficiency of the device from mixed solvents with slow evaporation process was about 1.5 times of the one from single solvents.     

Effects of amorphous poly(3‐hexylthiophene) on active‐layer structure and solar cells performance

A key challenge to the development of polymer‐based organic solar cells is the issue of long‐term stability, which is mainly caused by the unstable time‐dependent morphology of active layers. In this study, poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl C60‐butyric acid methyl ester (PCBM) blend is used as a model system to demonstrate that the long‐term stability of power conversion efficiency can be significantly improved by the addition of a small amount of amorphous regiorandom P3HT into semicrystalline regioregular one. The optical properties measured by UV–vis absorption and photoluminescence reveal that regiorandom P3HT can intimately mix with PCBM and prevent the segregation of PCBM. In addition, X‐ray scattering techniques were adopted to evidence the retardation of phase separation between P3HT and PCBM when regiorandom P3HT is added, which is further confirmed by optical microscopy that shows a reduction of large PCBM crystals after annealing at high temperature in the presence of regiorandom P3HT. The improvement of the long‐term stability is attributed to the capability of amorphous P3HT to be thermodynamically miscible with PCBM, which allows the active layer to form a more stable structure that evolves slower and hence decelerates the device decay. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 975–985     

Unveiling of polymer/fullerene blend films morphology by ellipsometrically determined optical order within polymer and fullerene phases

Optical properties of polymer/fullerene blend films upon thermal annealing are investigated by spectroscopic ellipsometry and described consistently within an optical model of the blend film. The optical model developed in this work treats both components, polymer and fullerene, as mixtures of reference materials, that is, their optically ordered and disordered phase. Then, the polymer/fullerene blend layer is also described as a mixture of these two components. In this manner, we extend an existing optical model, which accounts for the optical order within the polymer phases, on cases where the optically ordered PCBM phase occurs, too. Determination of the dielectric functions of all four reference materials allows for a unique quantitative characterization of a polymer/fullerene blend film by assigning to it thickness and the polymer to fullerene volume fraction of its layers as well as corresponding volume fractions of theirs optically ordered and disordered polymer and fullerene phases. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1094–1100     

Impact of side‐chain length on the phase structures of P3ATs and P3AT:PCBM films as revealed by SSNMR and FTIR

It is known that poly(3‐alkylthiophene) (P3AT) side‐chain length notably influences the photovoltaic performances of relating devices. However, comprehensively study on its impact on the structures of P3ATs and their blends with [6, 6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) is insufficient. By using solid‐state NMR and FTIR techniques, four P3ATs and their PCBM blends are investigated in this work, focusing on the phase structures as modulated by side‐chain length. Recently, we revealed multiple crystalline main‐chain packings of packing a and b together with a mesophase in poly(3‐butylthiophene) (P3BT) films (DOI: 10.1021/acs.macromol.6b01828). Here, the semicrystalline structures are investigated on poly(3‐hexylthiophene) (P3HT), poly(3‐octylthiophene) (P3OT), and poly(3‐dodecylthiophene) (P3DDT) with traditional form I modification, where packing a and the amorphous phase are probed. Furthermore, crystallized side chain within packing a is detected in both P3OT and P3DDT films, which shows a FTIR absorption at 806 cm⁻¹. Structural studies are also conducted on P3AT:PCBM blends. Compared with the pure P3ATs, the polymer crystallinities of the blends show reduction of about 40% for P3OT and P3DDT, whereas only about 10% for P3HT. Moreover, in P3BT:PCBM and P3HT:PCBM, the crystalline polymers and PCBM are phase separated, while in P3OT:PCBM and P3DDT:PCBM, blend components are mostly miscible. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 751–761     

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.

     

Transient Absorption Spectroscopy Studies on Polythiophene–Fullerene Bulk Heterojunction Organic Blend Films Sensitized with a Low‐Bandgap Polymer

Recently, the concept of near‐infrared sensitization is successfully employed to increase the light harvesting in large‐bandgap polymer‐based solar cells. To gain deeper insights into the operation mechanism of ternary organic solar cells, a comprehensive understanding of charge transfer–charge transport in ternary blends is a necessity. Herein, P3HT:PCPDTBT:PCBM ternary blend films are investigated by transient absorption spectroscopy. Hole transfer from PCPDTBT‐positive polarons to P3HT in the P3HT:PCPDTBT:PCBM 0.9:0.1:1 blend film can be visualized. This process evolves within 140 ps and is discussed with respect to the proposed charge‐generation mechanisms.

     

Synthesis of all‐conjugated poly(3‐hexylthiophene)‐block‐ poly(3‐(4′‐(3″,7″‐dimethyloctyloxy)‐3′‐pyridinyl)thiophene) and its blend for photovoltaic applications

New all‐conjugated block copolythiophene, poly(3‐hexylthiophene)‐block‐poly(3‐(4′‐(3″,7″‐dimethyloctyloxy)‐3′‐pyridinyl)thiophene) (P3HT‐b‐P3PyT) was successfully prepared by Grignard metathesis polymerization. The supramolecular interaction between [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) and P3PyT was proposed to control the aggregated size of PCBM and long‐term thermal stability of the photovoltaic cell, as evidenced by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and optical microscopy. The effect of different solvents on the electronic and optoelectronic properties was studied, including chloroform (CL), dichlorobenzene (DCB), and mixed solvent of CL/DCB. The optimized bulk heterojunction solar cell devices using the P3HT‐b‐P3PyT/PCBM blend showed a power conversion efficiency of 2.12%, comparable to that of P3HT/PCBM device despite the fact that former had a lower crystallinity or absorption coefficient. Furthermore, P3HT‐b‐P3PyT could be also used as a surfactant to enhance the long‐term thermal stability of P3HT/PCBM‐based solar cells by limiting the aggregated size of PCBM. This study represents a new supramolecular approach to design all‐conjugated block copolymers for high‐performance photovoltaic devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Interfacial free energy driven nanophase separation in poly(3-hexylthiophene)/[6,6]-phenyl-C61-butyric acid methyl ester thin films

The nanostructure of thermally annealed thin films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blends on hydrophobic and hydrophilic substrates was studied to unravel the relationship between the substrate properties and the phase structure of polymer blends in confined geometry. Indeed, the nature of the employed substrates was found to affect the extent of phase separation, the PCBM aggregation state and the texture of the whole system. In particular, annealing below the melting temperature of the polymer yielded the formation of PCBM nanometric crystallites on the hydrophobic substrates, while mostly amorphous microscopic aggregates were formed on the hydrophilic ones. Moreover, while an enhanced in-plane orientation of P3HT lamellae was promoted on hydrophobic substrates, a markedly tilted geometry was produced on the hydrophilic ones. The observed effects were interpreted in terms of a simple model connecting the interface free energy for the blend films to the different polymer chain mobility and diffusion velocity of PCBM molecules on the different substrates.     

Phase diagram of P3HT:PC70BM thin films based on variable-temperature spectroscopic ellipsometry

In this article, we present the research on the influence of the composition of thin films of a blend of poly (3-hexylthiophene −2,5-diyl) - P3HT with fullerene derivatives [6,6]-phenyl-C71-butyric acid methyl ester – PC70BM and [6,6]-phenyl-C61-butyric acid methyl ester – PC60BM on their thermal transitions. The influence of molar mass (Mw) of P3HT (Mw = 65.2; 54.2 and 34.1 kDa) and PCBM (PC60BM – Mw = 911 g/mol and PC70BM – Mw = 1031 g/mol) is examined in details. The article presents significantly expanded research compared to our previous work on thermal transitions in thin films of blend P3HT (Mw = 65.2 kDa) with PC60BM. For this reason, we also compare current results with previous ones. Here, we present for the first time a phase diagram of thin films of the P3HT(Mw = 65.2 kDa):PC70BM blend using variable-temperature ellipsometry. Our research reveals the presence of characteristic temperatures of pure phases in thin films of P3HT: PCBM blends. It turns out that the cold crystallization temperature of the P3HT phase in P3HT(Mw = 65.2 kDa):PC70BM blend films is lower than corresponding temperature in P3HT(Mw = 65.2 kDa):PC60BM blend films. At the same time, the cold crystallization temperature of the PC70BM phase behaves inversely. We demonstrate also that variable-temperature spectroscopic ellipsometry is a very sensitive technique for studying thermal transitions in these thin films. In addition, we show that the entire phase diagram can be determined based on the raw ellipsometric data analysis, e.g. using a delta angle at wavelength λ = 280 nm.     

Van der Waals effects on structure and optical properties in organic photovoltaics

We have recently reported that dispersion forces can have drastic effects on the structure and charge separation in organic photovoltaics (OPVs) (Martinez et al., J. Phys. Chem. C 121, 20 134 [2017]). Here we investigate dimer complexes formed by the polymer P3HT and the fullerene derivative PCBM. We show how van der Waals (vdW) interactions affect the geometrical structure, which has strong effects on the electronic structure and UV-Vis absorption spectrum. Time-dependent density functional theory calculations demonstrate that the experimentally observed blue-shift of the absorption maximum of P3HT/PCBM OPV cells with respect to pure P3HT results mainly from distortions in P3HT due to vdW interactions between donor and acceptor fragments. Reduced absorption in the red region of the UV-Vis spectrum results from distortions of P3HT and small charge transfer between P3HT and PCBM. These results are in qualitative agreement with experiments and recent theoretical results on the corresponding solid-state films.     

Microstructural behavior and failure mechanisms of organic semicrystalline thin film blends

Organic thin film blends of P3HT semiconducting polymers and PCBM fullerenes have enabled large‐scale semiconductor fabrication pertaining to flexible and stretchable electronics. However, molecular packing and film morphologies can significantly alter mechanical stability and failure behavior. To further understand and identify the fundamental mechanisms affecting failure, a multiphase microstructurally based formulation and nonlinear finite‐element fracture methodology were used to investigate the heterogeneous deformation and failure modes of organic semicrystalline thin film blends. The multiphase formulation accounts for the crystalline and amorphous behavior, polymer tie‐chains, and the PCBM aggregates. Face‐on packing orientations resulted in extensive inelastic deformation and crystalline rotation, and this was characterized by ductile failure modes and interfacial delamination. For edge‐on packing orientations, brittle failure modes and film cracking were due to lower inelastic deformation and higher film stress in comparison with the face‐on orientations. The higher crystallinity of P3HT and larger PCBM aggregates associated with larger domain sizes, strengthened the film and resulted in extensive film cracking. These predictions of ductile and brittle failure are consistent with experimental observations for P3HT:PCBM films. The proposed predictive framework can be used to improve organic film ductility and strength through the control of molecular packing orientations and microstructural mechanisms. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 896–907     

Morphology and Performance of Poly(2-methoxy-5-(20-ethyl-hexyloxy)-p-phenylenevinylene) (MEH-PPV)∶(6,6)-Phenyl-C61-butyric Acid Methyl Ester (PCBM) Based Polymer Solar Cells

Polymer solar cells were fabricated based on composite films of poly(2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV):fullerene derivative (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) with weight blend ratio of 1:3, 1:4 and 1:5, spin‐coated from chloroform (CF), chlorobenzene (CB), and o‐dichlorobenzene (ODCB) solutions, respectively. Photoinduced current and power conversion efficiency (PCE) of the devices show a dependence on the solvents. The solar cells have the highest PCE at 1:5 blend ratio. Transmission electron microscopy (TEM) morphology reveals that there are some voids in MEH‐PPV:PCBM films. The void number decreases with the solvent from CF to CB and ODCB. We found the voids are located at the bottom of the films through electron tomography technique by TEM and film bottom‐side morphology study by atomic force microscopy. The charge carrier transport efficiency and collection efficiency should decrease greatly due to the voids, and the more voids the film has, the more degree the efficiencies decrease. PCE of the solar cell prepared from CF is lower than that of the solar cells prepared from CB and ODCB. The void phenomenon of MEH‐PPV:PCBM based solar cell and method to investigate the void position provide an experimental evidence and research mentality to fabricate polymer solar cell with high performance.