Improved stability in P3HT:PCBM photovoltaics by incorporation of well‐designed polythiophene/graphene compositions

Morphological and photovoltaic stabilities of poly(3‐hexylthiophene) (P3HT):phenyl‐C₆₁‐butyric acid methyl ester (PC₇₁BM) solar cells were investigated in pristine and modified states. To this end, four types of patterned/assembled nanostructures, namely reduced graphene oxide (rGO)‐g‐poly(3‐dodecylthiophene)/P3HT patched‐like pattern, rGO–polythiophene/P3HT/PC₇₁BM nanofiber, rGO‐g‐P3HT/P3HT cake‐like pattern and supra(polyaniline (PANI)‐g‐rGO/P3HT), were designed on the basis of rGO and various conjugated polymers. Intermediately covered rGO nanosheets by P3HT crystals (supra(PANI‐g‐rGO/P3HT)) performed better than sparsely (patched‐like pattern) and fully (cake‐like pattern) covered ones in P3HT:PC₇₁BM solar cell systems. Supra(PANI‐g‐rGO/P3HT) nanohybrids largely phase‐separated in active layers (root mean square = 0.88 nm) and also led to the highest performance (power conversion efficiency of 5.74%). The photovoltaic characteristics demonstrated decreasing trends during air aging for all devices, but with distinct slopes. The steepest decreasing plots were obtained for the unmodified P3HT:PC₇₁BM devices (from 1.77% to 0.28%). The two supramolecules with the most ordered structures, that is, cake‐like pattern (10.12 mA cm^?2, 51%, 0.58 V, 2.2 × 10^?6 cm² V^?1 s^?1, 4.3 × 10^?5 cm² V^?1 s^?1, 0.69 nm and 2.99%) and supra(PANI‐g‐rGO/P3HT) (12.51 mA cm^?2, 57%, 0.63 V, 1.2 × 10^?5 cm² V^?1 s^?1, 3.4 × 10^?4 cm² V^?1 s^?1, 0.82 nm and 4.49%), strongly retained morphological and photovoltaic stabilities in P3HT:PC₇₁BM devices after 1 month of air aging. According to the morphological, optical, photovoltaic and electrochemical results, the supra(PANI‐g‐rGO/P3HT) nanohybrid was the best candidate for stabilizing P3HT:PC₇₁BM solar cells. © 2020 Society of Chemical Industry     

Efficiencies of various metallocene/reducing agent catalyst systems in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene block copolymers

Various metallocenes, including bis(η⁵‐cyclopentadienyl)cobalt, bis(η⁵‐cyclopentadienyl)nickel, and bis(η⁵‐cyclopentadienyl)titanium dichloride, combined with various reducing agents, including n‐butyllithium, phenyllithium, and triethylaluminum, have been evaluated for their catalytic efficiencies in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene (SBS) block copolymer. The efficiencies were determined by monitoring the extent of saturation of double bonds on the polybutadiene segment of the copolymer using FTIR and ¹H‐NMR spectroscopy. The cobaltocene/n‐butyllithium catalyst system was found the most active. The effects of H₂ pressure and the ratio of n‐butyllithium to cobaltocene ratio on the hydrogenation efficiency were also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1807–1815, 1999     

Realizing the enhancement of interfacial interaction in semicrystalline polymer/filler composites via interfacial crystallization

Polymer/filler composites have been widely used in various areas. One of the keys to achieve the high performance of these composites is good interfacial interaction between polymer matrix and filler. As a relatively new approach, the possibility to enhance polymer/filler interfacial interaction via crystallization of polymer on the surface of fillers, i.e., interfacial crystallization, is summarized and discussed in this paper. Interfacial crystallization has attracted tremendous interest in the past several decades, and some unique hybrid crystalline structures have been observed, including hybrid shish-kebab and hybrid shish-calabash structures in which the filler served as the shish and crystalline polymer as the kebab/calabash. Thus, the manipulation of the interfacial crystallization architecture offers a potential highly effective route to achieve strong polymer/filler interaction. This review is based on the latest development of interfacial crystallization in polymer/filler composites and will be organized as follows. The structural/morphological features of various interfacial crystallization fashions are described first. Subsequently, various influences on the final structure/morphology of hybrid crystallization and the nucleation and/or growth mechanisms of crystallization behaviors at polymer/filler interface are reviewed. Then recent studies on interfacial crystallization induced interfacial enhancement ascertained by different research methodologies are addressed, including a comparative analysis to highlight the positive role of interfacial crystallization on the resultant mechanical reinforcement. Finally, a conclusion, including future perspectives, is presented.     

Conjugated-polymer grafting on inorganic and organic substrates: A new trend in organic electronic materials

This review highlights recent developments in the grafting of conjugated polymers onto various substrates for organic electronic devices. The rapid development of multi-layer architectures demands the preparation of well-defined interfaces between both compatible and incompatible materials. It is promising therefore that interface-engineering is now known to help passivate charge trap states, control energy level alignments, enhance charge extraction, guide active-layer morphologies, and improve material compatibility, adhesion and device stability. In organic electronic devices, conjugated polymers are in contact with a wide range of constituents, such as metals, metal oxides, organic materials, and inorganic particles. Covalent bonds between these materials and macromolecules are desired to yield intimate contacts and well-defined interfaces. Following an overview of the various synthetic methodologies of conjugated polymers, the chemistry of tethering macromolecular chains onto nanoparticles and flat surfaces is described. The creation of functional hybrid materials offers the potential to deliver efficient and low-cost devices.     

Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene

The allotropes of carbon nanomaterials (carbon nanotubes, graphene) are the most unique and promising substances of the last decade. Due to their nanoscale diameter and high aspect ratio, a small amount of these nanomaterials can produce a dramatic improvement in the properties of their composite materials. Although carbon nanotubes (CNTs) and graphene exhibit numerous extraordinary properties, their reported commercialization is still limited due to their bundle and layer forming behavior. Functionalization of CNTs and graphene is essential for achieving their outstanding mechanical, electrical and biological functions and enhancing their dispersion in polymer matrices. A considerable portion of the recent publications on CNTs and graphene have focused on enhancing their dispersion and solubilization using covalent and non-covalent functionalization methods. This review article collectively introduces a variety of reactions (e.g. click chemistry, radical polymerization, electrochemical polymerization, dendritic polymers, block copolymers, etc.) for functionalization of CNTs and graphene and fabrication of their polymer nanocomposites. A critical comparison between CNTs and graphene has focused on the significance of different functionalization approaches on their composite properties. In particular, the mechanical, electrical, and thermal behaviors of functionalized nanomaterials as well as their importance in the preparation of advanced hybrid materials for structures, solar cells, fuel cells, supercapacitors, drug delivery, etc. have been discussed thoroughly.