Investigation of the Effect of Thermal Annealing on Poly(3‐hexylthiophene) Nanofibers by Scanning Probe Microscopy: From Single‐Chain Conformation and Assembly Behavior to the Interfacial Interactions with Graphene Oxide

Poly(3‐hexylthiophene) (P3HT) has been widely used in devices owing to its excellent properties and structural features. However, devices based on pure P3HT have not exhibited high performance. Strategies, such as thermal annealing and surface doping, have been used to improve the electrical properties of P3HT. In this work, different from previous studies, the effect of thermal annealing on P3HT nanofibers are examined, ranging from the single polymer chain conformation to chain packing, and the interfacial interactions with graphene oxide (GO) at nanoscale dimensions, by using scanning tunneling microscopy (STM), atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). High‐resolution STM images directly show the conformational changes of single polymer chains after thermal annealing. The morphology of P3HT nanofibers and the surface potential changes of the P3HT nanofibers and GO is further investigated by AFM and KPFM at the nanoscale, which demonstrate that the surface potentials of P3HT decrease, whereas that of GO increases after thermal annealing. All of the results demonstrate the stronger interfacial interactions between P3HT and GO occur after thermal treatments due to the changes in P3HT chain conformation and packing order.     

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

Controlling the self‐assembly morphology of π‐conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3‐hexylthiophene)‐block‐poly(phenyl isocyanide)s (P3HT‐b‐PPI) copolymers composed of π‐conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization‐driven asymmetric self‐assembly (CDASA) of the block copolymers lead to the formation of single‐handed helical nanofibers with controlled length, narrow dispersity, and well‐defined helicity. During the self‐assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single‐handed helical assemblies of the block copolymers exhibited interesting white‐light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers.     

Effect of the Side‐Chain‐Distribution Density on the Single‐Conjugated‐Polymer‐Chain Conformation

The spatial arrangement of the side chains of conjugated polymer backbones has critical effects on the morphology and electronic and photophysical properties of the corresponding bulk films. The effect of the side‐chain‐distribution density on the conformation at the isolated single‐polymer‐chain level was investigated with regiorandom (rra‐) poly(3‐hexylthiophene) (P3HT) and poly(3‐hexyl‐2,5‐thienylene vinylene) (P3HTV). Although pure P3HTV films are known to have low fluorescence quantum efficiencies, we observed a considerable increase in fluorescence intensity by dispersing P3HTV in poly(methyl methacrylate) (PMMA), which enabled a single‐molecule spectroscopy investigation. With single‐molecule fluorescence excitation polarization spectroscopy, we found that rra‐P3HTV single molecules form highly ordered conformations. In contrast, rra‐P3HT single molecules, display a wide variety of different conformations from isotropic to highly ordered, were observed. The experimental results are supported by extensive molecular dynamics simulations, which reveal that the reduced side‐chain‐distribution density, that is, the spaced‐out side‐chain substitution pattern, in rra‐P3HTV favors more ordered conformations compared to rra‐P3HT. Our results demonstrate that the distribution of side chains strongly affects the polymer‐chain conformation, even at the single‐molecule level, an aspect that has important implications when interpreting the macroscopic interchain packing structure exhibited by bulk polymer films.     

Exploring the synthesis and impact of end‐functional poly(3‐hexylthiophene)

In recent years, end‐functional poly(3‐hexylthiophene) (P3HT) has proven to be instrumental in the continued development and innovation within the broad conjugated polymer arena, enabling a variety of applications, particularly in organic electronics. The availability of P3HT with controlled molecular weights, low polydispersity, and importantly, a wide range of reactive end‐groups not only serves as a key building block for the preparation of conjugated block copolymers but also facilitates the development of hybrid nanocomposite materials via inorganic surface modification strategies. This Highlight focuses on the synthetic approaches to end‐functional P3HT and the impact of these systems in emerging technologies. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 831–841     

Conducting core‐sheath nanofibers for electroactive shape‐memory applications

Conducting nanofibers coated with polypyrrole (PPy) and poly(3‐hexylthiophene) (P3HT) exhibiting core‐sheath structures were prepared by vapor‐phase polymerization of the conducting polymers on electrospun polyurethane nanofibers. The synthesis of the conducting polymers was confirmed by Fourier transform infrared spectroscopy and energy‐disperse X‐ray spectroscopy. The surfaces of the PPy‐coated nanofibers were slightly rough, while very smooth and regular surfaces were observed in the case of the P3HT‐coated nanofibers. The initial polymerization rate of PPy was higher than that of P3HT. In addition, the electrical conductivities of the core‐sheath structured nanofiber webs of both types increased with polymerization time. The maximum sheet conductivity of the PPy and P3HT‐coated nanofiber webs was 5 × 10^?3 S/cm and 1 × 10^?2 S/cm, respectively. The webs of the conducting core‐sheath structured nanofibers were effective in generating sufficient electrical heating necessary for harnessing these materials for electroactive shape‐memory‐based applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Formation of star‐like and linear nanofibers via controlled crystallization of poly(3‐dodecylthiophene)

We report the crystalline behavior of poly(3‐dodecylthiophene) (P3DDT) in aged toluene solution and link structure differences with the nature of seed nuclei related to various dissolution way. By directly stirring the P3DDT toluene solution for dissolution, the surviving fragments served as seed nuclei and star‐like nanofibers were formed upon aging. While by heating the P3DDT solution for complete dissolution followed by cooling, the seed nuclei came from the π–π stacking of the planarized P3DDT chains and linear nanofibers were formed upon aging. Formation mechanisms and kinetics of different nanofibers are discussed in detail. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1268–1272     

Electrospun poly(3‐hexylthiophene)/poly(ethylene oxide)/graphene oxide composite nanofibers: effects of graphene oxide reduction

In this article, we report on the production by electrospinning of P3HT/PEO, P3HT/PEO/GO, and P3HT/PEO/rGO nanofibers in which the filler is homogeneously dispersed and parallel oriented along the fibers axis. The effect of nanofillers' presence inside nanofibers and GO reduction was studied, in order to reveal the influence of the new hierarchical structure on the electrical conductivity and mechanical properties. An in‐depth characterization of the purity and regioregularity of the starting P3HT as well as the morphology and chemical structure of GO and rGO was carried out. The morphology of the electrospun nanofibers was examined by both scanning and transmission electron microscopy. The fibrous nanocomposites are also characterized by differential scanning calorimetry to investigate their chemical structure and polymer chains arrangements. Finally, the electrical conductivity of the electrospun fibers and the elastic modulus of the single fibers are evaluated using a four‐point probe method and atomic force microscopy nanoindentation, respectively. The electrospun materials crystallinity as well as the elastic modulus increase with the addition of the nanofillers while the electrical conductivity is positively influenced by the GO reduction. Copyright © 2016 John Wiley & Sons, Ltd.     

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     

Green synthesis of polymer nanofibers and their composites as flame‐retardant materials for polymer nanocomposites

Polyaniline nanofibers and their composites with carbon nanotubes were developed as an effective flame‐retardant material using a facile green method. Polyaniline nanofibers were used as a smart flame‐retardant for acrylonitrile–butadiene–styrene polymer. The polyaniline nanofibers were dispersed in polymer matrix forming well‐dispersed polymer nanocomposites. Effect of polyaniline nanofiber mass ratio on the polymer nanocomposite properties was studied. Polyaniline nanofiber composites with carbon nanotubes were also dispersed in polymer matrix. The thermal stability and flammability properties of the polymer nanocomposites were investigated. The rate of burning of polymer nanocomposites achieved 82.5% reduction (7.32 mm/min) compared with virgin polymer (42.5 mm/min). The reduction in peak heat release rate and total heat release of the polymer nanocomposites containing nanofibers achieved 74 and 34%, respectively. Interestingly, the average mass loss rate was significantly reduced by 58% and the emission of carbon monoxide and carbon dioxide gases were suppressed by 20 and 47%, respectively. The effect of polyaniline nanofibers composites on the flammability of polymer nanocomposites was also studied. Polyaniline nanofibers and their composites were characterized using Fourier transform infrared spectroscopy and transmission and scanning electron microscopy. The dispersion of polyaniline nanofibers in polymer nanocomposites was characterized using transmission electron microscopy. The different polymer nanocomposites were characterized using thermogravimetric analysis, UL94 flame chamber, and cone calorimeter tests. Copyright © 2016 John Wiley & Sons, Ltd.     

Insights into poly(3‐hexylthiophene)‐b‐poly(ethylene oxide) block copolymer: Synthesis and solvent‐induced structure formation in thin films

We report the synthesis, characterization, and solvent‐induced structure formation in thin films of an amphiphilic rod‐coil conjugated block copolymer, poly(3‐hexylthiophene)‐b‐poly(ethylene oxide). The diblock copolymers were prepared by a facile click reaction and their characterizations as well as thermal, crystalline, optical properties, and self‐assembly behavior have been investigated in detail. A series of morphologies including two‐phase separated nanostructure, nanofibrils, and their mixed morphology could be obtained depending on the selectivity of solvents to different blocks. Structural analyses demonstrate there is a subtle balance between microphase separation of copolymer and the π‐π stacking of the conjugated P3HT and such balance can be controlled by changing the solvents of different selectivity in solution and the length of P3HT block. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Conjugated block copolymers via functionalized initiators and click chemistry

Conjugated block copolymers are potentially useful for organic electronic applications and the study of interfacial charge and energy transfer processes; yet few synthetic methods are available to prepare polymers with well‐defined conjugated blocks. Here, we report the synthesis and thin film morphology of a series of conjugated poly(3‐hexylthiophene)‐block‐poly(9,9‐dioctylfluorene) (P3HT‐b‐PF) and poly(3‐dodecylthiophene)‐block‐poly(9,9‐dioctylfluorene) (P3DDT‐b‐PF) block copolymers prepared by functional external initiators and click chemistry. Functional group control is quantified by proton nuclear magnetic resonance spectroscopy, size‐exclusion chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The thin film morphology of the resulting all‐conjugated block copolymers is analyzed by a combination of grazing‐incidence X‐ray scattering, atomic force microscopy, and transmission electron microscopy. Crystallization of the P3HT or P3DDT blocks is present in thin films for all materials studied, and P3DDT‐b‐PF films exhibit significant PF/P3DDT co‐crystallization. Processing conditions are found to impact thin film crystallinity and orientation of the π–π stacking direction of polymer crystallites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 154–163     

Grafting Poly(3‐hexylthiophene) from Silicon Nanocrystal Surfaces: Synthesis and Properties of a Functional Hybrid Material with Direct Interfacial Contact

Hybrid functional materials (HFMs) comprised of semiconductor nanoparticles and conjugated polymers offer the potential of synergetic photophysical properties. We have developed HFMs based upon silicon nanocrystals (SiNCs) and the conductive polymer poly(3‐hexylthiophene) (SiNC@P3HT) by applying surface‐initiated Kumada catalyst transfer polycondensation (SI‐KCTP). One unique characteristic of the developed SiNC@P3HT is the formation of a direct covalent bonding between SiNCs and P3HT. The presented method for obtaining direct interfacial attachment, which is not accessible using other methods, may allow for the development of materials with efficient electronic communication at the donor–acceptor interfaces. Systematic characterization provides evidence of a core–shell structure, enhanced interfacial electron and/or energy transfer between the P3HT and SiNC components, as well as formation of a type‐II heterostructure.     

Effect of modified graphene and microwave irradiation on the mechanical and thermal properties of poly(styrene‐co‐methyl methacrylate)/graphene nanocomposites

The effect of modified graphene (MG) and microwave irradiation on the interaction between graphene (G) and poly(styrene‐co‐methyl meth acrylate) [P(S‐co‐MMA)] polymer matrix has been studied in this article. Modification of graphene was performed using nitric acid. P(S‐co‐MMA) polymer was blended via melt blending with pristine and MG. The resultant nanocomposites were irradiated under microwave at three different time intervals (5, 10, and 20 min). Compared to pristine graphene, MG showed improved interaction with P(S‐co‐MMA) polymer (P) after melt mixing and microwave irradiation. The mechanism of improved dispersion and interaction of modified graphene with P(S‐co‐MMA) polymer matrix during melt mixing and microwave irradiation is due to the presence of oxygen functionalities on the surface of MG as confirmed from Fourier transform infrared spectroscopy. The formation of defects on modified graphene and free radicals on P(S‐co‐MMA) polymer chains after irradiation as explained by Raman spectroscopy and X‐Ray diffraction studies. The nanocomposites with 0.1 wt% G and MG have shown a 26% and 38% increase in storage modulus. After irradiation (10 min), the storage modulus further improved to 11.9% and 27.6% of nanocomposites. The glass transition temperature of nanocomposites also improved considerably after melt mixing and microwave irradiation (but only for polymer MG nanocomposite). However, at higher irradiation time (20 min), degradation of polymer nanocomposites occurred. State of creation of crosslink network after 10 min of irradiation and degradation after 20 min of irradiation of nanocomposites was confirmed from SEM studies. Copyright © 2014 John Wiley & Sons, Ltd.     

Nanocomposite structures of polypyrrole derivatives and poly (acrylonitrile‐co‐itaconic acid) produced by in situ polymerization as carbon nanofiber precursor

This study aimed to produce nanoparticles of poly (acrylonitrile‐co‐itaconic acid) (P (AN‐co‐IA)) containing conjugated polymers of pyrrole, N‐Methylpyrrole, 2,5‐dimethylpyrrole, and 1‐(Triisopropylsilyl)pyrrole which were synthesized by emulsion polymerization. Nanocomposite structures of P (AN‐co‐IA)/polypyrrole and polymer of pyrrole derivatives were produced via in situ polymerization, and the nanoparticle formation were followed by morphologic and ultraviolet‐visible (UV‐Vis) spectroscopic methods. Characterizations were made by Fourier transform infrared‐attenuated total reflectance (FTIR‐ATR) and Raman spectroscopy. Atomic force microscopy (AFM) was used for investigating the surface characteristics of the nanoparticles. Characterization results revealed that nanoparticles containing conjugated polymers had rougher surface than P (AN‐co‐IA) nanoparticles. It was also observed that the nanoparticles were well‐distributed although having some agglomerates. Moreover, depending on the type of monomer of conjugated polymer, the shape and size of the produced nanoparticles differed by conjunction with their polymerization rate. These findings can be used as a startup information for production of carbon nanofibers (CNFs) with desired properties after oxidation and carbonization, and as a high‐performance and cost‐effective flame and heat‐resistant material (oxidized copolymers of polyacrylonitrile nanofiber).     

Bay‐annulated indigo based near‐infrared sensitive polymer for organic solar cells

A new conjugated polymer (PBAIIDTT) based on bay‐annulated indigo and indacenodithieno[3,2‐b]thiophene was designed, synthesized, and characterized. PBAIIDTT shows strong absorption in 400–500 and 600–800 nm, and its HOMO and LUMO energy levels are −5.45 eV and −3.65 eV, respectively. In organic field‐effect transistors, the polymer exhibits a relatively high hole mobility of 0.39 cm² V⁻¹ s⁻¹. PBAIIDTT was added to poly(3‐hexylthiophene) (P3HT) and phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) based organic solar cells. Ternary blend solar cells with 10% PBAIIDTT show an increased short circuit current density due to the broadened photocurrent generated in the near‐infrared region, and a power conversion efficiency of 3.78%, which is higher than that of the P3HT:PC₆₁BM binary control devices (3.33%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 213–220     

Aqueous Stable Gold Nanostar/ZIF‐8 Nanocomposites for Light‐Triggered Release of Active Cargo Inside Living Cells

A plasmonic core–shell gold nanostar/zeolitic‐imidazolate‐framework‐8 (ZIF‐8) nanocomposite was developed for the thermoplasmonic‐driven release of encapsulated active molecules inside living cells. The nanocomposites were loaded, as a proof of concept, with bisbenzimide molecules as functional cargo and wrapped with an amphiphilic polymer that prevents ZIF‐8 degradation and bisbenzimide leaking in aqueous media or inside living cells. The demonstrated molecule‐release mechanism relies on the use of near‐IR light coupled to the plasmonic absorption of the core gold nanostars, which creates local temperature gradients and thus, bisbenzimide thermodiffusion. Confocal microscopy and surface‐enhanced Raman spectroscopy (SERS) were used to demonstrate bisbenzimide loading/leaking and near‐IR‐triggered cargo release inside cells, thereby leading to DNA staining.     

In‐Situ covalent synthesis of gold nanorods on GO surface as ultrasensitive Raman probe

In this paper, using thiolated graphene oxide (GO‐O‐SH) as substrate, gold nanorods (AuNRs) covalently linked to the GO surface by in‐situ seed growth method were first reported. The as‐prepared composites were characterized by UV–vis spectrum, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT‐IR). Experimental results indicated that the introduction of short flexible organic chain between GO and AuNRs contributed to the homogenous synthesis of gold rods, and uniform gold nanorods with aspect ratio within 3~8 were covalently linked to the surface of GO with high stability and yield. The strategy represented an outstanding improvement in comparison to the traditional route for fabricating GO@AuNRs composites. Furthermore, based on coupling of the two nanomaterials, the composites could act as high sensitive Raman probe with limit of detection (LOD) reaching 1 × 10^?12 M.     

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     

Double/single phase segregation and vertical stratification induced by crystallization in all‐crystalline tri/diblock copolymers and homopolymer blends of poly(3‐hexylthiophene) and poly(ethylene glycol)

Distinct stratified and non‐stratified morphologies were developed in poly(3‐hexylthiophene) (P3HT) and poly(ethylene glycol) (PEG)‐based homopolymer blends and diblock and triblock copolymer systems. By applying X‐ray photoelectron spectroscopy, only a double‐percolation mechanism including assembling of P3HT chains into the nanofibers in solution aging process with a marginal solvent like p‐xylene as well as crystallization of PEG phase in the cast thin films resulted in vertical stratification and networked fibrils. In cast thin films whose PEG phase, due to low molecular weight or being constrained between two rigid P3HT blocks in triblock copolymers was not crystallized, a non‐stratified discrete fibrillar morphology was acquired. Crystallization of PEGs in the thin films mainly participated in networking and expelling pre‐organized P3HT fibrils to the film surface. By performing the solution aging step in a good solvent such as o‐dichlorobenzene, the P3HTs remained in a coily‐like conformation, and casting the corresponding thin films reflected the non‐stratified discrete granular and featureless morphologies. Assembling the P3HT chains in the presence of PEG phase in cast films at most led to the low‐crystalline granules instead of highly crystalline nanofibrils. No significant crystallization in either homopolymer blends or block copolymer systems conduced to a featureless morphology with homogeneous distribution of existed materials. The surface morphology and ordering in various morphologies were studied employing atomic force microscopy, grazing incidence X‐ray diffraction, and ultraviolet–visible analyses. Copyright © 2016 John Wiley & Sons, Ltd.     

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.