Structural transitions of nanocrystalline domains in regioregular poly(3‐hexyl thiophene) thin films

The effects of solution processing and thermal annealing on thin film morphology and crystalline structures of regioregular poly(3‐hexyl thiophene) (RR P3HT) are studied in terms of molecular weight (M_w). Using grazing‐incidence X‐ray diffraction, π‐conjugated planes in drop‐cast films from chloroform solutions are found to be preferentially oriented parallel to the substrates regardless of M_w. However, the mesoscale nanocrystalline morphology of the drop‐cast films is significantly affected by M_w, exhibiting a distinctive morphological transition from short nanorods to long nanofibrils above a critical number‐averaged M_w (～ 3.6 kDa). This is probably due to the change in a conformation change from an extended‐chain to a folded‐chain, as M_w of RR P3HT increases. In contrast, spin‐casting of high M_w RR P3HT produces less ordered films with a lower crystallinity and mixed parallel/perpendicular orientations of π‐conjugated planes. The crystallinity and parallel π‐conjugated orientation of RR P3HT in spin‐cast films could be improved by thermal treatments at high‐temperatures either (1) above the glass transition temperature or (2) above the melting temperature of RR 3PHT followed by recrystallization upon cooling under vacuum. However, the charge mobility of the spin‐cast films for a field‐effect transistor application is still lower than that of the drop‐cast films. This would be attributed to the chain oxidation and the development of distinct grain boundaries between RR P3HT nanofibrils during the thermal treatments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1303–1312, 2007     

Molecular weight dependent structure and charge transport in MAPLE‐deposited poly(3‐hexylthiophene) thin films

In this work, poly(3‐hexylthiophene) (P3HT) films prepared using the matrix‐assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE‐deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side‐chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin‐cast films, though the MAPLE‐deposited films are more disordered. In‐plane carrier mobilities in the MAPLE‐deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE‐deposited simples are consistently lower than those in the solvent‐cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 652–662     

Molecular organization in MAPLE‐deposited conjugated polymer thin films and the implications for carrier transport characteristics

The morphological structure of poly(3‐hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin‐casting methods are investigated. The MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side‐chain stacking, π–π stacking, and conjugated backbone directions. Moreover, the average molecular orientations and relative degrees of crystallinity of MAPLE‐deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin‐casting technique. Despite the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in‐plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin‐cast samples, exhibiting similar transport activation energies (56 vs. 54 meV) to those reported in the literature for high mobility polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 39–48     

Effects of silica nanoparticle addition on polymer semiconductor wettability and carrier mobility in solution‐processable organic transistors on hydrophobic substrates

The effects of the addition of silica nanoparticles (SNPs) on wettability of regioregular poly(3‐hexylthiophene) (P3HT) organic semiconductor solutions on hydrophobic substrates and the carrier mobility in organic field‐effect transistors (OFETs) made of these films are investigated. The dewetting of films made from P3HT solutions on hydrophobic substrates modified with octadecyltrichlorosilane (ODTS) is markedly suppressed after the addition of SNPs with phenyl surfactants. This enables us to fabricate continuous P3HT/SNPs films with high crystallinity by the conventional spin‐coating technique, leading to higher mobility compared with P3HT FETs fabricated on non‐modified substrates. Moreover, the addition of SNPs with larger diameters compensates for the degradation of mobility associated with the increase in the concentration of SNPs. Solution‐processed P3HT/SNPs FETs on ODTS‐modified substrates exhibit a field‐effect mobility of 1.3 × 10^?2 cm² V^?1 s^?1, which is almost comparable to that of P3HT FETs without SNPs (2.1 × 10^?2 cm² V^?1 s^?1). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 509–516     

Synthesis of block copolymers comprised of poly(3‐hexylthiophene) segment with trisiloxane side chains and their application to organic thin film transistor

The demand of stretchability for a semiconducting polymer has increased to realize wearable devices and sensors. However, studies involving intrinsically stretchable π‐conjugated polymers are still limited. Here, we develop a soft‐polythiophene derivative, P3SiHT, with a trisiloxane unit in the side chains via a hexylene spacer unit. In addition, diblock (P3HT‐b‐P3SiHT) and triblock (P3HT‐b‐P3SiHT‐b‐P3HT) copolymers could be synthesized based on Kumada catalyst‐transfer polycondensation. The results of atomic force microscopy and grazing incidence small‐angle X‐ray scattering indicate that the block copolymer thin films form a phase‐separated structure between the P3HT and P3SiHT domains. The organic thin film transistor devices were prepared to assess the electrical properties of the block polymers. As a result, the block copolymers showed comparable or even higher hole mobility than that of P3HT homopolymer, thus due to the enhanced phase‐separation and thereby charge transportation. The mechanical test of the bulk films indicates that P3HT‐b‐P3SiHT‐b‐P3HT shows lower tensile modulus and longer elongation at break than P3HT homopolymer and other diblock copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1787–1794     

Synthesis,morphology, and field‐effect transistor characteristics of new crystalline–crystalline diblock copolymers of poly(3‐hexylthiophene‐block‐steryl acrylate)

We report the synthesis, morphology, and charge‐transporting characteristics of new crystalline–crystalline diblock copolymers, poly(3‐hexylthiophene‐block‐stearyl acrylate) (P3HT‐b‐PSA). Three different diblock copolymers, P1 , P2 , and P3 , with P3HT/PSA polymerization degree block ratios of 60/26, 60/50, and 60/360, respectively, were prepared for investigating the morphology‐property relationship and the dependence of optoelectronic properties on the block copolymer structure. Small‐ and wide‐angle X‐ray scattering indicated the presence of both P3HT and PSA crystalline domains and the presence of microphase separation among blocks. The transmission electron microscopy and atomic force microscopy results revealed that the diblock copolymers cast from chlorobenzene, tended to form needle‐like morphologies. The field‐effect mobilities of the diblock copolymers deposited on untreated SiO₂ substrates, decreased with increasing PSA block length. In a sharp contrast, the mobilities enhanced with increasing PSA content when the P3HT‐b‐PSA was deposited on phenyltrichlorosilane (PTS)‐treated substrates. The copolymers with a 60/360 P3HT/PSA ratio showed a good mobility of 4 × 10^?3 cm² V^?1 s^?1 and a high on/off ratio of 7 × 10⁶ on PTS‐treated substrates. This study highlighted the importance of the block ratio, the substrate and self‐assembly structures on the charge transport characteristics of the crystalline–crystalline conjugated diblock copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of poly(3‐hexylthiophene)‐block‐poly(ethylene)‐block‐poly(3‐hexylthiophene) via a combination of ring‐opening olefin metathesis polymerization and grignard metathesis polymerization

Novel rod–coil–rod ABA triblock copolymers, poly(3‐hexylthiophene)‐block‐poly(ethylene)‐block‐poly(3‐hexylthiophene) (P3HT‐b‐PE‐b‐P3HT) were synthesized by using a combination of a Ru‐catalyzed ring‐opening metathesis polymerization of 1,4‐cyclooctadiene in the presence of a suitable chain transfer agent (CTA) and a Ni‐catalyzed Grignard metathesis polymerization of 5‐chloromagnesio‐2‐bromo‐3‐hexylthiophene followed by hydrogenation. Using this methodology, the molecular weights of the poly(butadiene) (PBD) or the P3HT blocks were controlled by adjusting the initial monomer/CTA or the initial monomer/macroinitiator ratio, respectively. In addition, the triblock structure was confirmed by selective oxidative degradation of the PBD block found in the intermediate P3HT‐b‐PBD‐b‐P3HT copolymer produced in the aforementioned method, followed by analysis of the degradation products. Thermal analysis and atomic force microscopy of P3HT‐b‐PE‐b‐P3HT revealed that the material underwent phase separation in the solid state, a feature which may prove useful for improving charge mobilities within electronic devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3810–3817     

Poly(3‐hexylthiophene)‐b‐poly(3‐cyclohexylthiophene): Synthesis,microphase separation,thin film transistors,and photovoltaic applications

We report the synthesis, characterization, microphase separation, field‐effect charge transport, and photovoltaic properties of regioregular poly(3‐hexylthiophene)‐b‐poly(3‐cyclohexylthiophene) (P3HT‐b‐P3cHT). Two compositions of P3HT‐b‐P3cHT (HcH63 and HcH77) were synthesized with weight‐average molecular weights of 155,500 and 210,800 and polydispersity indices of 1.45 and 1.57, respectively. Solvent‐casted HcH77 was found to self‐assemble into nanowires with a width of 12.5 ± 0.9 nm and aspect ratios of 50–120, as observed by TEM imaging. HcH77 and HcH63 annealed 280 °C were observed by small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) to be microphase‐separated with characteristic length scales of 17.0–21.7 nm. The microphase‐separated domains were shown to be crystalline with interlayer backbone (100) d‐spacings of 1.69 and 1.40 nm, which correspond to the P3HT and P3cHT blocks, respectively. Field‐effect transistors fabricated from P3HT‐b‐P3cHT thin films showed a mobility of holes (0.0019 cm²/Vs) which is independent of thermal annealing. Bulk heterojunction solar cells based on HcH77/fullerene (PC₇₁BM) blend thin films had a maximum power conversion efficiency of 2.45% under 100 mW/cm² AM1.5 solar illumination in air. These results demonstrate that all‐conjugated block copolymers are suitable semiconductors for applications in field‐effect transistors and bulk heterojunction solar cells. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 614–626, 2010     

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.     

Evaluation of poly(4‐methyl‐1‐pentene) as a dielectric capacitor film for high‐temperature energy storage applications

Poly(4‐methyl‐1‐pentene) (P4MP) was characterized to evaluate its viability as a high‐temperature dielectric film for capacitors. Detailed investigation of thermal, mechanical, rheological, and dielectric properties was carried out to assess its high‐temperature performance and processability. P4MP was melt‐processable below 270 °C without degradation and application temperatures as high as 160–190 °C can be achieved. The dielectric constant and loss of melt‐processed P4MP films was comparable to biaxially oriented polypropylene (BOPP) capacitor films, although the dielectric strength was lower. Enhancements in dielectric strength up to 250–300% were achieved via solution‐processing P4MP films, which could be easily scaled up on a roll‐to‐roll platform to yield isotropic, free‐standing films as thin as 3–5 μm. The influence of crystal structure, crystallinity, and surface morphology of these films on the dielectric properties was examined. The dielectric strength was further increased by 450% through biaxial stretching of solution‐cast films, and a Weibull breakdown field of 514 V/μm was obtained. The dielectric constant was very stable as a function of frequency and temperature and the dielectric loss was restricted to <1–2%. Overall, these results suggest that BOP4MP is a promising candidate to obtain similar energy density as a BOPP capacitor film but at much higher operating temperatures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1497–1515     

Poly(3‐hexylthiophene) films prepared using binary solvent mixtures

Binary solvent mixtures were routinely used to induce the hierarchical assembly of poly(3‐hexylthiophene) (P3HT) in the liquid phase. This technique has garnered a lot of interest as a route to well‐organized films and composites, but, to date, the impact that the attributes of the liquid‐phase aggregates and solvent mixtures have on the organization of the films have only been partially scrutinized. The molecular weight and concentration dependence of P3HT assembly in three binary solvent mixtures containing chloroform and acetonitrile, n‐hexane, or dichloromethane were studied using ultraviolet/visible absorbance spectroscopy and dynamic light scattering techniques. Films drop cast under slow and rapid evaporation conditions were observed using optical and atomic force microscopy. In general, there is no evidence that the characteristics of the liquid phase P3HT aggregates impact the structures of the films, but films cast from these solvent mixtures under rapid evaporation conditions exhibit an array of disparate morphologies and mesoscale patterning. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 624–638     

High‐performance field‐effect transistors based on furan‐containing diketopyrrolopyrrole copolymer under a mild annealing temperature

Two furan‐flanked polymers poly{3,6‐difuran‐2‐yl‐2,5‐di(2‐octyldodecyl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐alt‐thienylenevinylene} (PDVFs), with a highly π‐extended diketopyrrolopyrrole backbone, are developed for solution‐processed high‐performance polymer field‐effect transistors (FETs). Atomic force microscopy and grazing incidence X‐ray scattering analyses indicate that PDVF‐8 and PDVF‐10 films exhibit a similar nodular morphology with the ultrasmall lamellar distances of 16.84 and 18.98 Å, respectively. When compared with the reported polymers with the same alkyl substitutes, this is the smallest d‐spacing value observed to date. This closed lamellar crystallinity facilitates charge carrier transport. Therefore, polymer thin‐film transistors fabricated from as‐spun PDVF‐8 films exhibit a high hole mobility exceeding 1.0 cm² V^?1 s^?1 with a current on/off ratio above 10⁶. After annealing treatment at 100 °C in air, the highest hole mobility of PDVF‐8‐based FETs was significantly improved to 1.90 cm² V^?1 s^?1, which is among the highest values of the reported FET devices fabricated from polymer thin films based on this mild annealing temperature. In contrast, long alkyl‐substituted PDVF‐10 exhibited a relatively low hole mobility of 1.65 cm² V^?1 s^?1 mainly resulting from low molecular weight. This work demonstrated that PDVFs would be promising semiconductors for developing cost‐effective and large‐scale production of flexible organic electronics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1970–1977     

Synthesis and morphology of all‐conjugated donor–acceptor block copolymers based on poly(3‐hexylthiophene) and poly(naphthalene diimide)

A series of all‐conjugated diblock and triblock copolymers comprised of poly(naphthalene diimide) (PNDI)‐based n‐type and the poly(3‐hexylthiophene) (P3HT) segments could be synthesized via the Kumada catalyst‐transfer polycondensation process. The crystalline structures and chain orientation of the block copolymer thin films were systematically studied by grazing incident wide‐angle X‐ray scattering (GIWAXS). The GIWAXS results indicated that both the P3HT and PNDI segments in the block copolymers form exclusive crystalline domains in which the P3HT domain aligns with an edge‐on rich orientation, and the PNDI domain aligns with a face‐on rich orientation. In contrast, the blend films of the P3HT and PNDI homopolymers also show two distinguished crystalline domains in which the P3HT domain aligns with an edge‐on rich orientation, and the PNDI domains align in different ways depending on the chemical structure of n‐type polymers, that is, PNDI1Th is isotropically dispersed, while PNDI2Th aligns with a face‐on rich orientation. In addition, the effect of thermal annealing on the crystalline behavior of the block copolymers is reported. The GIWAXS results indicated that thermal annealing increases the crystallinity of both segments without affecting their chain orientation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1139–1148     

Poly(L‐lactide)/C60 nanocomposites: Effects of C60 on crystallization of poly(L‐lactide)

The effects of solvent type and concentration of C₆₀ on the crystallization of poly(L ‐lactide) (PLLA) during solvent evaporation, heating from room temperature, and cooling from the melt were investigated by polarized optical microscopy and differential scanning calorimetry. The addition of C₆₀ enhanced the PLLA crystallization during solvent evaporation, during heating of the melt‐quenched films, and during cooling from the melt of As‐cast films, except for heating and cooling of the PLLA film with 1 wt % of C₆₀ prepared with dichloromethane. In the case of solvent evaporation, the difference in crystallinity between the PLLA films with and without C₆₀ became higher for the solvent with a lower boiling point. In the case of heating of melt‐quenched films, the addition of C₆₀ had a small effect on the crystallinity of PLLA, whereas significantly lowered the peak top and ending temperatures of cold crystallization, except for melt‐quenched PLLA film with 1 wt % of C₆₀ prepared with dichloromethane. The crystallinity of PLLA was determined by the solvent type, rather than by the C₆₀ concentration. In the case of cooling from the melt of As‐cast films, the addition of C₆₀ elevated the crystallinity and cold crystallization temperature values of PLLA films, except for PLLA films prepared with dichloromethane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2167–2176, 2007     

Synthesis and characterization of phenanthrocarbazole–diketopyrrolopyrrole copolymer for high‐performance field‐effect transistors

In this study, we successfully designed and synthesized a novel phenanthro[1,10,9,8‐c,d,e,f,g]carbazole ( PCZ )‐based copolymer poly[N‐(2‐octyldodecyl)‐4,8‐phenanthro[1,10,9,8‐c,d,e,f,g]carbazole‐alt‐2,5‐dihexadecyl‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione] ( PPDPP ) with an extended π‐conjugation along the vertical orientation of polymer main chain. This polymer exhibited excellent solubility in common solvent and high thermal stability, owning good properties for solution‐processed field‐effect transistors (FETs). Besides, absorption spectra demonstrated that annealing PPDPP thin films led to obviously red‐shifted maxima, indicating the formations of aggregation or orderly π–π stacking in their solid‐state films. X‐ray diffraction measurements indicated the crystallinity of PPDPP thin films was enhanced after high temperature annealing, which was favorable for charge transport. The solution‐processed PPDPP ‐based FET devices were fabricated with a bottom‐gate/bottom‐contact geometry. A high hole mobility of up to 0.30 cm²/Vs and a current on/off ratio above 10⁵ had been demonstrated. These results indicated that the copolymers constructed by this kind of ladder‐type cores could be promising organic semiconductors for high‐performance FET applications. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Poly(3‐hexyl thiophene)‐b‐poly(N‐isopropyl acrylamide): Synthesis and its composition dependent structural,solubility, thermoresponsive,electrochemical, and electronic properties

Conjugated block copolymers consisting of poly(3‐hexyl thiophene) (P3HT) and a thermoresponsive polymer poly(N‐isopropyl acrylamide) (PNIPAM) with varying composition have been synthesized by facile click reaction between alkyne terminated P3HT and azide terminated PNIPAM. The composition‐dependent solubility, thermoresponsive property in water, phase behavior, electrochemical, optical, and electronic properties of the block copolymers were systematically investigated. The block copolymers with higher volume fraction of PNIPAM form thermoresponsive spherical micelles with P3HT‐rich crystalline cores and PNIPAM coronas. Both X‐ray and atomic force microscopic studies indicated that the blocks copolymers showed well‐defined microphase separated nanostructures and the structure depended on the composition of the blocks. The electrochemical study of the block copolymers clearly demonstrated that the extent of charge transport through the block copolymer thin film was similar to P3HT homopolymer without any significant change in the band gap. The block copolymers showed improved or similar charge carrier mobility compared with the pure P3HT depending on the composition of the block copolymer. These P3HT‐b‐PNIPAM copolymers were interesting for fabrication of optoelectronic devices capable of thermal and moisture sensing as well as for studying the thermoresponsive colloidal structures of semiconductor amphiphilic systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1785–1794     

A model for charge transport in semicrystalline polymer thin films

A model for simulating the charge transport properties of semicrystalline polymer (SCrP) using Monte Carlo simulation is reinvented. The model is validated by reproducing the experimentally observed field and temperature dependence of mobility in Poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) thin films. This study also provides a new physical insight to the origin of much debated negative field dependence of mobility (NFDM) observed at low electric field strengths in P3HT thin films. The observed NFDM, which is not explainable with the mechanisms proposed earlier, is attributed to the weak dependence of transit time on the applied electric field strengths. In the semicrystalline films, the charge transport takes place mostly through the crystalline regions, in which the charge transport is weakly dependent on the strength of the applied electric field. In addition, a possible explanation for the origin of Arrhenius temperature dependence of mobility (lnμ ∝ 1/T) commonly observed in SCrP thin films is also proposed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 137–141     

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     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Crystallization‐dominated and microphase separation/crystallization‐coexisted structure of all‐conjugated phenylene–thiophene diblock copolymers

The crystallization‐dominated and microphase separation/crystallization‐coexisted structure of the all‐conjugated diblock copolymers poly(2,5‐dihexyloxy‐p‐phenylene)‐block‐(3‐hexylthiophene) (PPP‐b‐P3HT, denoted as BmTn) with different block compositions was affected by the aggregation state of the diblock copolymers in solvents with different solubilities. For B34T66, B62T38, and B75T25, the coexistence of microphase separation and crystallization was obtained in good solvent with few crystalline aggregates. For B34T66 with a longer P3HT block, densely stacked fiber crystal structures in thin films were found by using marginal solvents with crystalline aggregations in solutions. As for B62T38 and B75T25 with shorter P3HT block and longer PPP block, crystal structures were obtained by the use of solvents with a much larger solubility difference of the two blocks. Thus, microphase‐separated structures are prone to form from solutions with coil conformation and fiber crystals from solutions with larger aggregates, which resulted in the increased crystallinity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1718–1726